Thermoplastic resin and optical lens containing the same

Abstract

The present invention relates to a thermoplastic resin containing a structural unit (A) derived from a monomer represented by the following general formula (1). In the formula, R 1 The same or different, each represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a phenyl group, or a linear or branched alkyl group having 1 to 4 carbon atoms. Ring A represents a phenyl ring which can be substituted with 1 to 4 groups selected from a fluorine atom, a chlorine atom, a bromine atom, a phenyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a linear or branched alkyl group having 1 to 6 carbon atoms.

Description

Technical Field

[0001] This invention relates to a thermoplastic resin and an optical lens containing the thermoplastic resin. More specifically, this invention relates to a polycarbonate resin or polyester carbonate resin and an optical lens containing these resins. Background Technology

[0002] Optical lenses, used in the optical systems of various cameras such as cameras, film cameras, and camcorders, are made of optical glass or optical resin. Although optical glass has excellent properties in terms of heat resistance, transparency, dimensional stability, and chemical resistance, it also suffers from problems such as high material cost, poor processability, and low production efficiency.

[0003] On the other hand, optical lenses made of optical resins have the advantage of being mass-produced through injection molding. As high refractive index materials for camera lenses, polycarbonate, polyester carbonate, polyester resin, etc. are used.

[0004] When using optical resins as optical lenses, in addition to optical properties such as refractive index and Abbe number, properties such as heat resistance, transparency, low water absorption, chemical resistance, low birefringence, and resistance to damp heat are also required. 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 for this purpose (Patent Documents 1-5).

[0005] On the other hand, thermoplastic resins made from diol compounds with cyclic acetal structures (such as spiroethylene glycol) are effective as resins for various optical applications due to their excellent optical properties and impact resistance. However, with the expansion of various molding processes and usage environments, it is necessary to further improve heat resistance without compromising optical properties.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2018-2893

[0009] Patent Document 2: Japanese Patent Application Publication No. 2018-2894

[0010] Patent Document 3: Japanese Patent Application Publication No. 2018-2895

[0011] Patent Document 4: Japanese Patent Application Publication No. 2018-59074

[0012] Patent Document 5: WO2017 / 078073 Summary of the Invention

[0013] The problem that the invention aims to solve

[0014] The objective of this invention is to provide a thermoplastic resin with excellent optical properties such as refractive index and Abbe number, as well as excellent heat resistance, and an optical lens using the thermoplastic resin.

[0015] Technical solutions for solving the problem

[0016] After repeated and in-depth research to solve existing problems, the inventors discovered that by using a monomer with a specific structure, namely a diol compound with an aromatic ring and a cyclic acetal structure, as a raw material, a thermoplastic resin with excellent optical properties such as refractive index and Abbe number, as well as excellent heat resistance, can be obtained, thus completing the present invention.

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

[0018] <1> A thermoplastic resin containing structural units (A) derived from monomers represented by the following general formula (1).

[0019]

[0020] In the formula, R 1 "Identical" or "different" respectively refers to a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a phenyl group, or a straight-chain or branched alkyl group having 1 to 4 carbon atoms. "Ring A" represents a benzene ring that can be substituted by 1 to 4 groups selected from fluorine, chlorine, bromine, phenyl, straight-chain or branched alkoxy groups having 1 to 6 carbon atoms, and straight-chain or branched alkyl groups having 1 to 6 carbon atoms.

[0021] <2> As mentioned above <1> The thermoplastic resin is, in particular, a polycarbonate resin or a polyester carbonate resin.

[0022] <3> As mentioned above <1> or <2> The thermoplastic resin, wherein R in the above general formula (1) 1 They may be the same or different, namely methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or phenyl.

[0023] <4> As mentioned above <3> The thermoplastic resin, wherein, in the above general formula (1), R 1 They are the same or different, namely methyl or ethyl.

[0024] <5> As mentioned above <1> ~ <4> The thermoplastic resin according to any one of the above general formulas (1), wherein ring A is a benzene ring that can be substituted by 1 to 4 groups selected from straight-chain or branched alkoxy groups having 1 to 6 carbon atoms and straight-chain or branched alkyl groups having 1 to 6 carbon atoms.

[0025] <6> As mentioned above <1> ~ <5> The thermoplastic resin described in any one of the above general formulas (1), wherein R 1 It is methyl or ethyl, and ring A is a benzene ring that can be substituted by 1 to 4 groups selected from methyl and ethyl.

[0026] <7> As mentioned above <1> or <2> The thermoplastic resin wherein the monomer represented by the above general formula (1) is the monomer represented by the following general formula (1a).

[0027]

[0028] In the formula, R 2 "Same or different" respectively refers to hydrogen atom, fluorine atom, chlorine atom, bromine atom, phenyl, straight-chain or branched alkoxy group having 1 to 6 carbon atoms, or straight-chain or branched alkyl group having 1 to 6 carbon atoms. R 1 The meaning is the same as above.

[0029] <8> As mentioned above <1> or <2> The thermoplastic resin wherein the monomer represented by the above general formula (1) is the monomer represented by the following general formula (1b).

[0030]

[0031] In the formula, R 2 "Same or different" respectively refers to hydrogen atom, fluorine atom, chlorine atom, bromine atom, phenyl, straight-chain or branched alkoxy group having 1 to 6 carbon atoms, or straight-chain or branched alkyl group having 1 to 6 carbon atoms. R 1 The meaning is the same as above.

[0032] <9> As mentioned above <1> or <2> The thermoplastic resin wherein the monomer represented by the above general formula (1) is the monomer represented by the following general formula (1c).

[0033]

[0034] In the formula, R 2 "Same or different" respectively refers to hydrogen atom, fluorine atom, chlorine atom, bromine atom, phenyl, straight-chain or branched alkoxy group having 1 to 6 carbon atoms, or straight-chain or branched alkyl group having 1 to 6 carbon atoms. R 1 The meaning is the same as above.

[0035] <10> As mentioned above <1> ~ <9> The thermoplastic resin described in any one of the following statements contains structural units (B) derived from monomers represented by the following general formula (2) and / or structural units (C) derived from monomers represented by the following general formula (3).

[0036]

[0037] In equation (2), R a and R b The elements are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, aryl groups having 6 to 20 carbon atoms that may have substituents, heteroaryl groups having 6 to 20 carbon atoms that may have substituents containing one or more heterocyclic atoms selected from O, N, and S, aryloxy groups having 6 to 20 carbon atoms that may have substituents, and -C≡CR. h ,

[0038] R h The aryl group can have 6 to 20 carbon atoms and may have substituents, or a heteroaryl group can have 6 to 20 carbon atoms and may have substituents containing one or more heterocyclic atoms selected from O, N and S. X represents a single bond or a fluorenyl group that can have substituents. A and B each independently represent alkylene groups that can have 1 to 5 carbon atoms and may have substituents. m and n each independently represent integers from 0 to 6. a and b each independently represent integers from 0 to 10.

[0039]

[0040] In equation (3), R c and R d The groups are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, and aryl groups having 6 to 20 carbon atoms that may have substituents.

[0041] Y1 is a single bond, a fluorene group that may have substituents, or any of the structural formulas represented by the following formulas (4) to (10).

[0042]

[0043] In equations (4) to (10), R 61 R 62 R 71 and R 72 Each can independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 20 carbon atoms that may have substituents, or an aryl group with 6 to 30 carbon atoms that may have substituents, or represent R. 61 and R 62 or R 71 and R 72Carbon rings or heterocycles with 1 to 20 carbon atoms that are bonded together can have substituents.

[0044] r and s independently represent integers from 0 to 5000.

[0045] A and B independently represent alkylene groups with 1 to 5 carbon atoms that can have substituents, p and q independently represent integers from 0 to 4, and a and b independently represent integers from 0 to 10.

[0046] <11> As mentioned above <10> The thermoplastic resin wherein, in the above formulas (2) and (3), A and B respectively independently represent alkylene groups having 2 or 3 carbon atoms.

[0047] <12> As mentioned above <10> or <11> The thermoplastic resin, wherein the thermoplastic resin contains at least one structural unit from any one of BPEF, BNE, BNEF and DPBHBNA.

[0048] <13> As mentioned above <1> ~ <12> The thermoplastic resin described in any one of the following examples, wherein,

[0049] The above-mentioned thermoplastic resin also contains structural units derived from at least one monomer selected from the group consisting of the following monomers.

[0050]

[0051] In the above formula, R1 and R2 independently represent hydrogen atoms, methyl or ethyl, and R3 and R4 independently represent hydrogen atoms, methyl, ethyl or alkylene glycols with 2 to 5 carbon atoms.

[0052] <14> As mentioned above <1> ~ <13> The thermoplastic resin described in any one of the following examples, wherein the weight-average molecular weight (Mw) of the thermoplastic resin, converted to polystyrene, is 10,000 to 200,000.

[0053] <15> As mentioned above <1> ~ <14> The thermoplastic resin described in any one of the following examples, wherein the refractive index (nD) of the thermoplastic resin is 1.599 to 1.750.

[0054] <16> As mentioned above <1> ~ <15> The thermoplastic resin described in any one of the following examples, wherein the Abbe number (ν) of the thermoplastic resin is 25.0 to 33.0.

[0055] <17> As mentioned above <1> ~ <16> The thermoplastic resin described in any one of the following examples, wherein the glass transition temperature of the thermoplastic resin is 135 to 200°C.

[0056] <18> A thermoplastic resin composition comprising a modifier represented by the following general formula (1) and a thermoplastic resin.

[0057]

[0058] In the formula, R 1 "Identical" or "different" respectively refers to a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a phenyl group, or a straight-chain or branched alkyl group having 1 to 4 carbon atoms. "Ring A" represents a benzene ring that can be substituted by 1 to 4 groups selected from fluorine, chlorine, bromine, phenyl, straight-chain or branched alkoxy groups having 1 to 6 carbon atoms, and straight-chain or branched alkyl groups having 1 to 6 carbon atoms.

[0059] <19> An optical component, wherein the component comprises as described above <1> ~ <17> The thermoplastic resin described in any one of the above-mentioned materials or the above-mentioned materials <18> The thermoplastic resin composition described above.

[0060] <20> An optical lens, wherein the lens comprises the above-described... <1> ~ <17> The thermoplastic resin described in any one of the above-mentioned materials or the above-mentioned materials <18> The thermoplastic resin composition described above.

[0061] <21> An optical film, wherein the film contains the above-described... <1> ~ <17> The thermoplastic resin described in any one of the above-mentioned materials or the above-mentioned materials <18> The thermoplastic resin composition described above.

[0062] Invention Effects

[0063] According to the present invention, a thermoplastic resin with excellent optical properties such as refractive index and Abbe number, as well as excellent heat resistance, and an optical lens containing the resin can be provided. Detailed Implementation

[0064] In the following text, examples of synthesis and embodiments will be given to illustrate the present invention in detail. However, the present invention is not limited to the examples of synthesis and embodiments given, and any method may be used without obviously departing from the scope of the present invention.

[0065] <Thermoplastic Resins>

[0066] One embodiment of the present invention is a thermoplastic resin containing structural unit (A) derived from a monomer represented by the following general formula (1).

[0067]

[0068] In the formula, R 1"Identical" or "different" respectively refers to a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a phenyl group, or a straight-chain or branched alkyl group having 1 to 4 carbon atoms. "Ring A" represents a benzene ring that can be substituted by 1 to 4 groups selected from fluorine, chlorine, bromine, phenyl, straight-chain or branched alkoxy groups having 1 to 6 carbon atoms, and straight-chain or branched alkyl groups having 1 to 6 carbon atoms.

[0069] In general formula (1), R 1 Whether the terms are the same or different, they respectively represent hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, phenyl groups, or straight-chain or branched alkyl groups having 1 to 4 carbon atoms, preferably straight-chain or branched alkyl groups having 1 to 4 carbon atoms. As R 1 The alkyl group represented is a straight-chain or branched alkyl group having 1 to 4 carbon atoms, and is not particularly limited. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc. Among them, methyl, ethyl, isobutyl, and tert-butyl are preferred, methyl and ethyl are more preferred, and methyl is particularly preferred.

[0070] In general formula (1), ring A means that two acetal groups are bonded to each other on a benzene ring in an ortho, meta, or para position. Specifically, ring A includes the following structures.

[0071]

[0072] In the formula, ring A is the same as above.

[0073] In general formula (1), ring A is preferably a benzene ring that can be substituted by 1 to 4 groups selected from straight-chain or branched alkoxy groups having 1 to 6 carbon atoms and straight-chain or branched alkyl groups having 1 to 6 carbon atoms.

[0074] The substituent, "a straight-chain or branched alkoxy group having 1 to 6 carbon atoms," is not particularly limited, and examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy. Among these, methoxy, ethoxy, isopropoxy, isobutoxy, and tert-butoxy are preferred.

[0075] The substituent, "a straight-chain or branched alkyl group having 1 to 6 carbon atoms," is not particularly limited, and examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc. Among these, methyl, ethyl, isopropyl, isobutyl, and tert-butyl are preferred.

[0076] The ring A is particularly preferably an unsubstituted benzene ring, i.e., a divalent phenylene ring having the following structure.

[0077]

[0078] The inventors believe that the compound represented by general formula (1) is based on the interaction of the hydroxymethyl group and R in the two acetal groups. 1 The bonded carbon atoms have various stereoisomers. These isomers can be individual or a mixture.

[0079] The following describes in detail the three classes of compounds classified based on the substitution positions of the two acetal groups on ring A in compounds represented by general formula (1), namely the compounds represented by general formula (1a), general formula (1b) and general formula (1c).

[0080] The compounds represented by general formula (1a) are shown below.

[0081]

[0082] In the formula, R 2 "Same or different" respectively refers to hydrogen atom, fluorine atom, chlorine atom, bromine atom, phenyl, straight-chain or branched alkoxy group having 1 to 6 carbon atoms, or straight-chain or branched alkyl group having 1 to 6 carbon atoms. R 1 The meaning is the same as above.

[0083] In general formula (1a), as R 1 Preferably, it is a straight-chain or branched alkyl group having 1 to 4 carbon atoms, and examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Among them, methyl, ethyl, isobutyl, and tert-butyl are preferred.

[0084] In general formula (1a), as R 2 Preferably, it is a straight-chain or branched alkoxy group with hydrogen atoms and 1 to 6 carbon atoms, or a straight-chain or branched alkyl group with 1 to 6 carbon atoms. As R 2 The preferred atom is hydrogen.

[0085] As R 2 The term "alkoxy group with 1 to 4 carbon atoms in a straight or branched form" is not particularly limited and can include, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, etc. Among them, methoxy, ethoxy, isopropoxy, isobutoxy, and tert-butoxy are preferred.

[0086] As R 2 The term "alkyl group having 1 to 6 carbon atoms in a straight or branched form" is not particularly limited and can include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc. Among these, methyl, ethyl, isopropyl, isobutyl, and tert-butyl are preferred.

[0087] The inventors believe that the compound represented by general formula (1a) exists as isomers such as isomer A, isomer B, or isomer C. These isomers can be individual or a mixture.

[0088]

[0089]

[0090] In the formula, R 1 and R 2 The meaning is the same as above.

[0091] When the compound represented by general formula (1a) is a mixture of two or more isomers, the isomer ratio can be determined by gas chromatography (GC) analysis using the method described in the examples, and obtained by the area percentage method. Based on GC analysis, each isomer typically has its own characteristic peak. The isomer content ratio can be expressed as the percentage of the peak area of ​​each isomer relative to the total peak area of ​​the cyclic diol compound. The percentage of each isomer can be used as the isomer ratio. Alternatively, the hydroxyl groups of the cyclic diol compound of the present invention can be trimethylsilanized using N,O-bis(trimethylsilyl)trifluoroacetamide or the like before GC analysis.

[0092] The inventors believe that the compound represented by general formula (1a) exists as isomers such as (1a-A), (1a-B), or (1a-C) as described above. Two or three isomer peaks are detected in GC analysis, and these are considered to be isomers (1a-A), (1a-B), or (1a-C). The isomer ratio obtained from GC analysis can be in the range of isomer (1a-A): isomer (1a-B): isomer (1a-C) = 10 to 1:10 to 1:1.

[0093] Specific examples of compounds represented by general formula (1a) include, for example, isophthalaldehyde trimethylolpropane diacetate, isophthalaldehyde trimethylolpropane diacetate, 5-methylisophthalaldehyde trimethylolpropane diacetate, 4-methylisophthalaldehyde trimethylolpropane diacetate, 4-chloroisophthalaldehyde trimethylolpropane diacetate, 5-chloroisophthalaldehyde trimethylolpropane diacetate, 5-bromoisophthalaldehyde trimethylolpropane diacetate, 4-bromoisophthalaldehyde trimethylolpropane diacetate, 2-bromoisophthalaldehyde trimethylolpropane diacetate, 4,6-dimethylisophthalaldehyde trimethylolpropane diacetate, and 2,4-dimethylisophthalaldehyde trimethylolpropane diacetate. Dimethyl 2-hydroxymethyl ethane diacetate, 2,5-dichloro-m-phthalaldehyde diacetate, 4,6-dichloro-m-phthalaldehyde diacetate, 4,6-dibromo-m-phthalaldehyde diacetate, 2,5-dibromo-m-phthalaldehyde diacetate, 5-tert-butyl-m-phthalaldehyde diacetate, 2,4,5,6-tetrafluoro-m-phthalaldehyde diacetate, 5-(bromomethyl)-m-phthalaldehyde diacetate, 4-isopropyl-m-phthalaldehyde diacetate, 4,6-diisopropyl-m-phthalaldehyde diacetate, 2-bromo-5-tert-butyl-2- 4-Phenylo-isophthalaldehyde trimethylolpropane diacetate, 5-Phenylo-isophthalaldehyde trimethylolpropane diacetate, 4-Pheny-6-methyl-isophthalaldehyde trimethylolpropane diacetate, 4,5-Diethyl-6-methyl-isophthalaldehyde trimethylolpropane diacetate, 5-Hexyl-isophthalaldehyde trimethylolpropane diacetate, 4-Hexyl-isophthalaldehyde trimethylolpropane diacetate, 5-Butoxy-isophthalaldehyde trimethylolpropane diacetate, 2-Methoxy-isophthalaldehyde trimethylolpropane diacetate, 4-Methoxy-isophthalaldehyde trimethylolpropane diacetate, 5-Methoxy-isophthalaldehyde trimethylolpropane diacetate Hydroxymethyl ethane diacetate, 2-methoxy-4-methyl-isophthalaldehyde tris(hydroxymethyl)ethane diacetate, 2-methyl-4-methoxy-isophthalaldehyde tris(hydroxymethyl)ethane diacetate, 2-methoxy-5-methyl-isophthalaldehyde tris(hydroxymethyl)ethane diacetate, 4-methyl-6-methoxy-isophthalaldehyde tris(hydroxymethyl)ethane diacetate, 4,6-dimethoxy-isophthalaldehyde tris(hydroxymethyl)ethane diacetate, 2-methoxy-4-ethyl-isophthalaldehyde tris(hydroxymethyl)ethane diacetate, 4,6-dimethyl-2-methoxy-isophthalaldehyde tris(hydroxymethyl)ethane diacetate, 2,4-dimethoxy-6-methyl-isophthalaldehyde tris(hydroxymethyl)ethane diacetate, 2...4-Dimethyl-6-methoxy-isophthalaldehyde trimethylolpropane diacetate, 4-ethyl-5-methyl-6-methoxy-isophthalaldehyde trimethylolpropane diacetate, 5-methyl-isophthalaldehyde trimethylolpropane diacetate, 4-methyl-isophthalaldehyde trimethylolpropane diacetate, 4-chloro-isophthalaldehyde trimethylolpropane diacetate, 5-chloro-isophthalaldehyde trimethylolpropane diacetate, 5-bromo-isophthalaldehyde trimethylolpropane diacetate, 4-bromo-isophthalaldehyde trimethylolpropane diacetate, 2-bromo-isophthalaldehyde trimethylolpropane diacetate, 4,6-dimethyl-isophthalaldehyde trimethylolpropane diacetate, 2,4- Dimethyl isophthalaldehyde trimethylolpropane diacetate, 2,5-dichloro-isophthalaldehyde trimethylolpropane diacetate, 4,6-dichloro-isophthalaldehyde trimethylolpropane diacetate, 4,6-dibromo-isophthalaldehyde trimethylolpropane diacetate, 2,5-dibromo-isophthalaldehyde trimethylolpropane diacetate, 5-tert-butyl-isophthalaldehyde trimethylolpropane diacetate, 2,4,5,6-tetrafluoro-isophthalaldehyde trimethylolpropane diacetate, acetal, 4-isopropyl-isophthalaldehyde trimethylolpropane diacetate, 4,6-diisopropyl-isophthalaldehyde trimethylolpropane diacetate, 2-bromo-5-tert-butyl-isophthalaldehyde trimethylolpropane diacetate Methylpropane diacetal, 4-phenyl-isophthalaldehyde trimethylolpropane diacetal, 5-phenyl-isophthalaldehyde trimethylolpropane diacetal, 4-phenyl-6-methyl-isophthalaldehyde trimethylolpropane diacetal, 4,5-diethyl-6-methyl-isophthalaldehyde trimethylolpropane diacetal, 5-hexyl-isophthalaldehyde trimethylolpropane diacetal, 4-hexyl-isophthalaldehyde trimethylolpropane diacetal, 5-butoxy-isophthalaldehyde trimethylolpropane diacetal, 2-methoxy-isophthalaldehyde trimethylolpropane diacetal, 4-methoxy-isophthalaldehyde trimethylolpropane diacetal, 5-methoxy-isophthalaldehyde trimethylolpropane diacetal Alkyl diacetate, 2-methoxy-4-methyl-isophthalaldehyde trimethylolpropane diacetate, 2-methyl-4-methoxy-isophthalaldehyde trimethylolpropane diacetate, 2-methoxy-5-methyl-isophthalaldehyde trimethylolpropane diacetate, 4-methyl-6-methoxy-isophthalaldehyde trimethylolpropane diacetate, 4,6-dimethoxy-isophthalaldehyde trimethylolpropane diacetate, 2-methoxy-4-ethyl-isophthalaldehyde trimethylolpropane diacetate, 4,6-dimethyl-2-methoxy-isophthalaldehyde trimethylolpropane diacetate, 2,4-dimethoxy-6-methyl-isophthalaldehyde trimethylolpropane diacetate, 2...Examples of preferred compounds include 4-dimethyl-6-methoxy-isophthalaldehyde trimethylolpropane diacetate and 4-ethyl-5-methyl-6-methoxy-isophthalaldehyde trimethylolpropane diacetate. Among these, preferred compounds include isophthalaldehyde trimethylolpropane diacetate, isophthalaldehyde trimethylolpropane diacetate, 5-methyl-isophthalaldehyde trimethylolpropane diacetate, 5-methyl-isophthalaldehyde trimethylolpropane diacetate, 4-methyl-isophthalaldehyde trimethylolpropane diacetate, and 4-methyl-isophthalaldehyde trimethylolpropane diacetate. Particularly preferred compounds include isophthalaldehyde trimethylolpropane diacetate and isophthalaldehyde trimethylolpropane diacetate.

[0094] The compounds represented by general formula (1b) are shown below.

[0095]

[0096] In the formula, R 1 and R 2 The meaning is the same as above.

[0097] R is the preferred option in general formula (1b) 1 The preferred R in general formula (1a) 1 The meaning is the same. Furthermore, R is the preferred option in general formula (1b). 2 The preferred R in general formula (1a) 2 They have the same meaning.

[0098] The inventors believe that the compound represented by general formula (1b) exists as isomers such as (1b-A), (1b-B), or (1b-C). These isomers can be individual or mixtures.

[0099]

[0100] Isomer (1b-A)

[0101]

[0102] Isomer (1b-B)

[0103]

[0104] Isomer (1b-C)

[0105] In the formula, R 1 and R 2 The meaning is the same as above.

[0106] When the compound represented by general formula (1b) is a mixture of two or more isomers, the isomer ratio can be determined by gas chromatography (GC) analysis using the method described in the examples, and obtained by the area percentage method. Based on GC analysis, each isomer typically has its own characteristic peak. The isomer content ratio can be expressed as the percentage of the peak area of ​​each isomer relative to the total peak area of ​​the cyclic diol compound. The percentage of each isomer can be used as the isomer ratio. Alternatively, the hydroxyl groups of the cyclic diol compound of the present invention can be trimethylsilanized using N,O-bis(trimethylsilyl)trifluoroacetamide or the like before GC analysis.

[0107] The inventors believe that the compound represented by general formula (1b) exists as isomers such as (1b-A), (1b-B), or (1b-C) as described above. Two or three isomer peaks are detected in GC analysis, and these are considered to be isomers (1b-A), (1b-B), or (1b-C). The isomer ratio obtained from GC analysis can be in the range of isomer (1b-A): isomer (1b-B): isomer (1b-C) = 10 to 1:10 to 1:1.

[0108] Specific examples of compounds represented by general formula (1b) include, for example, terephthalaldehyde trimethylolpropane diacetate, terephthalaldehyde trimethylolethane diacetate, 2-methylterephthalaldehyde trimethylolethane diacetate, 3-methylterephthalaldehyde trimethylolethane diacetate, 3-chloroterephthalaldehyde trimethylolethane diacetate, 2-chloroterephthalaldehyde trimethylolethane diacetate, 2-bromoterephthalaldehyde trimethylolethane diacetate, 3-bromoterephthalaldehyde trimethylolethane diacetate, 3,6-dimethylterephthalaldehyde trimethylolethane diacetate, 2,3-dimethylterephthalaldehyde trimethylolethane diacetate, 2,5-dichloroterephthalaldehyde trimethylolethane diacetate, and 3,6-dichloroterephthalaldehyde trimethylolethane diacetate. Diacetal, 3,6-dibromo-terephthalaldehyde trimethylolethane diacetal, 2,5-dibromo-terephthalaldehyde trimethylolethane diacetal, 2-tert-butyl-terephthalaldehyde trimethylolethane diacetal, 2,3,5,6-tetrafluoro-terephthalaldehyde trimethylolethane diacetal, 3-isopropyl-terephthalaldehyde trimethylolethane diacetal, 3,6-diisopropyl-terephthalaldehyde trimethylolethane diacetal, 2-bromo-5-tert-butyl-terephthalaldehyde trimethylolethane diacetal, 3-phenyl-terephthalaldehyde trimethylolethane diacetal, 2-phenyl-terephthalaldehyde trimethylolethane diacetal, 3-phenyl-6-methyl-terephthalaldehyde trimethylolethane diacetal, 3,5-diethyl-6-methyl-terephthalaldehyde trimethylolethane diacetal 2-Hexyl-terephthalaldehyde trimethylolethane diacetate, 3-Hexyl-terephthalaldehyde trimethylolethane diacetate, 2-Butoxy-terephthalaldehyde trimethylolethane diacetate, 3-Methoxy-terephthalaldehyde trimethylolethane diacetate, 2-Methoxy-terephthalaldehyde trimethylolethane diacetate, 2-Methoxy-3-methyl-terephthalaldehyde trimethylolethane diacetate, 2-Methyl-3-methoxy-terephthalaldehyde trimethylolethane diacetate, 2-Methoxy-5-methyl-terephthalaldehyde trimethylolethane diacetate, 3-Methyl-6-methoxy-terephthalaldehyde trimethylolethane diacetate, 3,6-Dimethoxy-terephthalaldehyde trimethylolethane diacetate, 2-Methoxy-3-ethyl-terephthalaldehyde trimethylolethane diacetate, 3 6-Dimethyl-2-methoxy-terephthalaldehyde trimethylolpropane diacetate, 2,3-dimethoxy-6-methyl-terephthalaldehyde trimethylolpropane diacetate, 2,3-dimethyl-6-methoxy-terephthalaldehyde trimethylolpropane diacetate, 3-ethyl-5-methyl-6-methoxy-terephthalaldehyde trimethylolpropane diacetate, 2-methyl-terephthalaldehyde trimethylolpropane diacetate, 3-methyl-terephthalaldehyde trimethylolpropane diacetate, 3-chloro-terephthalaldehyde trimethylolpropane diacetate, 2-chloro-terephthalaldehyde trimethylolpropane diacetate, 2-bromo-terephthalaldehyde trimethylolpropane diacetate, 3-bromo-terephthalaldehyde trimethylolpropane diacetate, 3,6-dimethyl-terephthalaldehyde trimethylolpropane diacetate, 2,3-Dimethylterephthalaldehyde trimethylolpropane diacetate, 2,5-Dichloroterephthalaldehyde trimethylolpropane diacetate, 3,6-Dichloroterephthalaldehyde trimethylolpropane diacetate, 3,6-Dibromoterephthalaldehyde trimethylolpropane diacetate, 2,5-Dibromoterephthalaldehyde trimethylolpropane diacetate, 2-tert-butylterephthalaldehyde trimethylolpropane diacetate, 2,3,5,6-Tetrafluoroterephthalaldehyde trimethylolpropane diacetate, 3-Isopropylterephthalaldehyde trimethylolpropane diacetate Acetal, 3,6-diisopropylterephthalaldehyde trimethylolpropane diacetal, 2-bromo-5-tert-butylterephthalaldehyde trimethylolpropane diacetal, 3-phenylterephthalaldehyde trimethylolpropane diacetal, 2-phenylterephthalaldehyde trimethylolpropane diacetal, 3-phenyl-6-methylterephthalaldehyde trimethylolpropane diacetal, 3,5-diethyl-6-methylterephthalaldehyde trimethylolpropane diacetal, 2-hexylterephthalaldehyde trimethylolpropane diacetal, 3-hexylterephthalaldehyde Trimethylolpropane diacetal, 2-butoxy-terephthalaldehyde trimethylolpropane diacetal, 3-methoxy-terephthalaldehyde trimethylolpropane diacetal, 2-methoxy-terephthalaldehyde trimethylolpropane diacetal, 2-methoxy-3-methyl-terephthalaldehyde trimethylolpropane diacetal, 2-methyl-3-methoxy-terephthalaldehyde trimethylolpropane diacetal, 3-methyl-6-methoxy-terephthalaldehyde trimethylolpropane diacetal, 3,6-dimethoxy-terephthalaldehyde trimethylolpropane diacetal Aldehydes, 2-methoxy-3-ethylterephthalaldehyde trimethylolpropane diacetal, 2-methoxy-5-methylterephthalaldehyde trimethylolpropane diacetal, 3,6-dimethyl-2-methoxyterephthalaldehyde trimethylolpropane diacetal, 2,3-dimethoxy-6-methylterephthalaldehyde trimethylolpropane diacetal, 2,3-dimethyl-6-methoxyterephthalaldehyde trimethylolpropane diacetal, 3-ethyl-5-methyl-6-methoxyterephthalaldehyde trimethylolpropane diacetal, etc. Among the preferred compounds are terephthalaldehyde trimethylolpropane diacetate, terephthalaldehyde trimethylolpropane diacetate, 2-methylterephthalaldehyde trimethylolpropane diacetate, 2-methylterephthalaldehyde trimethylolpropane diacetate, 3-methylterephthalaldehyde trimethylolpropane diacetate, and 3-methylterephthalaldehyde trimethylolpropane diacetate, etc. Particularly preferred compounds include terephthalaldehyde trimethylolpropane diacetate and terephthalaldehyde trimethylolpropane diacetate, etc.

[0109] The compounds represented by general formula (1c) are shown below.

[0110]

[0111] In the formula, R 1 and R 2 The meaning is the same as above.

[0112] R is the preferred option in general formula (1c) 1 The preferred R in general formula (1a) 1 The meaning is the same. Furthermore, R is the preferred option in general formula (1c). 2 The preferred R in general formula (1a) 2 They have the same meaning.

[0113] The inventors believe that the compound represented by the general formula (1c) exists as isomers such as (1c-A), (1c-B), or (1c-C). These isomers can be individual or a mixture.

[0114]

[0115] In the formula, R 1 and R 2 The meaning is the same as above.

[0116] When the compound represented by general formula (1c) is a mixture of two or more isomers, the isomer ratio can be determined by gas chromatography (GC) analysis using the method described in the examples, and obtained by the area percentage method. Based on GC analysis, each isomer typically has its own characteristic peak. The isomer content ratio can be expressed as the percentage of the peak area of ​​each isomer relative to the total peak area of ​​the cyclic diol compound. The percentage of each isomer can be used as the isomer ratio. Alternatively, the hydroxyl groups of the cyclic diol compound of the present invention can be trimethylsilanized using N,O-bis(trimethylsilyl)trifluoroacetamide or the like before GC analysis.

[0117] The inventors believe that compounds represented by general formula (1c) exist as isomers such as (1c-A), (1c-B), or (1c-C) as described above. Two or three isomer peaks are detected in GC analysis, and these are considered to be isomers (1c-A), (1c-B), or (1c-C). The isomer ratio obtained from GC analysis can be in the range of isomer (1c-A): isomer (1c-B): isomer (1c-C) = 10 to 1:10 to 1:1.

[0118] Specific examples of compounds represented by general formula (1c) include, for example, phthalaldehyde trimethylolpropane diacetate, phthalaldehyde trimethylolpropane diacetate, 3-methylphthalaldehyde trimethylolpropane diacetate, 4-methylphthalaldehyde trimethylolpropane diacetate, 3-chlorophthalaldehyde trimethylolpropane diacetate, 3-bromophthalaldehyde trimethylolpropane diacetate, 3,6-dimethylphthalaldehyde trimethylolpropane diacetate, 3,4-dimethylphthalaldehyde trimethylolpropane diacetate, 3,5-dimethylphthalaldehyde trimethylolpropane diacetate, 4,5-dimethylphthalaldehyde trimethylolpropane diacetate, and 3,6-dichlorophthalaldehyde trimethylolpropane diacetate. Aldehydes, 3,6-dibromophthalaldehyde tris(hydroxymethyl)ethane diacetate, 3,6-diethyl-4-methylphthalaldehyde tris(hydroxymethyl)ethane diacetate, 3-hexylphthalaldehyde tris(hydroxymethyl)ethane diacetate, 3-butoxyphthalaldehyde tris(hydroxymethyl)ethane diacetate, 3-methoxyphthalaldehyde tris(hydroxymethyl)ethane diacetate, 3-methoxy-6-methylphthalaldehyde tris(hydroxymethyl)ethane diacetate, 3-methyl-6-methoxyphthalaldehyde tris(hydroxymethyl)ethane diacetate, 3,6-dimethoxyphthalaldehyde tris(hydroxymethyl)ethane diacetate, 3-methoxy-6-ethylphthalaldehyde tris(hydroxymethyl)ethane diacetate, 3,6-dimethyl-4-methoxyphthalaldehyde tris(hydroxymethyl)ethane diacetate, 3 6-Dimethoxy-4-methylphthalaldehyde trimethylolpropane diacetate, 3-methylphthalaldehyde trimethylolpropane diacetate, 4-methylphthalaldehyde trimethylolpropane diacetate, 3-chlorophthalaldehyde trimethylolpropane diacetate, 3-bromophthalaldehyde trimethylolpropane diacetate, 3,6-dimethylphthalaldehyde trimethylolpropane diacetate, 3,4-dimethylphthalaldehyde trimethylolpropane diacetate, 3,5-dimethylphthalaldehyde trimethylolpropane diacetate, 4,5-dimethylphthalaldehyde trimethylolpropane diacetate, 3,6-dichlorophthalaldehyde trimethylolpropane diacetate, 3,6-dibromophthalaldehyde trimethylolpropane diacetate, 3,6-di Ethyl-4-methylphthalaldehyde trimethylolpropane diacetate, 3-hexylphthalaldehyde trimethylolpropane diacetate, 3-butoxyphthalaldehyde trimethylolpropane diacetate, 3-methoxyphthalaldehyde trimethylolpropane diacetate, 3-methoxy-6-methylphthalaldehyde trimethylolpropane diacetate, 3-methyl-6-methoxyphthalaldehyde trimethylolpropane diacetate, 3,6-dimethoxyphthalaldehyde trimethylolpropane diacetate, 3-methoxy-6-ethylphthalaldehyde trimethylolpropane diacetate, 3,6-dimethyl-4-methoxyphthalaldehyde trimethylolpropane diacetate, 3,6-dimethoxy-4-methylphthalaldehyde trimethylolpropane diacetate, etc.Among the preferred compounds are phthalaldehyde trimethylolpropane diacetal, phthalaldehyde trimethylolpropane diacetal, 3-methylphthalaldehyde trimethylolpropane diacetal, 3-methylphthalaldehyde trimethylolpropane diacetal, 4-methylphthalaldehyde trimethylolpropane diacetal, and 4-methylphthalaldehyde trimethylolpropane diacetal. Particularly preferred compounds include phthalaldehyde trimethylolpropane diacetal and phthalaldehyde trimethylolpropane diacetal.

[0119] The method of manufacturing the compound represented by general formula (1) is not particularly limited. It can be manufactured by, for example, the process shown in the following <Reaction Formula 1>, by reacting the compound represented by general formula (3) with the compound represented by general formula (4) (acetalization reaction).

[0120] <Reaction Formula 1>

[0121]

[0122] In the formula, R 1 The meaning of ring A is the same as above.

[0123] Specifically, it can be produced by reacting the compound represented by general formula (1) with the compound represented by general formula (3) and the compound represented by general formula (4) in the presence of an acidic catalyst (acetalization reaction).

[0124] The reaction can usually be carried out in a solvent (such as toluene). It can be achieved by heating the solvent under reflux, causing the generated water to azeotropically with the solvent and then removing it. There are no particular limitations on the acid catalyst; any known acid catalyst with catalytic activity can be used. Examples include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, trifluoroacetic acid, and trifluoromethanesulfonic acid; solid acids such as cation exchange resins, zeolites, silica alumina, and heteropoly acids (e.g., phosphotungstic acid, phosphomolybdic acid); and various Lewis acids.

[0125] The amount of the compound represented by general formula (4) used is typically 0.5 to 3 moles, preferably 0.8 to 2 moles, relative to 1 mole of the compound represented by general formula (3).

[0126] The compounds represented by general formula (1a), general formula (1b) and general formula (1c) contained in the compound represented by general formula (1) can also be prepared in the same manner as in <Reaction Formula 1>.

[0127] The compound represented by general formula (1a) can be prepared by reacting the compound represented by general formula (3a) with the compound represented by general formula (4) in the presence of an acidic catalyst (acetalization reaction) as shown in the following <Reaction Formula 2>.

[0128] <Reaction 2>

[0129]

[0130] In the formula, R 1 and R 2 The meaning is the same as above.

[0131] The compound represented by general formula (1b) can be prepared by reacting the compound represented by general formula (3b) with the compound represented by general formula (4) in the presence of an acidic catalyst (acetalization reaction) as shown in the following <Reaction Formula 3>.

[0132] <Reaction Formula 3>

[0133]

[0134] In the formula, R 1 and R 2 The meaning is the same as above.

[0135] The compound represented by general formula (1c) can be prepared by reacting the compound represented by general formula (3c) with the compound represented by general formula (4) in the presence of an acidic catalyst (acetalization reaction) as shown in the following <Reaction Formula 4>.

[0136] <Reaction Formula 4>

[0137]

[0138] In the formula, R 1 and R 2 The meaning is the same as above.

[0139] In one embodiment of the present invention, the thermoplastic resin is a polyester resin, polycarbonate resin, polyester carbonate resin, epoxy resin, polyurethane resin, polyacrylate resin, polymethyl methacrylate resin, etc. Although there are no particular limitations, polycarbonate resin or polyester carbonate resin is preferred, more preferably a resin containing a structural unit (A) represented by the following formula, and particularly preferably a resin containing at least one of the structural units (A1), (A2) and (A3) represented by the following formula.

[0140]

[0141] In the formula, R 1 The meaning of ring A is the same as that in the above general formula (1).

[0142]

[0143] In the formula, R 1 and R2 The meaning is the same as in the above general formula (1a).

[0144]

[0145] In the formula, R 1 and R 2 The meaning is the same as in the general formula (1b) above.

[0146]

[0147] In the formula, R 1 and R 2 The meaning is the same as in the above general formula (1c).

[0148] In a thermoplastic resin according to one embodiment of the present invention, the proportion of the structural unit (A) represented by the above formula in all structural units is not particularly limited, but is preferably 1 to 80 mol% of all structural units, more preferably 1 to 60 mol%, and particularly preferably 5 to 50 mol%.

[0149] That is, in addition to the structural unit (A) represented by the above formula, the thermoplastic resin of one embodiment of the present invention may also contain aliphatic dihydroxy compound derived structural units and / or aromatic dihydroxy compound derived structural units that are commonly used as structural units of polycarbonate resin or polyester carbonate resin.

[0150] Specifically, various compounds can be cited as aliphatic dihydroxy compounds, particularly 1,4-cyclohexanediethanol, tricyclodecanediethanol, 1,3-adamantanediethanol, 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-dioxane-2-yl)-2-methylpropane-1-ol, isosorbide, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, etc.

[0151] As aromatic dihydroxy compounds, various compounds can be cited, 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)cycloalkanes, bis(4-hydroxyphenyl)oxides, bis(4-hydroxyphenyl)sulfides, bis(4-hydroxyphenyl)sulfones, bis(4-hydroxyphenyl) sulfoxides, bis(4-hydroxyphenyl) ketones, and bisphenoxyethanolfluorene, etc.

[0152] In addition, the thermoplastic resin of one embodiment of the present invention preferably contains structural units (B) derived from the monomer represented by the following formula (2).

[0153]

[0154] In equation (2), R a and R b The elements are independently selected from halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, aryl groups having 6 to 20 carbon atoms that may have substituents, heteroaryl groups having 6 to 20 carbon atoms that may have substituents containing one or more heterocyclic atoms selected from O, N, and S, aryloxy groups having 6 to 20 carbon atoms that may have substituents, and -C≡CR. h R h It refers to an aryl group with 6 to 20 carbon atoms that may have substituents, or a heteroaryl group with 6 to 20 carbon atoms that may have substituents and contains one or more heterocyclic atoms selected from O, N and S.

[0155] R a and R b Preferably, it is a hydrogen atom, an aryl group with 6 to 20 carbon atoms that may have substituents, or a heteroaryl group with 6 to 20 carbon atoms that may have substituents and contains one or more heterocyclic atoms selected from O, N, and S. More preferably, it is a hydrogen atom, an aryl group with 6 to 20 carbon atoms that may have substituents. Even more preferably, it is a hydrogen atom, an aryl group with 6 to 12 carbon atoms that may have substituents.

[0156] In formula (2), X represents a single bond or a fluorenyl group that may have substituents, and X is preferably a single bond or a fluorenyl group that may have substituents and has a total number of carbon atoms of 12 to 20.

[0157] In formula (2), A and B independently represent alkylene groups having 1 to 5 carbon atoms that may have substituents, preferably alkylene groups having 2 or 3 carbon atoms.

[0158] In equation (2), m and n independently represent integers from 0 to 6, preferably integers from 0 to 3, and more preferably 0 or 1.

[0159] In equation (2), a and b independently represent integers from 0 to 10, preferably integers from 1 to 3, and more preferably 1 or 2.

[0160] Specific examples of structural unit (B) include structural units derived from 2,2'-bis(2-hydroxyethoxy)-1,1'-dinaphthalene (BNE), DPBHBNA, etc.

[0161]

[0162] Furthermore, the thermoplastic resin of one embodiment of the present invention preferably has a structural unit (C) derived from a monomer represented by the following formula (3).

[0163]

[0164] In equation (3), R c and R d The substituents are independently selected from halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, and aryl groups having 6 to 20 carbon atoms that may have substituents.

[0165] R c and R d Preferably, it is a hydrogen atom, an aryl group with 6 to 20 carbon atoms that may have substituents, or a heteroaryl group with 6 to 20 carbon atoms that may have substituents and contains one or more heterocyclic atoms selected from O, N, and S. More preferably, it is a hydrogen atom, an aryl group with 6 to 20 carbon atoms that may have substituents. Even more preferably, it is a hydrogen atom, an aryl group with 6 to 12 carbon atoms that may have substituents.

[0166] In formula (3), Y1 is a single bond, a fluorene group that may have substituents, or any of the structural formulas represented by formulas (4) to (10) below, preferably a single bond or the structural formula represented by formula (4) below.

[0167]

[0168] In equations (4) to (10), R 61 R 62 R 71 and R 72 Each can independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 20 carbon atoms that may have substituents, or an aryl group with 6 to 30 carbon atoms that may have substituents, or represent R. 61 With R 62 or R 71 With R 72 Carbon rings or heterocycles with 1 to 20 carbon atoms that can be formed by mutual bonding and may have substituents.

[0169] In equations (4) to (10), r and s independently represent integers from 0 to 5000.

[0170] In formula (3) above, A and B independently represent alkylene groups having 1 to 5 carbon atoms, preferably alkylene groups having 2 or 3 carbon atoms. In formula (3) above, p and q independently represent integers from 0 to 4, preferably 0 or 1. Furthermore, in formula (3) above, a and b independently represent integers from 0 to 10, preferably integers from 0 to 5, more preferably integers from 0 to 2, for example, 0 or 1.

[0171] Specific examples of structural unit (C) include those derived 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)naphthyl-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-phenyleneethylidene)bisphenol), bisphenol P-CDE (4,4'-cyclododecylene bisphenol), and bisphenol P-HTG (4,4'-(3,3,5-trimethylcyclohexylene)bisphenol). The structural units include bisphenol P-MIBK (4,4'-(1,3-dimethylbutylene)bisphenol), bisphenol PEO-FL (bisphenoxyethanolfluorene), bisphenol P-3MZ (4-[1-(4-hydroxyphenyl)-3-methylcyclohexyl]phenol), bisphenol OC-FL (4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylene]bisphenol), bisphenol Z, BP-2EO (2,2'-[[1,1'-biphenyl]-4,4'-dimethylbis(oxo)bisethanol), S-BOC (4,4'-(1-methylethylene)bis(2-methylphenol), TrisP-HAP (4,4',4”-ethylenetriol), etc. Among these, the structural unit (C) is preferably a structural unit derived from BPEF or BNEF.

[0172]

[0173] Although the thermoplastic resin of one embodiment of the present invention requires structural unit (A) as a necessary unit, it may also be a polymer containing structural unit (B) but not structural unit (C), a polymer containing structural unit (C) but not structural unit (B), a copolymer containing structural unit (B) and structural unit (C), a mixture of polymer containing structural unit (B) and polymer containing structural unit (C), and combinations thereof. Examples of polymers containing structural unit (B) but not structural unit (C) include polymers containing structural units of formulas (I-1) to (I-3); examples of copolymers containing structural units (B) and structural unit (C) include polymers containing structural units of formulas (II-1) to (II-4).

[0174]

[0175] (In formula (I-1), m and n are integers from 1 to 10, preferably integers from 1 to 5, and more preferably 1.)

[0176] The number of repeating units in formula (I-3) is an integer from 1 to 10, preferably an integer from 1 to 5, and more preferably 1.

[0177] Furthermore, as a polymer having multiple structural units, although either a block copolymer or a random copolymer with a value of, for example, 100 or more, can be used, a random copolymer is preferred, and a random copolymer with a value of 1 is more preferred.

[0178]

[0179] In equations (II-1) to (II-4), m and n are independent and are integers from 1 to 10, preferably integers from 1 to 5, and more preferably 1.

[0180] Furthermore, as a polymer having multiple structural units, although either a block copolymer or a random copolymer with a value of, for example, 100 or more, can be used, a random copolymer is preferred, and a random copolymer with a value of 1 is more preferred.

[0181] 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 structural unit (B) to the polymer having 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.

[0182] The thermoplastic resin of one embodiment of the present invention preferably further contains a structural unit from at least one monomer selected from the group consisting of the following monomers.

[0183]

[0184] In the above formula, R1 and R2 independently represent hydrogen atoms, methyl or ethyl, and R3 and R4 independently represent hydrogen atoms, methyl, ethyl or alkylene glycols with 2 to 5 carbon atoms.

[0185] In a preferred embodiment of the polycarbonate resin of the present invention, alcohol compounds such as phenols generated as byproducts during manufacturing, unreacted diol components, or diesters of carbonate may sometimes exist as impurities.

[0186] Since impurities such as phenolic compounds and alcoholic compounds and carbonates can reduce the strength of the molded body or produce odorous gases, their content is preferably as low as possible.

[0187] The content of residual phenolic compounds relative to 100% by mass of polycarbonate resin is preferably 3000 ppm or less, more preferably 1000 ppm or less, and particularly preferably 300 ppm or less.

[0188] The content of the residual diol component relative to 100% by mass of the polycarbonate resin is preferably 1000 ppm or less, more preferably 100 ppm or less, and particularly preferably 10 ppm or less.

[0189] The residual diester content relative to 100% by mass of polycarbonate resin is preferably 1000 ppm or less, more preferably 100 ppm or less, and particularly preferably 10 ppm or less.

[0190] In particular, the content of compounds such as phenol and tert-butylphenol is preferably low, and these compounds are preferably within the above-mentioned range.

[0191] The content of residual phenolic compounds in polycarbonate resin can be measured by analyzing phenolic compounds extracted from polycarbonate resin using gas chromatography.

[0192] The content of residual alcohol compounds in polycarbonate resin can also be measured by analyzing alcohol compounds extracted from polycarbonate resin using gas chromatography.

[0193] The content of residual diol components and diesters in polycarbonate resins can also be measured by analyzing these compounds extracted from polycarbonate resins using gas chromatography.

[0194] The content of byproducts such as phenolic compounds, alcohols, diols, and carbonates can be reduced to undetectable levels. However, from a production efficiency perspective, trace amounts are acceptable as long as they do not compromise the overall effect. Furthermore, even trace amounts can improve plasticity during resin melting.

[0195] The content of residual phenolic compounds, diol components, or carbonates relative to 100% by mass of polycarbonate resin can be, for example, 0.01 ppm or more, 0.1 ppm or more, or 1 ppm or more.

[0196] The content of residual alcohol compounds relative to 100% by mass of polycarbonate resin can be, for example, 0.01 ppm or more, 0.1 ppm or more, or 1 ppm or more.

[0197] It should be noted that the content of by-product alcohols such as phenols, diol components, and diesters in polycarbonate resin can be adjusted to the above-mentioned range by appropriately adjusting the polycondensation conditions and equipment settings. Alternatively, it can be adjusted according to the conditions of the extrusion process after polycondensation.

[0198] For example, the residual amount of by-product alcohol compounds such as phenols is related to the type of diester used in the polymerization of polycarbonate resin, the polymerization temperature, and the polymerization pressure. By adjusting these conditions, the residual amount of by-product alcohol compounds such as phenols can be reduced.

[0199] For example, when using dialkyl carbonates such as diethyl carbonate to produce polycarbonate resins, there is a tendency for the molecular weight to not increase easily, for low molecular weight polycarbonates to form, and for the content of by-product alkyl alcohol compounds to increase. These alkyl alcohols are highly volatile, and if they remain in the polycarbonate resin, they may deteriorate the resin's moldability. Furthermore, when the residual amount of by-product alcohol compounds such as phenols is high, problems such as the generation of odorous gases may occur during resin molding, or the resin skeleton may undergo a cracking reaction during material compounding, resulting in a decrease in molecular weight. Therefore, the content of residual by-product alcohol compounds in the resulting polycarbonate resin is preferably 3000 ppm or less relative to the polycarbonate resin (100% by mass). The content of residual alcohol compounds relative to 100% by mass of the polycarbonate resin is preferably 3000 ppm or less, more preferably 1000 ppm or less, and particularly preferably 300 ppm or less.

[0200] <Physical Properties of Thermoplastic Resins>

[0201] (1) Refractive index (nD)

[0202] In one embodiment of the invention, one characteristic of the thermoplastic resin is a high refractive index, preferably 1.599 to 1.750, more preferably 1.599 to 1.650, and particularly preferably 1.600 to 1.650. In this invention, the refractive index can be measured by the method described in the embodiments below.

[0203] (2) Abbe number (ν)

[0204] In one embodiment of the present invention, the Abbe number of the thermoplastic resin is preferably 25.0 to 33.0, more preferably 25.5 to 32.0, and particularly preferably 26.0 to 30.0. In the present invention, the Abbe number can be measured by the method described in the embodiments described later.

[0205] (3) Glass transition temperature (Tg)

[0206] In one embodiment of the invention, one characteristic of the thermoplastic resin is its high heat resistance, with a glass transition temperature (Tg) preferably of 135–200°C, more preferably of 140–180°C, and particularly preferably of 140–170°C. In this invention, the glass transition temperature can be measured by the method described in the embodiments below.

[0207] (4) Converted weight-average molecular weight of polystyrene (Mw)

[0208] In one embodiment of the present invention, the equivalent weight-average molecular weight of the thermoplastic resin polystyrene is preferably 10,000 to 200,000, more preferably 10,000 to 100,000, and particularly preferably 10,000 to 80,000.

[0209] <Thermoplastic Resin Composition>

[0210] Another embodiment of the present invention is a thermoplastic resin composition containing the above-described thermoplastic resin and additives. The thermoplastic resin composition of this embodiment can be used with resins other than the thermoplastic resin of the present invention containing structural unit (A), without compromising the intended effects of this embodiment. Such resins are not particularly limited, and examples include at least one resin selected from polycarbonate resins, polyester resins, polyester carbonate 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 products can be used with these resins, and one or more can be added to the thermoplastic resin composition alone or in combination.

[0211] [Antioxidants]

[0212] Thermoplastic resin compositions preferably contain antioxidants as additives.

[0213] As an antioxidant, it is preferred to contain at least one of phenolic antioxidants and phosphite antioxidants.

[0214] Examples of phenolic antioxidants include 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-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-methylpropionyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidene di-m-cresol, and 3-(3,5-di-tert-butyl-4- Octadecyl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] pentaerythritol ester, 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 tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] pentaerythritol ester, etc., preferably pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0215] Examples of phosphite antioxidants include 2-ethylhexyl diphenyl phosphite, isodeyl diphenyl phosphite, triisodecyl phosphite, triphenyl phosphite, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxy-3,9-diphosspiro[5.5]undecane, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosspiro[5.5]undecane, and 2,2'-methylenebis(4,6-di-tert-butylphenyl)2-ethylhexyl Phosphite, tris(2,4-di-tert-butyl) phosphite, tris(nonylphenyl) phosphite, tetra-C12-15 alkyl(propane-2,2-diacylbis(4,1-phenylene)) bisphosphite, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosspiro[5.5]undecane, etc., preferably 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosspiro[5.5]undecane.

[0216] As antioxidants, any one of the above can be used alone, or a mixture of two or more can be used.

[0217] In the thermoplastic resin composition, the antioxidant is preferably present at a concentration of 1 ppm to 3000 ppm by weight, based on the total weight of the resin composition. More preferably, the antioxidant content in the thermoplastic resin composition is 50 ppm to 2500 ppm by weight, further preferably 100 ppm to 2000 ppm by weight, particularly preferably 150 ppm to 1500 ppm by weight, and even more preferably 200 ppm to 1200 ppm by weight.

[0218] [Mold Release Agent]

[0219] Thermoplastic resin compositions preferably contain a mold release agent as an additive.

[0220] Examples of release agents include ester compounds, such as glycerol monoglycerides, diglycerides, and other fatty acid glycerides of glycerol fatty acids; propylene glycol fatty acid esters, sorbitol fatty acid esters, and other diol fatty acid esters; higher alcohol fatty acid esters; and full esters or monofatty acid esters of aliphatic polyols and aliphatic carboxylic acids. When using esters of aliphatic polyols and aliphatic carboxylic acids as release agents, any of the monoesters, full esters, etc., can be used, but esters other than full esters, such as monoesters, are also acceptable.

[0221] Specific examples of mold release agents include the following substances.

[0222] That is, sorbitol fatty acid esters such as sorbitol stearate, sorbitol laurate, sorbitol oleate, sorbitol trioleate, sorbitol trisorheate, sorbitol stearate, sorbitol tristearate, and sorbitol caprylate;

[0223] Propylene glycol fatty acid esters such as propylene glycol monostearate, propylene glycol monooleate, propylene glycol monobehenate, propylene glycol monolaurate, and propylene glycol monopalmitate;

[0224] Higher alcohol fatty acid esters such as stearyl stearate; including glyceryl monostearate, glyceryl mono-12-hydroxy stearate, glyceryl monooleate, glyceryl mono-behenate, glyceryl mono-caprylate, glyceryl mono-decanoate, glyceryl monolaurate, and other glyceryl mono / distearate, glyceryl mono / distearate, glyceryl mono / dibehenate, glyceryl mono / dioleate, and other glyceryl mono / diesters of fatty acid esters.

[0225] Glyceryl diacetyl monolaurate and other glycerol fatty acid esters; acetylated monoglycerides.

[0226] Citric acid fatty acid monoglycerides, succinic acid fatty acid monoglycerides, diacetyl tartaric acid fatty acid monoglycerides, and other glycerol fatty acid monoglycerides; stearic acid diglycerides, lauric acid diglycerides, oleic acid diglycerides, monostearic acid diglycerides, monolauric acid diglycerides, monomyristic acid diglycerides, monooleic acid diglycerides, tetrastearic acid, decalauric acid, decalauric acid, polyglycerol polyricinoleate, and other polyglycerol fatty acid esters.

[0227] In the thermoplastic resin composition, the mold release agent preferably contains 1 to 5000 ppm by weight based on the total weight of the resin composition. More preferably, the mold release agent content in the thermoplastic resin composition is 50 to 4000 ppm by weight, further preferably 100 to 3500 ppm by weight, particularly preferably 500 to 13000 ppm by weight, and even more preferably 1000 to 2500 ppm by weight.

[0228] [Other Additives]

[0229] In addition to the antioxidants and release agents mentioned above, other additives may be added to the thermoplastic resin composition. Examples of additives that may be included in the thermoplastic resin composition include compounding agents, catalyst deactivators, heat stabilizers, plasticizers, fillers, ultraviolet absorbers, rust inhibitors, dispersants, defoamers, leveling agents, flame retardants, lubricants, dyes, pigments, blue light agents, nucleating agents, clarifying agents, etc.

[0230] 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.

[0231] The aforementioned additives may have an adverse effect on transmittance, so it is preferable not to add them in excess; for example, the total amount added should be within the range mentioned above.

[0232] Furthermore, another embodiment of the present invention is a thermoplastic resin composition containing a modifier and a thermoplastic resin represented by the following general formula (1).

[0233]

[0234] In general formula (1), R 1 The meaning of ring A is the same as in general formula (1) above. That is, the novel cyclic diol compound represented by general formula (1) can also be used as a modifier.

[0235] In one embodiment of the present invention, the modifier is formulated in a ratio of thermoplastic resin to modifier of 99.9:0.1 to 70:30 by mass. Preferably, the mass ratio is 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, when the mass ratio of thermoplastic resin to modifier is within the above range, a resin composition with high fluidity and good moldability can be provided.

[0236] <Optical Components>

[0237] The thermoplastic resin or thermoplastic resin composition of the present invention (hereinafter referred to as "resin composition") is applicable to 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 cards, sheets, films, optical fibers, lenses, prisms, optical films, bases, filters, hard coatings, etc. Because the resin composition of the present invention has high fluidity, it 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 another preferred embodiment of the present invention, the optical component manufactured using the resin composition of the present invention can be an optical film.

[0238] When manufacturing optical components containing the resin composition of the present invention by injection molding, it is preferable to mold at a barrel temperature of 260–350°C and a mold temperature of 90–170°C. More preferably, it is preferable to mold 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 will undergo decomposition and coloring; when it is below 260°C, the melt viscosity is likely to increase, leading to molding difficulties. In addition, when the mold temperature is above 170°C, it is likely that the molded part made of the resin composition will be difficult to remove from the mold. On the other hand, when the mold temperature is below 90°C, the resin will cure prematurely in the mold during the molding process, making it difficult to control the shape of the molded part or to fully transfer the shape attached to the mold.

[0239] <Optical Lenses>

[0240] In one embodiment of the present invention, the resin composition can be used for optical lenses. Optical lenses manufactured using the resin composition of the present invention have high refractive index and good heat resistance, and therefore can be used in fields such as telescopes, binoculars, and television projectors where expensive high-refractive-index glass lenses have traditionally been used.

[0241] For example, in the case of a smartphone lens, a lens molded from thermoplastic resin containing structural unit (A) can be stacked with a lens molded from resin containing any structural unit of formula (II-1) to (II-4) or from resin containing structural units of monomers from any of the following formulas, and used as a lens unit.

[0242]

[0243] In the above formula, R1 and R2 independently represent hydrogen atoms, methyl or ethyl, and R3 and R4 independently represent hydrogen atoms, methyl, ethyl or alkylene glycols with 2 to 5 carbon atoms.

[0244] The optical lens of this invention can be implemented using an aspherical lens, depending on the requirements. Since an aspherical lens can achieve essentially zero spherical aberration with a single lens, it eliminates the need to combine multiple spherical lenses to eliminate spherical aberration, enabling lightweight construction and reduced manufacturing costs. Therefore, aspherical lenses are particularly useful as camera lenses among optical lenses.

[0245] Furthermore, due to the high molding fluidity of the optical lens of the present invention, it is particularly useful as a material for thin, 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. Additionally, 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, the shape is preferably a meniscus lens with one convex and one concave side.

[0246] 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 more preferred from the perspective of manufacturing cost.

[0247] <Optical film>

[0248] In one embodiment of the present invention, the resin composition can be used for optical films. In particular, optical films made using the polycarbonate resin of the present invention have excellent transparency and heat resistance, and are therefore suitable for films for liquid crystal substrates, optical memory cards, etc.

[0249] To minimize the incorporation 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.

[0250] Example

[0251] Comparative examples are given below along with embodiments of the present invention to illustrate the invention in detail, but the present invention is not limited to these embodiments.

[0252] <Compounds Used>

[0253] m-Phenylbenzaldehyde: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0254] terephthalaldehyde: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0255] Phthalate: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0256] p-Toluenesulfonic acid monohydrate: manufactured by NACALAI TESQUE Co., Ltd.

[0257] Trimethylolethane and Trimethylolpropane: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0258] Bisphenoxyethanol fluorene (BPEF): Manufactured by Tokyo Chemical Industry Co., Ltd.

[0259] Diphenyl carbonate: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0260] Gas Chromatography (GC) Analysis

[0261] The purity of the cyclic diol compound was determined by gas chromatography (GC) analysis under the following conditions and methods, and by the area percentage method.

[0262] (Sample preparation)

[0263] Add 50 ml of methanol to 0.5 g of the cyclic diol compound and shake well at room temperature to prepare a methanol solution of the cyclic diol compound, which can be used as an analytical sample.

[0264] [Measurement Conditions]

[0265] Instrument: Shimadzu Corporation GC-2020

[0266] Chromatographic column: DB-1 30m × 0.25mm × 0.25μm manufactured by Agilent Technologies, Inc.

[0267] Column temperature: 80℃ (residence time 5 min) — heating rate 10℃ / min — 320℃ (residence time 5 min)

[0268] Injection temperature / detector temperature: 300℃ / 325℃

[0269] Flow split ratio: 30

[0270] Column flow rate: 1.17 ml / min

[0271] Purge flow rate: 10.0 ml / min

[0272] Detector: FID

[0273] Carrier gas: Helium

[0274] Airflow velocity: 30cm / sec

[0275] Injection volume: 1 μl

[0276] Melting point

[0277] The melting point of the cyclic diol compound was measured using a differential calorimeter (DSC6220) manufactured by SII Nanotechnology. A 10.7 mg sample was placed in an aluminum pot manufactured by SII Nanotechnology and sealed. Under a nitrogen flow of 50 ml / min, the temperature was increased from 30 °C to 200 °C at a rate of 10 °C / min, and the endothermic peak was observed. The temperature indicated by the peak was taken as the melting point.

[0278] Infrared Absorption Spectroscopy (IR Spectroscopy)

[0279] The IR spectra of the cyclic diol compounds were obtained using an infrared spectrometer (Spectrum 400 manufactured by Perkinelmer Japan Co., Ltd.) via the ATR (attenuated total reflectance) method.

[0280] <Refractive index (nD)>

[0281] According to JIS B 7071-2∶2018, polycarbonate resin was molded into V-shaped blocks, which were used as samples. The temperature was measured using a refractometer (Shimadzu KPR-3,000) at 23°C.

[0282] <Abbe number (ν)>

[0283] Using the same specimen (V-block) as the specimen used for 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.

[0284] ν=(nD-1) / (nF-nC)

[0285] nD: Refractive index at wavelength 589nm

[0286] nC: Refractive index at a wavelength of 656 nm

[0287] nF: Refractive index at wavelength 486nm

[0288] Glass transition temperature (Tg)

[0289] Measurements were taken using a differential scanning calorimeter (Hitachi High Technology Corporation X-DSC7000) based on JIS K7121-1987, with a heating program of 10°C / min.

[0290] <Weight-average molecular weight (Mw)>

[0291] The weight-average molecular weight of the resin was measured by gel permeation chromatography (GPC) and calculated based on standard polystyrene. The apparatus, column, and measurement conditions used are shown below.

[0292] GPC device: HLC-8420GPC manufactured by Tosoh Co., Ltd.

[0293] Chromatographic column: 3 TSKgel SuperHM-M columns manufactured by Tosoh Corporation

[0294] TSKgel guardcolumn SuperH-H × 1 piece made by Tosoh Co., Ltd.

[0295] TSKgel SuperH-RC made by Tosoh Co., Ltd. × 1 piece

[0296] Detector: RI detector

[0297] Standard Polystyrene: Tosoh Corporation Standard Polystyrene Reagent Kit PStQuick C

[0298] Sample solution: 0.2% by mass tetrahydrofuran solution

[0299] After filtering with a syringe filter (GL Chromatography Disc manufactured by GL Science Co., Ltd., pore size: 0.45 μm), the solution was injected into the chromatographic column.

[0300] Eluent: Tetrahydrofuran

[0301] Eluent flow rate: 0.6 mL / min

[0302] Column temperature: 40℃

[0303] [Synthesis example 1]

[0304] 13.4 g (0.1 mol) of isophthalaldehyde, 0.67 g of p-toluenesulfonic acid monohydrate, 26.4 g (0.22 mol) of trimethylolethane, 60 ml of toluene, and 60 ml of N,N-dimethylformamide were added to a 500 mL four-necked flask equipped with a stirrer, thermometer, and a Dean Stark separatory distillation receiver with a cooling tube. The mixture was then heated and stirred under reflux for approximately 6 hours while the generated water was being expelled. The reaction mixture was brought to room temperature, neutralized with 1 g of triethylamine, and 59 ml of toluene was removed by distillation under reduced pressure. Then, 100 g of ion-exchanged water was added, and the mixture was cooled with ice water. The resulting crystals were filtered, and the crystals were first washed twice with 50 ml of ion-exchanged water, then twice with 100 ml of 60 °C hot water, and finally twice with 50 ml of ion-exchanged water. The wet crystals were dried under reduced pressure at 80°C to obtain 26.7 g (0.08 mol) of isophthalaldehyde trimethylolethane diacetal with a purity of 99.7 GC area%. The melting point of the crystals was 165.9°C.

[0305] The obtained isophthalaldehyde trihydroxymethyl ethane diacetal was confirmed by IR spectroscopy.

[0306] IR (cm) ﹣1 )∶653,690,714,803,891,962,982,1007,1024,1043,1100,1164,1378,2866,2955,3349

[0307] [Synthesis example 2]

[0308] 13.4 g (0.1 mol) of isophthalaldehyde, 0.67 g of p-toluenesulfonic acid monohydrate, 29.5 g (0.22 mol) of trimethylolpropane, 60 ml of toluene, and 60 ml of N,N-dimethylformamide were added to a 500 mL four-necked flask equipped with a stirrer, thermometer, and a separating distillation receiving tube with a cooling tube. The mixture was then heated and stirred under reflux for approximately 8 hours while the generated water was being expelled. The reaction mixture was brought to room temperature, neutralized with 1 g of triethylamine, and then distilled off 60 ml of toluene under reduced pressure. 150 g of ion-exchanged water was added, and the mixture was cooled with ice water. The resulting crystals were filtered, and the crystals were first washed twice with 50 ml of ion-exchanged water, then twice with 100 ml of 60 °C hot water, and finally twice with 50 ml of ion-exchanged water. The wet crystals were dried under reduced pressure at 80 °C to obtain isophthalaldehyde trimethylolpropane diacetal with a purity of 92.7 GC area%. The generated crystals were dissolved in 60g of isopropanol by heating. After removing 40g of isopropanol by distillation, 100ml of water was added. The precipitated crystals were filtered out, washed twice with 50ml of deionized water, and dried under reduced pressure at 80℃ to obtain 27.0g (0.07mol) of isophthalaldehyde trimethylolpropane diacetal with a purity of 98.5 GC area%. The melting point of the crystals was 95.5℃.

[0309] The obtained isophthalaldehyde trimethylolpropane diacetal was confirmed by IR spectroscopy.

[0310] IR (cm) ﹣1 )∶712,803,933,971,1030,1101,1165,1377,2859,2962,3374

[0311] [Synthesis example 3]

[0312] 13.4 g (0.1 mol) of terephthalaldehyde, 0.67 g of p-toluenesulfonic acid monohydrate, 26.4 g (0.22 mol) of trimethylolethane, 60 ml of toluene, and 60 ml of N,N-dimethylformamide were added to a 500 mL four-necked flask equipped with a stirrer, thermometer, and a separating distillation receiving tube with a cooling tube. The mixture was then heated and stirred under reflux for approximately 6 hours while the generated water was being expelled. The reaction mixture was brought to room temperature, neutralized with 1 g of triethylamine, and then distilled off 50 ml of toluene under reduced pressure. 100 g of ion-exchanged water was added, and the mixture was cooled with ice water. The resulting crystals were filtered, and the crystals were first washed twice with 50 ml of ion-exchanged water and then twice with 50 ml of 60 °C hot water. The wet crystals were dried under reduced pressure at 100 °C to obtain 30.4 g (0.09 mol) of terephthalaldehyde trimethylolethane diacetate with a purity of 99.7 GC area%. The crystal has a melting point of 247.3℃.

[0313] The obtained terephthalaldehyde trimethylolethane diacetal was confirmed by IR spectroscopy.

[0314] IR (cm) ﹣1 )∶656,778,804,918,964,977,993,1016,1042,1094,1374,2844,2933,2959,3413

[0315] [Synthesis example 4]

[0316] 13.4 g (0.1 mol) of terephthalaldehyde, 0.67 g of p-toluenesulfonic acid monohydrate, 26.4 g (0.2 mol) of trimethylolpropane, 60 ml of toluene, and 60 ml of N,N-dimethylformamide were added to a 500 mL four-necked flask equipped with a stirrer, thermometer, and a separating distillation receiving tube with a cooling tube. The mixture was then heated and stirred under reflux for approximately 10 hours while the generated water was being expelled. The reaction mixture was brought to room temperature, neutralized with 1 g of triethylamine, and then distilled off 50 ml of toluene under reduced pressure. 150 g of ion-exchanged water was added, and the mixture was cooled with ice water. The resulting crystals were filtered, and the crystals were first washed twice with 50 ml of ion-exchanged water, and then twice with 50 ml of 60 °C hot water. The wet crystals were dried under reduced pressure at 100 °C to obtain terephthalaldehyde trimethylolpropane diacetal with a purity of 96.9 GC area%. 140 g of isopropanol was added to the obtained crystals and heated to dissolve them. After removing the isopropanol by distillation, the precipitated crystals were filtered out and rinsed twice with 50 ml of deionized water. The wet crystals were then dried under reduced pressure at 100 °C to obtain 30.0 g (0.08 mol) of terephthalaldehyde trimethylolpropane diacetal with a purity of 97.0 GC area%. The melting point of the crystals was 187.2 °C.

[0317] The obtained terephthalaldehyde trimethylolpropane diacetal was confirmed by IR spectroscopy.

[0318] IR (cm) ﹣1 )∶801,971,1000,1018,1099,1379,2855,2928,2967,3355

[0319] [Synthesis example 5]

[0320] To a 1000 mL four-necked flask equipped with a stirrer, thermometer, and a separating distillation receiving tube with a cooling tube, 40.2 g (0.3 mol) of o-phthalaldehyde, 1.0 g of p-toluenesulfonic acid monohydrate, 75.6 g (0.63 mol) of trimethylolethane, 180 mL of xylene, and 180 mL of N-methylpyrrolidone were added. The mixture was then heated and stirred under reflux for approximately 4 hours while the generated water was being drained. After removing 170 mL of xylene by distillation under reduced pressure, the reaction mixture was brought to room temperature, neutralized with 25 mL of saturated sodium bicarbonate, and then 400 g of deionized water was added. 100 mL of ethyl acetate was then added, and the organic layer was separated from the aqueous layer using a separatory funnel. Another 100 mL of ethyl acetate was added to the separated aqueous layer. This process of separating the organic layer from the aqueous layer and obtaining the aqueous layer was repeated twice. The resulting organic layer was treated with a rotary evaporator to concentrate the organic layer, yielding 90.2 g (0.27 mol) of phthalaldehyde trimethylolethane diacetal with a purity of 99.2% (GC area percentage).

[0321] The obtained phthalaldehyde trimethylolethane diacetal was confirmed by IR spectroscopy.

[0322] IR (cm) ﹣1 )∶663,698,760,920,948,969,1003,1021,1042,1082,1099,1203,1386,1455,2850,2955,3414

[0323] (Example 1)

[0324] As raw materials, 22.6470 g (0.0516 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF) represented by the following structural formula, 7.4982 g (0.0222 mol) of isophthalaldehyde trimethylolethane diacetate obtained in Synthesis Example 1 (hereinafter referred to as Compound 1), 16.2833 g (0.0760 mol) of diphenyl carbonate (DPC), and 0.6201 × 10⁻⁶ sodium bicarbonate were used. ﹣4 g(0.7381×10 ﹣6The esterification reaction was initiated by adding mol of the ester (polycarbonate) into a 300 mL reactor equipped with a stirrer and distillation apparatus, and setting the system to a nitrogen atmosphere of 101.3 kPa. The reactor was then immersed in an oil bath heated to 200 °C to begin the esterification 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 a period of 10 minutes. While reducing the pressure, the temperature was raised to 210 °C. After 60 minutes, the temperature was raised to 220 °C. After 80 minutes, the pressure was reduced to 20.00 kPa over a period of 10 minutes. The temperature was then raised to 240 °C while reducing the pressure to 0 kPa. This state was maintained for 30 minutes. Nitrogen gas was then introduced into the reaction system to restore the pressure to 101.3 kPa, yielding polycarbonate resin.

[0325] The resulting polycarbonate resin has a refractive index of 1.6125, an Abbe number of 25.98, a Tg of 142℃, and a polystyrene equivalent weight-average molecular weight (Mw) of 34459. The content of the diol compounds used as raw materials and the physical properties of the resulting resin are shown in Table 1 below.

[0326] (Example 2)

[0327] In addition to using compound 1 (24.9709 g, 0.0738 mol), diphenyl carbonate (DPC) (16.2833 g, 0.0760 mol), and sodium bicarbonate (0.6201 × 10⁻⁶) as raw materials, the other components used were also compound 1 (24.9709 g, 0.0738 mol), diphenyl carbonate (DPC) (16.2833 g, ﹣4 g(0.7381×10 ﹣6 Except for (mol), the process was carried out in the same manner as in Example 1 to obtain polycarbonate resin.

[0328] The resulting polycarbonate resin has a refractive index of 1.536, an Abbe number of 38.01, a Tg of 134℃, and a polystyrene equivalent weight-average molecular weight (Mw) of 34425. The content of the diol compounds used as raw materials and the physical properties of the resulting resin are shown in Table 1 below.

[0329] (Example 3)

[0330] As raw materials, 20.9233 g (0.0477 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF) represented by the following structural formula, 6.9132 g (0.0204 mol) of terephthalaldehyde trimethylolethane diacetate obtained in Synthesis Example 3 (hereinafter referred to as Compound 2), 15.0581 g (0.0703 mol) of diphenyl carbonate (DPC), and 0.5725 × 10⁻⁶ sodium bicarbonate were used. ﹣4 g(0.6814×10 ﹣6The esterification reaction was initiated by adding mol of the ester (polycarbonate) into a 300 mL reactor equipped with a stirrer and distillation apparatus, and setting the system to a nitrogen atmosphere of 101.3 kPa. The reactor was then immersed in an oil bath heated to 200 °C to begin the esterification 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 a period of 10 minutes. While reducing the pressure, the temperature was raised to 210 °C. After 70 minutes, the temperature was raised to 220 °C. After 90 minutes, the pressure was reduced to 20.00 kPa over a period of 10 minutes. The temperature was then raised to 240 °C while reducing the pressure to 0 kPa. This state was maintained for 30 minutes. Nitrogen gas was then introduced into the reaction system to restore the pressure to 101.3 kPa, yielding polycarbonate resin.

[0331] The resulting polycarbonate resin has a refractive index of 1.6095, an Abbe number of 26.09, a Tg of 153℃, and a polystyrene equivalent weight-average molecular weight (Mw) of 16844. The content of the diol compounds used as raw materials and the physical properties of the resulting resin are shown in Table 1 below.

[0332] (Example 4)

[0333] Except for the amounts shown in Table 1 below, polycarbonate resin was obtained in the same manner as in Example 3. The physical properties of the resulting resin are shown in Table 1 below.

[0334] (Comparative Example 1)

[0335] In addition to being used as raw materials, 42.5953 g (0.0971 mol) of BPEF, 12.6658 g (0.0416 mol) of spirodiol (3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane) (SPG) represented by the following structural formula, 30.6188 g (0.1429 mol) of DPC and 1.1656 × 10⁻⁶ sodium bicarbonate were used. ﹣4 g(1.3874×10 ﹣6 Except for (mol), the process was carried out in the same manner as in Example 1 to obtain polycarbonate resin.

[0336] The resulting 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 the diol compounds used as raw materials and the physical properties of the resulting resin are shown in Table 1 below.

[0337] (Comparative Example 2)

[0338] In addition to being used as raw materials, 42.2300 g (0.0416 mol) of spirodiol (3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane) (SPG), 30.6188 g (0.1429 mol) of DPC and 1.1656 × 10⁻⁶ sodium bicarbonate were used. ﹣4 g(1.3874×10 ﹣6 Apart from mol), the same procedure as in Example 1 was performed, and the reaction was attempted, but crystals formed during the reaction, and polycarbonate resin was not obtained.

[0339] BPEF

[0340]

[0341] Spirodiol (SPG)

[0342]

[0343] Compound 1: isophthalaldehyde, tris(hydroxymethyl)ethane, diacetal

[0344]

[0345] Compound 2: terephthalaldehyde, tris(hydroxymethyl)ethane, diacetal

[0346]

[0347] [Table 1]

[0348]

[0349] *After preparing the sample solution, the presence of insoluble matter was visually confirmed. Since the solution was injected into the column using a syringe filter (GL chromatographic disk manufactured by GL Science Co., Ltd., pore size: 0.45 μm), only data for the dissolved portion are available.

Claims

1. A thermoplastic resin, characterized in that, Structural unit (A) containing a monomer represented by the following general formula (1), The thermoplastic resin is selected from polyester resin, polycarbonate resin, or polyester-carbonate resin. In the formula, R 1 "Identical" or "different" respectively refers to a hydrogen atom, fluorine atom, chlorine atom, bromine atom, phenyl, or a straight-chain or branched alkyl group having 1 to 4 carbon atoms; ring A represents a benzene ring that can be substituted by 1 to 4 groups selected from fluorine atom, chlorine atom, bromine atom, phenyl, straight-chain or branched alkoxy group having 1 to 6 carbon atoms, and straight-chain or branched alkyl group having 1 to 6 carbon atoms.

2. The thermoplastic resin according to claim 1, characterized in that, The thermoplastic resin is a polycarbonate resin or a polyester carbonate resin.

3. The thermoplastic resin as described in claim 1 or 2, characterized in that, In the general formula (1) R 1 They may be the same or different, namely methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or phenyl.

4. The thermoplastic resin according to claim 3, characterized in that, In the general formula (1), R 1 They are the same or different, namely methyl or ethyl.

5. The thermoplastic resin as described in claim 1 or 2, characterized in that, In the general formula (1), ring A is a benzene ring that can be substituted by 1 to 4 groups selected from straight-chain or branched alkoxy groups having 1 to 6 carbon atoms and straight-chain or branched alkyl groups having 1 to 6 carbon atoms.

6. The thermoplastic resin according to claim 1 or 2, characterized in that, In the general formula (1), R 1 It is methyl or ethyl, and ring A is a benzene ring that can be substituted by 1 to 4 groups selected from methyl and ethyl.

7. The thermoplastic resin according to claim 1 or 2, characterized in that, The monomer represented by the general formula (1) is the monomer represented by the following general formula (1a). In the formula, R 2 The same or different, respectively representing hydrogen atom, fluorine atom, chlorine atom, bromine atom, phenyl, straight-chain or branched alkoxy group having 1 to 6 carbon atoms, or straight-chain or branched alkyl group having 1 to 6 carbon atoms, R 1 The meaning is the same as above.

8. The thermoplastic resin according to claim 1 or 2, characterized in that, The monomer represented by the general formula (1) is the monomer represented by the following general formula (1b). In the formula, R 2 The same or different, respectively representing hydrogen atom, fluorine atom, chlorine atom, bromine atom, phenyl, straight-chain or branched alkoxy group having 1 to 6 carbon atoms, or straight-chain or branched alkyl group having 1 to 6 carbon atoms, R 1 The meaning is the same as above.

9. The thermoplastic resin according to claim 1 or 2, characterized in that, The monomer represented by the general formula (1) is the monomer represented by the following general formula (1c). In the formula, R 2 The same or different, respectively representing hydrogen atom, fluorine atom, chlorine atom, bromine atom, phenyl, straight-chain or branched alkoxy group having 1 to 6 carbon atoms, or straight-chain or branched alkyl group having 1 to 6 carbon atoms, R 1 The meaning is the same as above.

10. The thermoplastic resin according to claim 1 or 2, characterized in that, The thermoplastic resin contains structural units (B) derived from monomers represented by the following general formula (2) and / or structural units (C) derived from monomers represented by the following general formula (3). In equation (2), R a and R b The elements are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, aryl groups having 6 to 20 carbon atoms that may have substituents, heteroaryl groups having 6 to 20 carbon atoms that may have substituents containing one or more heterocyclic atoms selected from O, N, and S, aryloxy groups having 6 to 20 carbon atoms that may have substituents, and -C≡CR. h , R h This indicates an aryl group with 6 to 20 carbon atoms that may have substituents, or a heteroaryl group with 6 to 20 carbon atoms that may have substituents and contains one or more heterocyclic atoms selected from O, N, and S. X represents a single bond or a fluorene group that may have substituents. A and B independently represent alkylene groups with 1 to 5 carbon atoms that can have substituents. m and n independently represent integers from 0 to 6. a and b represent integers from 0 to 10 independently; In equation (3), R c and R d The groups are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, and aryl groups having 6 to 20 carbon atoms that may have substituents. Y1 is a single bond, a fluorene group that may have substituents, or any of the structural formulas represented by the following formulas (4) to (10). In equations (4) to (10), R 61 R 62 R 71 and R 72 Each can independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 20 carbon atoms that may have substituents, or an aryl group with 6 to 30 carbon atoms that may have substituents, or represent R. 61 and R 62 Or R 71 and R 72 Carbon rings or heterocycles with 1 to 20 carbon atoms that are bonded together can have substituents. r and s independently represent integers from 0 to 5000. A and B independently represent alkylene groups with 1 to 5 carbon atoms that can have substituents. p and q represent integers from 0 to 4 independently. a and b represent integers from 0 to 10 independently.

11. The thermoplastic resin according to claim 10, characterized in that, In formulas (2) and (3), A and B independently represent alkylene groups with 2 or 3 carbon atoms, respectively.

12. The thermoplastic resin according to claim 10, characterized in that, The thermoplastic resin contains at least structural units from any one of BPEF, BNE, BNEF, and DPBHBNA.

13. The thermoplastic resin according to claim 1 or 2, characterized in that, The thermoplastic resin further contains structural units derived from at least one monomer selected from the group consisting of the following monomers: In the above formula, R1 and R2 independently represent hydrogen atoms, methyl or ethyl, and R3 and R4 independently represent hydrogen atoms, methyl, ethyl or alkylene glycols with 2 to 5 carbon atoms.

14. The thermoplastic resin according to claim 1 or 2, characterized in that, The thermoplastic resin has a weight-average molecular weight (Mw) of 10,000 to 200,000 when converted to polystyrene.

15. The thermoplastic resin according to claim 1 or 2, characterized in that, The refractive index nD of the thermoplastic resin is 1.599 to 1.

750.

16. The thermoplastic resin according to claim 1 or 2, characterized in that, The Abbe number ν of the thermoplastic resin is 25.0 to 33.

0.

17. The thermoplastic resin according to claim 1 or 2, characterized in that, The glass transition temperature of the thermoplastic resin is 135–200°C.

18. An optical component, characterized in that, It contains the thermoplastic resin as described in any one of claims 1 to 17.

19. An optical lens, characterized in that, It contains the thermoplastic resin as described in any one of claims 1 to 17.

20. An optical film, characterized in that, It contains the thermoplastic resin as described in any one of claims 1 to 17.

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