Thermoplastic resin and molded body containing thermoplastic resin

Abstract

Provided are: a thermoplastic resin which is excellent in terms of properties required in optical applications and the like, such as refractive index and chromatic aberration; and a molded body containing this type of thermoplastic resin.　The following thermoplastic resin can be given as an example of a means for solving the problem mentioned above. This thermoplastic resin contains a silane constituent unit (S), an ester constituent unit (I) and a diol constituent unit (A). The silane constituent unit (S) is derived from any of a diaryldialkoxysilane, a diaryldiaryloxysilane or a diarylmonoalkoxymonoaryloxysilane. The ester constituent unit (I) is derived from any of a dicarboxylic acid represented by any of general formulae (1) to (6) shown in the description of the present application, a monocarboxylic acid monoester or a carboxylic acid diester. The diol constituent unit (A) is derived from any of a diol compound represented by general formulae (7) to (10) shown in the description of the present application.

Description

Thermoplastic resin and molded article containing thermoplastic resin

[0001] The present invention relates to a thermoplastic resin, particularly a thermoplastic resin containing a structural unit derived from a specific compound such as a silane compound, and a molded article containing the thermoplastic resin.

[0002] BACKGROUND ART Conventionally, various thermoplastic resins have been used in a wide range of fields. Thermoplastic resins are formed into various molded articles by techniques such as injection molding, and are used in a wide range of industrial fields, such as electrical and electronic equipment, office automation equipment, heavy electrical machinery, precision machinery, and automotive fields.

[0003] Aromatic polysiloxane polymers, also known as polyarylenesiloxanes, are known as thermoplastic resins used as materials for molded articles (see, for example, Patent Documents 1 and 2). In recent years, the importance of polysiloxane compounds such as polyarylenesiloxanes has increased, and polyarylenesiloxanes are used, for example, as release layers in photocopying, photoresist materials, plasticizers for resins such as polycarbonate resins, and components of powder surface coating systems.

[0004] Special table No. 08-502537 Publication No. 2015-512999

[0005] Conventional thermoplastic resins do not necessarily have properties suitable for specific applications, and thermoplastic resins with excellent properties are needed as materials for molded products in optical applications, etc. For example, thermoplastic resins used in optical applications generally need to have high refractive indexes and Abbe numbers, as well as suppressed chromatic aberration, but thermoplastic resins with sufficiently low chromatic aberration have not been easily achieved, at least.

[0006] Thus, there is a demand for new thermoplastic resins that have excellent properties in terms of optical applications, such as refractive index, Abbe number, and chromatic aberration.

[0007] The present invention relates to, for example, the following thermoplastic resins and molded articles containing the thermoplastic resins: [1] A thermoplastic resin having a silane structural unit (S), an ester structural unit (I), and a diol structural unit (A), wherein the silane structural unit (S) is derived from any of silane compounds including a diaryldialkoxysilane, a diaryldiaryloxysilane, and a diarylmonoalkoxymonoaryloxysilane, and the ester structural unit (I) is derived from any of dicarboxylic acids, monocarboxylic acid monoesters, and carboxylic acid diesters represented by any of the following general formulas (1) to (6): (In general formula (1), R １ and R ２ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may have a substituent; R ａ represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and m represents an integer of 0 to 4. (In general formula (2), R １ and R ２ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent, R ａ and R ｂ each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and m and n each independently represent an integer of 0 to 3. (In general formula (3), R １ and R ２ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may have a substituent; R ａ represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and m represents an integer of 0 to 4. (In general formula (4), R ５ and R ６each independently represents a halogen atom, an alkyl group which may have a substituent, or an aryl group; a and b each independently represent an integer of 0 to 4; R ７ and R ８ each independently represents a C1-8 alkylene group which may have a substituent; c and d each independently represent an integer of 1 to 5; R ９ and R １０ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent. (In general formula (5), R １１ each independently represents an alkylene group having 1 to 4 carbon atoms; R １２ each independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a halogen atom; each n independently represents 0 or an integer of 1 to 4; R １３ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 4 carbon atoms which may have a substituent. (In general formula (6), R ２１ , R ２２ each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, R ２３ ~R ３０ each independently represents a hydrogen atom, an aliphatic group having 1 to 12 carbon atoms, or an aromatic group having 6 to 20 carbon atoms; a and b each independently represent an integer of 0 or more; R ３１ , R ３２ each independently represents a hydrogen atom, a methyl group, an ethyl group, or a phenyl group which may have a substituent.) A thermoplastic resin, wherein the diol structural unit (A) is derived from any of the diol compounds represented by the following general formulas (7) to (10): In general formula (7), Ra and Rb are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which contains one or more heterocyclic atoms selected from O, N, and S and which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡C-Rh, Rh represents an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more heterocyclic atoms selected from O, N, and S and which may have a substituent, X represents a single bond or a fluorene group which may have a substituent, A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent; m and n each independently represent an integer of 0 to 6; and a and b each independently represent an integer of 0 to 10. (In general formula (8), Rc and Rd are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 20 carbon atoms which may have a substituent; A and B are each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent; p and q are each independently an integer of 0 to 4; a and b are each independently an integer of 0 to 10; Y １ represents a single bond, —O—, —S—, —SO—, —SO ２ represents -, -CO-, or a divalent group represented by any one of formulas (i) to (vi). (In general formula (i), R ８ ~R １７ each independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms; in the general formulae (ii) to (vi), R １８ and R１９ each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms which may have a substituent, or １８ and R １９ are bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms; R ２０ represents an alkylene group having 1 to 9 carbon atoms which may have a substituent, c represents an integer of 0 to 20, and d represents an integer of 1 to 500. A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, p and q each independently represent an integer of 0 to 4, and a and b each independently represent an integer of 0 to 10. (In general formula (9), R ４１ and R ４２ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may have a substituent, and a represents an integer of 2 to 16. (In the general formula (10), R is H, CH ３ or C ２ H ５ Represents.)

[0008] [2] The thermoplastic resin according to the above [1], wherein the silane structural unit (S) is derived from a diaryldialkoxysilane. [3] The thermoplastic resin according to the above [1] or [2], for example, the above [2], wherein the diaryldialkoxysilane has a C6-20 aryl group which may have a substituent and a C1-8 alkoxy group which may have a substituent. [4] The thermoplastic resin according to any of the above [1] to [3], for example, the above [3], wherein the diaryldialkoxysilane is represented by the following formula (11): [5] The thermoplastic resin according to any one of [1] to [4] above, for example, the thermoplastic resin according to [1] above, wherein the content of the silane structural unit (S) is 2 to 50 mol % based on the total number of moles of all structural units in the thermoplastic resin. [6] The thermoplastic resin according to any one of [1] to [5] above, for example, the thermoplastic resin according to [1] above, wherein the content of the ester structural unit (I) is 3 to 45 mol % based on the total number of moles of all structural units in the thermoplastic resin. [7] The thermoplastic resin according to any one of [1] to [6] above, for example, the thermoplastic resin according to [1] above, wherein the content of the diol structural unit (A) is 30 to 70 mol % based on the total number of moles of all structural units in the thermoplastic resin. [8] The thermoplastic resin according to any one of [1] to [7] above, for example, the thermoplastic resin according to [1] above, wherein the ester structural unit (I) is ester-bonded to the diol structural unit (A). [9] The thermoplastic resin according to any one of [1] to [8] above, for example, [1] above, wherein the thermoplastic resin is either a polyester carbonate resin or a polyester resin.

[0009]

[10] The thermoplastic resin according to any one of [1] to [9] above, for example, the thermoplastic resin according to [1] above, wherein the silane structural unit (S) is bonded to the diol structural unit (A) via a (silyl) ether bond.

[11] The thermoplastic resin according to any one of [1] to

[10] above, for example, the thermoplastic resin according to [1] above, wherein the compound of general formula (7) includes either BNE or DPBN.

[12] The thermoplastic resin according to any one of [1] to

[11] above, for example, the thermoplastic resin according to [1] above, wherein the compound of general formula (8) includes either BNEF or BPEF.

[13] The thermoplastic resin according to any one of [1] to

[12] above, for example, the thermoplastic resin according to [1] above, wherein the compound of general formula (9) includes 1,12-dodecanediol.

[0010]

[14] The thermoplastic resin according to any one of [1] to

[13] above, for example, [1] above, wherein the general formula (1) comprises dimethyl terephthalate.

[15] The thermoplastic resin according to any one of [1] to

[14] above, for example, [1] above, wherein the general formula (2) comprises dimethyl 2,6-naphthalenedicarboxylate.

[16] The thermoplastic resin according to any one of [1] to

[15] above, for example, [1] above, wherein the general formula (4) comprises FDPM.

[17] The thermoplastic resin according to any one of [1] to

[16] above, for example, [1] above, wherein the general formula (5) comprises the following formula (12):

[18] The thermoplastic resin according to any one of [1] to

[17] above, for example, [1] above, wherein the general formula (6) includes any one of the following formulas (13) and (14):

[0011]

[19] The thermoplastic resin according to any one of [1] to

[18] above, for example, the thermoplastic resin according to [1] above, wherein θgF is 0.70 or less, or θhF is 1.40 or less.

[20] The thermoplastic resin according to any one of [1] to

[19] above, for example, the thermoplastic resin according to [1] above, wherein the weight average molecular weight (Mw) of the thermoplastic resin in terms of polystyrene is 5,000 to 100,000.

[21] The thermoplastic resin according to any one of [1] to

[20] above, for example, the thermoplastic resin according to [1] above, wherein the refractive index (nd) of the thermoplastic resin is 1.681 to 1.720.

[22] The thermoplastic resin according to any one of [1] to

[21] above, for example, the thermoplastic resin according to [1] above, wherein the Abbe number (vd) of the thermoplastic resin is 15.0 to 19.6.

[23] The thermoplastic resin according to any one of [1] to

[22] above, for example, [1] above, wherein the Tg of the thermoplastic resin is 137 to 170 ° C.

[0012]

[24] A molded article comprising any one of the above [1] to

[23] , for example, the thermoplastic resin described in the above [1].

[25] The molded article described in the above

[24] , which is an optical lens.

[0013] According to the present invention, it is possible to realize a thermoplastic resin having excellent properties such as sufficiently suppressed chromatic aberration and being particularly suitable for optical applications, and a molded article containing such a thermoplastic resin, such as an optical lens, etc. Furthermore, according to the present invention, it is possible to provide a thermoplastic resin having a high refractive index and Abbe number and being particularly suitable for optical applications.

[0014] FIG. 1 shows a powder X-ray diffraction (PXRD) measurement chart of 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthryl (a compound represented by chemical formula (12)) obtained in Example 18. The vertical axis indicates the intensity range of 0 to 30,000 (cps), and the horizontal axis indicates the 2θ range of 0 to 50 (°). FIG. 1 shows a differential scanning calorimetry (DSC) analysis chart of 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthryl (a compound represented by chemical formula (12)) obtained in Example 18.

[0015] The thermoplastic resin of the present invention contains a silane structural unit (S), an ester structural unit (I), and a diol structural unit (A). The silane structural unit (S) is a structural unit derived from a specific silane compound such as a dialkoxysilane. The ester structural unit (I) is a structural unit derived from a specific dicarboxylic acid, monocarboxylic acid monoester, or carboxylic acid diester. The diol structural unit (A) is a structural unit derived from a specific diol compound. The type of thermoplastic resin is not particularly limited, but examples include polyester resins and polyester carbonate resins. Thermoplastic resins will be described in detail below.

[0016] [I. Thermoplastic Resin] <I-1. Types of Structural Units> (1) Silane Structural Unit (S) The silane structural unit (S) in the thermoplastic resin is derived from a silane compound selected from diaryldialkoxysilane, diaryldiaryloxysilane, and diarylmonoalkoxymonoaryloxysilane. The silane compound that produces the silane structural unit (S) may be any one selected from diaryldialkoxysilane, diaryldiaryloxysilane, and diarylmonoalkoxymonoaryloxysilane, or may be a mixture of two or more of these.

[0017] The silane compound for forming the silane structural unit (S) may also be selected from monoaryl monoalkyl silane compounds, such as monoaryl monoalkyl dialkoxy silanes, monoaryl monoalkyl diaryloxy silanes, and diaryl monoalkoxy monoaryloxy silanes; and dialkyl silane compounds, such as dialkyl dialkoxy silanes, dialkyl diaryloxy silanes, and dialkyl monoalkoxy monoaryloxy silanes. As the silane compound constituting the silane structural unit (S), a single type of compound may be used, or multiple types may be used in combination as a mixture.

[0018] The silane compound is preferably a diaryldialkoxysilane. The silane compound preferably has an aryl group having 6 to 30 carbon atoms (C6-30), which may have a substituent, more preferably an aryl group having 6 to 20 carbon atoms, and even more preferably an aryl group having 6 to 12 carbon atoms. Examples of the aryl group include a naphthyl group, a phenyl group, and a benzyl group. The silane compound preferably has an alkoxy group having 1 to 8 carbon atoms (C1-8), which may have a substituent, more preferably an alkoxy group having 1 to 6 carbon atoms, and even more preferably an alkoxy group having 1 to 3 carbon atoms or 1 to 2 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propyloxy group.

[0019] Preferred examples of the above-mentioned silane compounds as raw materials for the silane structural unit (S) include dinaphthyldimethoxysilane (DNDMS: the above formula (11)), mononaphthylmonophenyldimethoxysilane, mononaphthylmonophenyldimethoxysilane, and diphenyldimethoxysilane (DPDMS).

[0020] The silane structural unit (S) is a structural unit containing a silyl ether bond moiety represented by the following formula (a), i.e., —OSi(R ｉ R ｉｉ)O-moiety. Therefore, the type of silane compound used for polymerization of the thermoplastic resin can be appropriately selected depending on the type of silane structural unit (S) formed in the main chain.

[0021] R in the above formula (a) ｉ and R ｉｉ are each independently an aryl group having 6 to 30 carbon atoms which may have a substituent, or an alkyl group having 1 to 20 carbon atoms which may have a substituent. ｉ and R ｉｉ When R is an aryl group which may have a substituent, it preferably has a total of 6 to 20 carbon atoms, more preferably has a total of 6 to 12 carbon atoms, and particularly preferably has a total of 6 to 8 carbon atoms. ｉ and R ｉｉ When the alkyl group is an alkyl group which may have a substituent, the total number of carbon atoms is preferably 1 to 14 or 1 to 10, more preferably 1 to 6, and particularly preferably 1 or 2.

[0022] Examples of the substituent in the silane structural unit (S) include a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth)acryloxy group, a glycidyloxy group, a mercapto group, etc. In addition, the alkyl group substituted in the silane structural unit (S) may also include an aryl group such as a phenyl group or a naphthyl group, and the substituent in the aryl group such as a phenyl group or a naphthyl group in the silane structural unit (S) may also include an alkyl group. Note that the number of carbon atoms in the substituted portion is the total number of carbon atoms including the number of carbon atoms in the substituent. R ｉ and R ｉｉ Preferred examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a phenyl group, and a benzyl group, and more preferred are a methyl group and a phenyl group.

[0023] The silane compound forming the silane building block (S) is selected from the group consisting of silane compounds represented by the general formula Si(R ｉ R ｉｉ ) (OR) ２When expressed as ｉ and R ｉｉ As shown in the above formula (a), R are each independently selected from an aryl group having 6 to 30 carbon atoms which may have a substituent and an alkyl group having 1 to 20 carbon atoms which may have a substituent. ｉ and R ｉｉ The preferred embodiment of is as described above.

[0024] The silane compound has the general formula Si(R ｉ R ｉｉ ) (OR) ２ The OR groups in each of the formulas independently represent either an alkoxy group or an aryloxy group. The two -OR groups, which are alkoxy groups and / or aryloxy groups in the silane compound, are not introduced into the polymer chain (main chain) of the thermoplastic resin, but rather generate by-products such as methanol and phenol (MeOH, PhOH). For this reason, the type of alkoxy group or aryloxy group is not particularly limited. However, in order to make it possible to remove by-products in the polymerization step from the reaction system as easily as possible, R contained in the -OR group is preferably an alkoxy group or aryloxy group having a relatively small number of carbon atoms, for example, an alkoxy group having 3 or less carbon atoms or an aryloxy group having 8 or less carbon atoms, and more preferably a methoxy group, an ethoxy group, or a phenoxy group (-OC ６ H ５ group), benzyloxy group, etc., and particularly preferred is a methoxy group or a phenoxy group.

[0025] (2) Ester structural unit (I) The ester structural unit (I) in the thermoplastic resin is a structural unit derived from a dicarboxylic acid, a monocarboxylic acid monoester, or a carboxylic acid diester represented by any one of the following formulas (1) to (6): The structural units of each formula are described below.

[0026] In formula (1), R １ and R ２ R each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may have a substituent. １ and R ２is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may have a substituent, and more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms which may have a substituent.

[0027] In general formula (1), R ａ represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. ａ is preferably a hydrogen atom, an alkyl group of 1 to 10 carbon atoms which may have a substituent, or an aryl group of 6 to 20 carbon atoms which may have a substituent, more preferably a hydrogen atom, an alkyl group of 1 to 5 carbon atoms which may have a substituent, or an aryl group of 6 to 10 carbon atoms which may have a substituent, and particularly preferably a hydrogen atom or an alkyl group of 1 to 3 carbon atoms which may have a substituent. In general formula (1), m is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably an integer of 0 or 1, and particularly preferably 0.

[0028] Preferred specific examples of the monomer compound for forming the ester structural unit (I) represented by formula (1) include terephthalic acid, terephthalic acid monoesters, and terephthalic acid diesters such as dimethyl terephthalate.

[0029] In formula (2), R １ and R ２ R each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may have a substituent. １ and R ２ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may have a substituent, and more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms which may have a substituent.

[0030] In general formula (2), R ａ and R ｂeach independently represents a hydrogen atom, a halogen, an optionally substituted alkyl group, or an optionally substituted aryl group, preferably a hydrogen atom, an optionally substituted alkyl group of 1 to 10 carbon atoms, or an optionally substituted aryl group of 6 to 20 carbon atoms, more preferably a hydrogen atom, an optionally substituted alkyl group of 1 to 5 carbon atoms, or an optionally substituted aryl group of 6 to 10 carbon atoms, and particularly preferably a hydrogen atom or an optionally substituted alkyl group of 1 to 3 carbon atoms. In general formula (2), m and n each independently represent an integer of 0 to 3, preferably an integer of 0 to 2, more preferably an integer of 0 or 1, and particularly preferably 0.

[0031] Specific examples of the monomer compound for forming the ester structural unit (I) represented by formula (2) include naphthalenedicarboxylic acids such as naphthalenedicarboxylic acid, naphthalenedicarboxylic acid monoesters, and naphthalenedicarboxylic acid dimethyl esters.

[0032] In general formula (3), R １ and R ２ R each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may have a substituent. １ and R ２ represents preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may have a substituent, and more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms which may have a substituent.

[0033] In general formula (3), R ａ represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. ａis preferably a hydrogen atom, an alkyl group of 1 to 10 carbon atoms which may have a substituent, or an aryl group of 6 to 20 carbon atoms which may have a substituent, more preferably a hydrogen atom, an alkyl group of 1 to 5 carbon atoms which may have a substituent, or an aryl group of 6 to 10 carbon atoms which may have a substituent, and particularly preferably a hydrogen atom or an alkyl group of 1 to 3 carbon atoms which may have a substituent. In general formula (3), m is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably an integer of 0 or 1, and particularly preferably 0.

[0034] In formula (4), R ５ and R ６ are each independently selected, i.e., may be the same or different, and are a halogen, an optionally substituted alkyl group, or an aryl group. ５ and R ６ are preferably each independently an aryl group having 6 to 20 carbon atoms which may have a substituent, or an alkyl group having 1 to 12 carbon atoms which may have a substituent, more preferably an aryl group having 6 to 12 carbon atoms or an alkyl group having 1 to 8 carbon atoms which may have a substituent, and even more preferably an aryl group having 6 to 10 carbon atoms or an alkyl group having 1 to 4 carbon atoms.

[0035] In formula (4), a and b are each independently an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. The substitution numbers a and b are each independently selected, i.e., they may be the same or different. When a and b are plural (2 or more), the R substituted on each benzene ring of the fluorene is ５ Comrades and R ６ The types may be the same or different.

[0036] R ５ and R ６The optional substituent of is not particularly limited, but is preferably a substituent that is inert to the reaction, and examples thereof include non-reactive substituents such as a cyano group, a halogen atom (such as a fluorine atom, a chlorine atom, or a bromine atom), and a hydrocarbon group [for example, an alkyl group, an aryl group, or a C6-10 aryl group such as a phenyl group], and may be a halogen atom, a cyano group, or an alkyl group (particularly an alkyl group). Examples of the alkyl group include a C1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or a t-butyl group (for example, a C1-8 alkyl group, particularly a C1-4 alkyl group such as a methyl group). R ５ and R ６ The position of the substituent may be, for example, the 2-position, the 7-position, or the 2- and 7-positions of the fluorene.

[0037] R in formula (4) ７ and R ８ are each independently a C1-8 alkylene group which may have a substituent. ７ and R ８ Examples of alkylene groups include linear or branched alkylene groups, such as C1-8 alkylene groups such as methylene, ethylene, trimethylene, propylene, 2-ethylethylene, and 2-methylpropane-1,3-diyl. Of these, preferred alkylene groups are linear or branched C1-6 alkylene groups (for example, C1-4 alkylene groups such as methylene, ethylene, trimethylene, propylene, and 2-methylpropane-1,3-diyl). In formula (4), c and d are each independently an integer of 1 to 5. c and d are preferably integers of 1 to 4, more preferably integers of 1 or 2, and even more preferably 1.

[0038] R in formula (4) ９ and R １０ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent. ９ and R １０ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may have a substituent, and more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms which may have a substituent.

[0039] Specific examples of the monomer compound for forming the ester structural unit (I) represented by formula (4) include 9,9-fluorene-dicarboxylic acid, 9,9-fluorene-dicarboxylic acid monoester, and 9,9-fluorene-dicarboxylic acid diesters such as 9,9-fluorene-methyl dipropionate (FDPM).

[0040] In formula (5), R １１ are each independently an alkylene group having 1 to 4 carbon atoms. １１ is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. １２ are each independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a halogen atom. １２ is preferably an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms or an aryl group having 6 to 10 carbon atoms. Each n in formula (5) is independently 0 or an integer of 1 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0041] R in formula (5) １３ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 4 carbon atoms. １３ is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, or an alkenyl group having 2 carbon atoms, and even more preferably a hydrogen atom or an alkyl group having 1 carbon atom.

[0042] Specific examples of the monomer compound for forming the ester structural unit (I) represented by formula (5) include the compound represented by formula (12) above, such as BIPOL-DMB.

[0043] In formula (6), R ２１ and R ２２are each independently an aromatic group or a hydrocarbon group having 1 to 12 carbon atoms which may contain a substituent. ２１ and R ２２ is preferably an alkylene group having 1 to 10 carbon atoms which may have a substituent, more preferably an alkylene group having 1 to 10 carbon atoms, even more preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably an alkylene group having 1 to 3 carbon atoms, such as a methylene group.

[0044] In formula (6), R ２３ ~R ３０ are each independently a hydrogen atom, an aliphatic group having 1 to 12 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. ２３ ~R ３０ is preferably a hydrogen atom, an aliphatic group having 1 to 8 carbon atoms, or an aromatic group having 6 to 12 carbon atoms, more preferably a hydrogen atom, an aliphatic group having 1 to 4 carbon atoms, or an aromatic group having 6 to 10 carbon atoms, and even more preferably a hydrogen atom, an aliphatic group having 1 to 2 carbon atoms, or an aromatic group having 6 to 8 carbon atoms. a and b in formula (6) are each independently an integer of 0 or more, preferably 1 or 2, and more preferably 1. R in formula (6) ３１ , R ３２ are each independently a hydrogen atom, a methyl group, an ethyl group, or a phenyl group which may have a substituent, preferably a hydrogen atom, a methyl group, or a phenyl group which may have a substituent, and more preferably a hydrogen atom or a phenyl group which may have a substituent.

[0045] Specific examples of the monomer compound for forming the ester structural unit (I) represented by formula (6) include compounds represented by the above formula (13) or (14), such as BINOL-DC and BINOL-DP. The monomer compound represented by general formula (6) may be a monocarboxylic acid monoester or diester corresponding to BINOL-DC, which is the dicarboxylic acid represented by formula (13), or a monocarboxylic acid monoester corresponding to BINOL-DP, which is the diester represented by formula (14).

[0046] Examples of the substituent in the ester structural unit (I) include a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth)acryloxy group, a glycidyloxy group, a mercapto group, and the like. The substituents on the alkyl group in the ester structural unit (I) also include aryl groups such as a phenyl group and a naphthyl group, and the substituents on the aryl group in the ester structural unit (I) also include alkyl groups. The number of carbon atoms in the substituted moiety is the total number of carbon atoms, including the number of carbon atoms in the substituent. The thermoplastic resin may contain one type of ester structural unit (I) alone, or may contain two or more types in combination.

[0047] (3) Diol Structural Unit (A) The diol structural unit (A) in the thermoplastic resin is a structural unit derived from a diol compound represented by any one of the following formulas (7) to (10): The structural units of each formula are described below.

[0048] In formula (7), Ra and Rb are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N, and S and which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡C-Rh. Ra and Rb in formula (7) are preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkoxyl group having 1 to 10 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 12 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 12 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, a heteroaryl group having 6 to 12 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, an aryloxy group having 6 to 12 carbon atoms which may have a substituent, or -C≡C-Rh.

[0049] Ra and Rb are more preferably a hydrogen atom, an alkyl group of 1 to 6 carbon atoms which may have a substituent, an alkoxyl group of 1 to 6 carbon atoms which may have a substituent, a cycloalkyl group of 5 to 8 carbon atoms which may have a substituent, a cycloalkoxyl group of 5 to 8 carbon atoms which may have a substituent, an aryl group of 6 to 10 carbon atoms which may have a substituent, a heteroaryl group of 6 to 10 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, an aryloxy group of 6 to 10 carbon atoms which may have a substituent, or -C≡C-Rh. Ra and Rb are more preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms which may have a substituent, an aryl group having 6 to 10 carbon atoms which may have a substituent, a heteroaryl group having 6 to 10 carbon atoms which contains one or more heterocyclic atoms selected from O, N and S and which may have a substituent, or -C≡C-Rh, and particularly preferably a hydrogen atom, an aryl group having 6 to 10 carbon atoms which may have a substituent, a heteroaryl group having 6 to 10 carbon atoms which contains one or more heterocyclic atoms selected from O, N and S and which may have a substituent, or -C≡C-Rh.

[0050] Rh in formula (7) is an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more heterocyclic atoms selected from O, N, and S and which may have a substituent. Rh is preferably an aryl group having 6 to 12 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 12 carbon atoms which contains one or more heterocyclic atoms selected from O, N, and S and which may have a substituent, more preferably an aryl group having 6 to 10 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 10 carbon atoms which contains one or more heterocyclic atoms selected from O, N, and S and which may have a substituent, and even more preferably an aryl group having 6 to 10 carbon atoms which may have a substituent.

[0051] X in formula (7) is a single bond or an optionally substituted fluorene group, preferably an optionally substituted fluorene group having a total of 12 to 20 carbon atoms, more preferably an optionally substituted fluorene group having a total of 12 to 16 carbon atoms. A and B in formula (7) are each independently an optionally substituted alkylene group having 1 to 5 carbon atoms, preferably an optionally substituted alkylene group having 1 to 3 carbon atoms, and even more preferably an optionally substituted alkylene group having 1 or 2 carbon atoms. m and n in formula (7) are each independently an integer of 0 to 6, preferably an integer of 0 to 3, and more preferably an integer of 0 or 1. a and b in formula (7) are each independently an integer of 0 to 10, preferably an integer of 0 to 6, more preferably an integer of 0 to 3, and even more preferably an integer of 0 or 1.

[0052] Specific examples of the monomer compound for forming the diol structural unit (A) represented by formula (7) include 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (BNE) and 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene (DPBN).

[0053] In formula (8), Rc and Rd are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. Rc and Rd in formula (8) are preferably a group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkoxyl group having 1 to 10 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 12 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 12 carbon atoms which may have a substituent, or an aryl group having 6 to 12 carbon atoms which may have a substituent.

[0054] Rc and Rd in formula (8) are more preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms which may have a substituent, an alkoxyl group having 1 to 3 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 8 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 8 carbon atoms which may have a substituent, or an aryl group having 6 to 10 carbon atoms which may have a substituent, and particularly preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms which may have a substituent, or an aryl group having 6 to 10 carbon atoms which may have a substituent.

[0055] A and B in formula (8) are each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent, preferably an alkylene group having 1 to 3 carbon atoms which may have a substituent, and more preferably an alkylene group having 1 or 2 carbon atoms which may have a substituent. p and q in formula (8) are each independently an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably an integer of 0 or 1. a and b in formula (8) are each independently an integer of 0 to 10, preferably an integer of 0 to 6, more preferably an integer of 0 to 3, and more preferably an integer of 0 or 1.

[0056] Y in formula (8) １ represents a single bond, —O—, —S—, —SO—, —SO ２ represents -, -CO-, or a divalent group represented by any one of formulas (i) to (vi). R in general formula (i) ８ ~R １７ each independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms, preferably hydrogen or an alkyl group having 1 or 2 carbon atoms, more preferably hydrogen. １８ and R １９ each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms which may have a substituent, or１８ and R １９ are bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms. In general formula (ii), c represents an integer of 0 to 20, preferably c represents an integer of 0 to 10, more preferably c represents an integer of 1 to 5, and even more preferably c represents an integer of 1 to 3.

[0057] R １８ and R １９ Preferably, R each independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 3 carbon atoms which may have a substituent, an aryl group having 6 to 10 carbon atoms which may have a substituent, an aralkyl group having 7 to 12 carbon atoms which may have a substituent, or an alkenyl group having 3 to 8 carbon atoms which may have a substituent. １８ and R １９ More preferably, each independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an aryl group having 6 to 8 carbon atoms which may have a substituent. １８ and R １９ preferably bonded to each other to form a carbocyclic ring having 6 to 12 carbon atoms or a heterocyclic ring having 6 to 12 carbon atoms, and more preferably bonded to each other to form a carbocyclic ring having 6 to 10 carbon atoms or a heterocyclic ring having 6 to 10 carbon atoms.

[0058] R in general formula (vi) ２０ is an alkylene group having 1 to 9 carbon atoms which may have a substituent, preferably an alkylene group having 1 to 6 carbon atoms which may have a substituent, more preferably an alkylene group having 1 to 3 carbon atoms which may have a substituent, and even more preferably an alkylene group having 1 or 2 carbon atoms which may have a substituent. In general formula (vi), d represents an integer of 1 to 500. Preferably, d represents an integer of 1 to 200, more preferably, d represents an integer of 1 to 100, and even more preferably, d represents an integer of 1 to 20.

[0059] Y in formula (8) １ is preferably represented by general formula (iii). １is preferably a fluorene group, more preferably a fluorene group having a total of 12 to 20 carbon atoms which may have a substituent, and even more preferably a fluorene group having a total of 12 to 16 carbon atoms which may have a substituent.

[0060] Specific examples of the monomer compound for forming the diol structural unit (A) represented by formula (8) include 9,9-bis[6-(2-hydroxyethoxy)naphthalen-2-yl]fluorene (BNEF), 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), and 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (BPPEF), and more preferably BNEF and BPEF.

[0061] In formula (9), R ４１ and R ４２ R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may have a substituent. ４１ and R ４２ is preferably a hydrogen atom or an alkyl group having 1 or 2 carbon atoms which may have a substituent, more preferably a hydrogen atom or an alkyl group having 1 carbon atom which may have a substituent, and even more preferably a hydrogen atom. a in formula (9) represents an integer of 2 to 16, preferably an integer of 4 to 14 or an integer of 3 to 12, and more preferably an integer of 8 to 14 or an integer of 6 to 12.

[0062] Specific examples of the monomer compound for forming the diol structural unit (A) represented by formula (9) include alkanediols such as 1,12-dodecanediol.

[0063] In the general formula (10), R is H, CH ３ or C ２ H ５ and preferably H or C ２ H ３ is.

[0064] Examples of the substituent in the diol structural unit (A) include a hydroxyl group, a halogen, an amino group, a vinyl group, a carboxyl group, a cyano group, a (meth)acryloxy group, a glycidyloxy group, and a mercapto group. The substituents on the alkyl group in the diol structural unit (A) include aryl groups such as a phenyl group and a naphthyl group, and the substituents on the aryl group in the diol structural unit (A) may also include an alkyl group. The number of carbon atoms in the substituted moiety is the total number of carbon atoms, including the number of carbon atoms in the substituent. The thermoplastic resin may contain one type of diol structural unit (A) alone, or two or more types in combination.

[0065] (4) Optional Structural Unit (Structural Unit (Z)) The thermoplastic resin may contain a structural unit (optional structural unit (Z)) other than the silane structural unit, the ester structural unit (I), and the diol structural unit (A), which can be said to be the main components constituting the main chain. For example, it is a structural unit derived from the following diol compound.

[0066] The structural unit (Z) that can be contained in the thermoplastic resin is a structural unit represented by the following formula (I 1 ) ~ (I 6 These diol compounds are each derived from a diol compound represented by the formula (I). 1 ) ~ (I 6 ) may be abbreviated as

[0067] Diol compound (I 1 ) is represented by the following formula (I 1 ) [In the formula, R 1 and R 2 are independently −(CR 5 R 6 ) q1 - or -(-O-(CR 5 R 6 ) q2 -) q3 - (wherein, R 5 and R 6 are independently H or C 1-6represents an alkyl group, q1 represents an integer of 0 or more and 10 or less, q2 represents an integer of 1 or more and 10 or less, q3 represents an integer of 1 or more and 10 or less, and when q1 or q2 is an integer of 2 or more, a plurality of R 5 or R 6 may be the same or different), R 3 and R 4 are independently one or more halogeno groups selected from the group consisting of chloro, bromo and iodo, C 1-20 Aliphatic hydrocarbon group, C 1-20 Alkoxyl group, C 3-20 Cycloalkyl group, C 6-20 Aromatic hydrocarbon group, C 7-20 Aralkyl group, C 6-20 Aromatic hydrocarbon oxy group, or C 3-20 represents a cycloalkoxyl group; 1 is one of the groups shown below, (In the formula, R 7 and R 8 is independently selected from the group consisting of H, chloro, bromo and iodo, one or more halogeno groups, C optionally having a substituent α 1-20 an aliphatic hydrocarbon group, C optionally having a substituent α 1-20 an alkoxyl group, C optionally having a substituent β; 6-20 represents an aromatic hydrocarbon group, or R 7 and R 8 are bonded to form C 3-20 may form a carbocyclic or 5- to 12-membered heterocyclic ring, R 9 and R 10 are independently H or C 1-6 represents an alkyl group, and when r1 is an integer of 2 or more, a plurality of R 9 or R 10 may be the same or different, R 11 ~R 18 is independently one or more halogeno groups selected from the group consisting of chloro, bromo and iodo, C optionally having a substituent α 1-20 an aliphatic hydrocarbon group, C optionally having a substituent α 1-20 C optionally having an alkoxyl group or a substituent β 6-12represents an aromatic hydrocarbon group, R 19 C which may have a substituent α 1-9 represents an alkylene group, r1 represents an integer of 1 or more and 20 or less, and r2 represents an integer of 1 or more and 500 or less.

[0068] The above formula (I 1 In the formula (I), p1 and p2 independently represent an integer of 0 to 4, and the substituent α is C 1-6 Alkoxyl group, C 1-7 is one or more substituents selected from an acyl group, one or more halogeno groups selected from the group consisting of chloro, bromo, and iodo, an amino group, a nitro group, a cyano group, and a carbamoyl group, and the substituent β is C 1-6 Alkyl group, C 1-6 Alkoxyl group, C 1-7 The substituents are one or more selected from an acyl group, one or more halogeno groups selected from the group consisting of chloro, bromo and iodo, an amino group, a nitro group, a cyano group, and a carbamoyl group.

[0069] - (CR 5 R 6 ) q1 Examples of - include an ethylene group (-CH2CH2-), and -O-(CR 5 R 6 ) q2 Examples of - include -O-CH2CH2- and -O-CH(CH3)CH2-. 1 -(-O-(CR 5 R 6 ) q2 -) q3 -, HO-R from the viewpoint of stability 1 -Ph is HO-(-O-(CR 5 R 6 ) q2 -) q3 It does not become -Ph, but HO-(-(CR 5 R 6 ) q2 -O-) q3-Ph. q2 is preferably 2 or greater. Examples of the "halogeno group" include chloro, bromo, and iodo, with chloro or bromo being preferred, and chloro being more preferred.

[0070] "C 1-20 The term "aliphatic hydrocarbon group" refers to a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, 1-20 Alkyl group, C 2-20 alkenyl groups, and C 2-20 Examples of the alkyl group include an alkynyl group. 1-20 Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-pentadecyl, and n-icosyl. 1-10 Alkyl group or C 1-6 alkyl group, more preferably C 1-4 Alkyl group or C 1-2 C is an alkyl group, and even more preferably methyl. 2-20 Examples of alkenyl groups include ethenyl (vinyl), 1-propenyl, 2-propenyl (allyl), isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, pentenyl, hexenyl, octenyl, decenyl, pentadecenyl, and icosenyl. 2-10 Alkenyl group or C 2-6 It is an alkenyl group, more preferably ethenyl (vinyl) or 2-propenyl (allyl). 2-20 Examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, octynyl, decynyl, pentadecynyl, and icosynyl. 2-10 Alkynyl group or C 2-6 Alkynyl group, more preferably C 2-4 Alkynyl group or C 2-3 It is an alkynyl group.

[0071] "C 1-20The term "alkoxyl group" refers to a linear or branched monovalent aliphatic hydrocarbon oxy group having 1 to 20 carbon atoms. Examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, n-pentoxy, and n-hexoxy, and preferably C 1-10 Alkoxyl group or C 1-6 is an alkoxyl group, more preferably C 1-4 Alkoxyl group or C 1-2 It is an alkoxy group, and even more preferably methoxy. 3-20 The term "cycloalkyl group" refers to a monovalent cyclic saturated aliphatic hydrocarbon group having 3 to 20 carbon atoms. Examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. Preferably, C 3-10 It is a cycloalkyl group. 6-20 The term "aromatic hydrocarbon group" refers to a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms. Examples include phenyl, indenyl, naphthyl, biphenyl, acenaphthenyl, fluorenyl, phenalenyl, phenanthrenyl, anthracenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, and perylenyl, and preferably C 6-12 It is an aromatic hydrocarbon group, and more preferably phenyl. 7-20 The term "aralkyl group" refers to an alkyl group substituted with one aromatic hydrocarbon group and having 7 to 20 carbon atoms. Examples include benzyl, phenethyl, phenylpropyl, naphthylmethyl, naphthylethyl, and biphenylmethyl, with benzyl being preferred.

[0072] "C 6-20 The term "aromatic hydrocarbon oxy group" refers to a monovalent aromatic hydrocarbon oxy group having 6 to 20 carbon atoms. Examples include phenoxy, indenyloxy, naphthyloxy, biphenyloxy, acenaphthenyloxy, fluorenyloxy, phenalenyloxy, phenanthrenyloxy, anthracenyloxy, triphenylenyloxy, pyrenyloxy, chrysenyloxy, naphthacenyloxy, and perylenyloxy. Preferably, C 6-12It is an aromatic hydrocarbon oxy group, more preferably phenoxy. 3-20 The term "cycloalkoxyl group" refers to a monovalent cyclic saturated aliphatic hydrocarbon oxy group having 3 to 20 carbon atoms. Examples include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, adamantyloxy, and cyclododecanyl. Preferably, C 3-12 The substituent α is a cycloalkyloxy group. 1-6 Alkoxyl group, C 1-7 Examples of the substituent β include one or more substituents selected from an acyl group, one or more halogeno groups selected from the group consisting of chloro, bromo, and iodo, an amino group, a nitro group, a cyano group, and a carbamoyl group. 1-6 Alkyl group, C 1-6 Alkoxyl group, C 1-7 Examples of the substituent include an acyl group, one or more halogeno groups selected from the group consisting of chloro, bromo and iodo, an amino group, a nitro group, a cyano group, and one or more substituents selected from a carbamoyl group.

[0073] "Amino group" includes unsubstituted amino groups (-NH2) as well as one C 1-6 Mono C substituted with alkyl group 1-6 Alkylamino group and two C 1-6 Alkyl-substituted diC 1-6 The amino group includes an alkylamino group. Examples of such an amino group include amino (—NH2); mono-C groups such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, t-butylamino, n-pentylamino, and n-hexylamino. 1-6 Alkylamino groups: di-C groups such as dimethylamino, diethylamino, di(n-propyl)amino, diisopropylamino, di(n-butyl)amino, diisobutylamino, di(n-pentyl)amino, di(n-hexyl)amino, ethylmethylamino, methyl(n-propyl)amino, n-butylmethylamino, ethyl(n-propyl)amino, and n-butylethylamino; 1-6An alkylamino group can be exemplified. An unsubstituted amino group is preferable. 1-7 The term "acyl group" refers to the remaining atomic group obtained by removing OH from an aliphatic carboxylic acid having 1 to 7 carbon atoms. Examples include formyl, acetyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, isobutylcarbonyl, t-butylcarbonyl, n-pentylcarbonyl, and n-hexylcarbonyl, and preferably C 1-4 It is an acyl group, more preferably acetyl. The number of substituents of the substituent α is not particularly limited as long as it is substitutable, but can be, for example, 1 or more and 20 or less. The number of the substituents is preferably 10 or less, more preferably 5 or less or 3 or less, and even more preferably 2 or less or 1. The number of substituents of the substituent β is not particularly limited as long as it is substitutable, but can be, for example, 1 or more and 10 or less. The number of the substituents is preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less or 1.

[0074] R 7 and R 8 C is formed by bonding 5-20 The carbocyclic ring is a C ring optionally having a substituent β. 3-20 Examples of the condensed ring include a cycloalkyl group and a condensed ring of a cycloalkyl group and an aromatic hydrocarbon group. Examples of the condensed ring include acenaphthenyl and fluorenyl. R 7 and R 8 Examples of the 5- to 12-membered heterocycle formed by bonding include oxiranyl, aziridinyl, tetrahydrofuranyl, tetrahydrothiophenyl, pyrrolidinyl, oxathiolanyl, piperidinyl, 1(3H)-isobenzofuranonyl, and the like.

[0075] Diol compound (I 1Specific examples of the bis(4-hydroxyphenyl)methane include the following compounds: bis(4-hydroxyphenyl)methane, bis(2-hydroxyphenyl)methane, 2,4'-dihydroxydiphenylmethane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone, bis(2-hydroxyphenyl)sulfone, bis(4-hydroxy-3-methylphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4- 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-methylphenyl)ethane, bis(4-hydroxy-3-methylphenyl)methane, 2,2-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl) 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cycloundecane, 1,1-bis(4-hydroxyphenyl)cyclododecane, 2,2-bis(4-hydroxy-3-allylphenyl)propane, 3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl)cyclohexane, 9,9-bis(4-hydroxy-3-ethylphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxyphenyl)cyclohexane bis(4-hydroxyphenyl)fluorene, α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethyldiphenyl random copolymer siloxane, α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisphenol, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisphenol, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 1,1-bis(4-hydroxyphenyl)-2-methylpropane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)decane, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-t-butylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-t-butylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-isopropylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-cyclohexylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, 4-(9-(4-hydroxyethoxy)phenyl)-9H-fluoren-9-yl)phenol, 2,2-bis(4-(2-hydroxyethoxy)phenyl)propane, 4,4-bis(2-hydroxyethoxy)biphenyl, 2,2'(9H-fluorene-9,9'-diyl)bis(ethan-1-ol), 9H- (fluorene-9,9-diyl)dimethanol, 2,2'-(1,4-phenylene)bis(ethan-1-ol), 2,2'-(1,4-phenylene)bis(methane-1-ol), 2,2'-(1,4-phenylenebis(oxy))bis(ethan-1-ol), 1,1-bis(4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane, 1,1-bis(4-hydroxy-3-phenylphenyl)cyclododecane, 1,1-bis(4-hydroxy-3-t-butylphenyl)cyclododecane, 1, 1-bis(4-hydroxy-3-sec-butylphenyl)cyclododecane, 1,1-bis(4-hydroxy-3-allylphenyl)cyclododecane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclododecane, 1,1-bis(4-hydroxy-3-fluorophenyl)cyclododecane, 1,1-bis(4-hydroxy-3-chlorophenyl)cyclododecane, 1,1-bis(4-hydroxy-3-bromophenyl)cyclododecane, 7-ethyl-1,1-bis(4-hydroxyphenyl)cyclododecane, 5,6-dimethyl-1,Examples include 1-bis(4-hydroxyphenyl)cyclododecane.

[0076] Among these, bis(4-hydroxyphenyl)methane, bis(2-hydroxyphenyl)methane, 2,4'-dihydroxydiphenylmethane, bis(4-hydroxyphenyl)ether, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, 1,1-bis(4-hydroxyphenyl)cyclododecane, and 1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane are particularly preferred. Furthermore, representative diol compounds (I) 1 ) are shown below. [In the formula, R 1 and R 2 has the same meaning as above.] However, in some cases, the diol compound (I 1 ) bisphenol A, bisphenol AP, bisphenol B, bisphenol BP, bisphenol E, bisphenol F, bisphenol TMC, and bisphenol Z may be excluded.

[0077] Diol compound (I 2 ) is represented by the following formula (I 2 ) [In the formula, R 1 and R 2 is represented by the above formula (I 1 ) R 1 and R 2 and X 2 is represented by the formula (I 1 ) X 1 The diol compound (I) 2Specific examples of fluorenes include 9,9-bis[6-(1-hydroxymethoxy)naphthalen-2-yl]fluorene, 9,9-bis[6-(2-hydroxyethoxy)naphthalen-2-yl]fluorene, 9,9-bis[6-(3-hydroxypropoxy)naphthalen-2-yl]fluorene, and 9,9-bis[6-(4-hydroxybutoxy)naphthalen-2-yl]fluorene. Of these, 9,9-bis[6-(2-hydroxyethoxy)naphthalen-2-yl]fluorene is preferred.

[0078] Diol compound (I 3 ) is represented by the following formula (I 3 ) is expressed as HO-R 1 -X 3 -R 2 -OH (I 3 ) [wherein, R 1 and R 2 is represented by the above formula (I 1 ) or formula (I ２ ) R 1 and R 2 and X 3 is C 15-32 represents a divalent aromatic hydrocarbon group.] C 15-32 Examples of the divalent aromatic hydrocarbon group include C groups such as fluoranthenylene, acephenanthrylene, aceanthrylene, triphenylene, pyrenylene, chrysenylene, naphthacenylene, pleiadenylene, picenylene, perylenylene, biphenylene, pentaphenylene, pentacenylene, tetraphenylenylene, hexaphenylene, hexacenylene, rubycenylene, coronenylene, trinaphthylenylene, heptaphenylene, heptacenylene, pyranthrene, and ovalenylene. 15-32 Divalent condensed polycyclic aromatic hydrocarbon groups include terphenylene and quaterphenylene. 3 ) in 3 is a substituent R which is an alkyl group or an aryl group. 3 C having 15-32 It may be a divalent aromatic hydrocarbon group. 3 R above 3The number of groups is not particularly limited as long as it is substitutable, but can be, for example, 1 or more and 10 or less, preferably 8 or less or 5 or less, and more preferably 1 or 2.

[0079] Diol compound (I 3 Specific examples of the binaphthalenediol compounds include those represented by the following formula: [In the formula, R 1 and R 2 has the same meaning as above.] Examples of such binaphthalene diol compounds include 2,2'-bis(1-hydroxymethoxy)-1,1'-binaphthalene, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene, 2,2'-bis(3-hydroxypropyloxy)-1,1'-binaphthalene, 2,2'-bis(4-hydroxybutoxy)-1,1'-binaphthalene, etc. Of these, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene is preferred.

[0080] Diol compound (I 4 ) is represented by the following formula (I 4 ) is expressed as HO-R 20 -X 4 -R 21 -OH (I 4 ) [wherein, R 20 and R 21 are independently −(CR 5 R 6 ) m1 - or -(-O-(CR 5 R 6 ) m2 -) m3 - (wherein, R 5 and R 6 is represented by the formula (I 1 ) in R ５ , R ６ and m １ represents an integer of 1 or more and 10 or less, m ２ represents an integer of 1 or more and 10 or less, m ３ represents an integer of 1 or more and 10 or less, m １ or m ２ is an integer of 2 or more, a plurality of R 5 or R 6may be the same or different), and X 4 represents a divalent group containing one or more hydrocarbon rings or heterocycles. ２ is preferably 2 or more.

[0081] - (CR 5 R 6 ) m1 Examples of - include an ethylene group (-CH2CH2-), and -O-(CR 5 R 6 ) m2 Examples of - include -O-CH2CH2- and -O-CH(CH3)CH2-. 1 -(-O-(CR 5 R 6 ) m2 -) m3 -, HO-R from the viewpoint of stability 1 -X 3 - is HO-(-O-(CR 5 R 6 ) m2 -) m3 -X 3 It does not become -, HO-(-(CR 5 R 6 ) m2 -O-) m3 -X 3 The divalent group containing one or more hydrocarbon rings or heterocycles is a divalent C which may have a substituent β. 6-32 Aromatic hydrocarbon group, divalent C optionally having a substituent β 3-20 a cycloalkyl group, a divalent C group optionally having a substituent β; 6-32 Divalent C optionally having an aromatic hydrocarbon group and a substituent β 3-20 Divalent groups each having one or more cycloalkyl groups can be mentioned. 6-32 The aromatic hydrocarbon group may contain a heteroatom selected from an oxygen atom, a sulfur atom, and a nitrogen atom, so long as the aromatic hydrocarbon group as a whole exhibits aromaticity. 6-32 The aromatic hydrocarbon group is not particularly limited, but examples thereof include the following: Divalent C 3-20The cycloalkyl group may also contain a heteroatom selected from an oxygen atom, a sulfur atom, and a nitrogen atom. 3-14 The cycloalkyl group is not particularly limited, but examples thereof include the following. Divalent C optionally having a substituent β 6-32 Divalent C optionally having an aromatic hydrocarbon group and a substituent β 3-20 The divalent group each having one or more cycloalkyl groups is not particularly limited, but examples thereof include the following.

[0082] Diol compound (I 5 ) is represented by the following formula (I 5 ) is expressed as HO-R 1 -X 5 -R 2 -OH (I 5 ) [wherein, R 1 and R 2 is represented by the above formula (I 1 ) to formula (I ３ ) R 1 and R 2 and X 5 represents a divalent saturated heterocyclic group.] The divalent saturated heterocyclic group is not particularly limited, but examples thereof include the following.

[0083] Diol compound (I 6 ) is represented by the following formula (I 6 ) [In the formula, X 6 is C 1-10 represents an alkylene group, and n represents an integer of 13 or more and 50 or less.] C 1-10 The alkylene group refers to a linear or branched divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms. Examples include -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH(CH3)-, -CH(CH3)CH2-, and -CH2CH2CH2CH2-. 6 ) in X 6 may be the same or different, and multiple X 5 When -O-X is present, 6The arrangement of - may be random or block. 1-10 The alkylene group is 2-10 An alkylene group is preferred. The diol compound may be used alone or in combination of two or more. For example, by using two or more diol compounds in combination, a copolymerized polyester carbonate or polyester can be produced satisfactorily. However, from the viewpoint of production efficiency, it is preferable to use only one diol compound alone. When two or more diol compounds are used, the number of diol compounds is preferably 5 or less, more preferably 3 or less, and even more preferably 2. By copolymerizing two or more diol compounds using the method of the present invention, the range of physical properties of the resulting polyester carbonate or polyester is broadened, making it easier to adjust the physical properties.

[0084] C 1-4 The amounts of the halogenated hydrocarbon and the diol compound to be used are not particularly limited as long as the reaction proceeds and the desired product is obtained. 1-4 The above reaction also proceeds when a diol compound is used in an amount of 1 mole per mole of halogenated hydrocarbon. 1-4 The molar ratio of the diol compound to the halogenated hydrocarbon ([diol compound] / [C 1-4 It is preferable that the molar ratio [of nucleophilic functional group-containing compounds] is 0.001 or more and 1 or less. The molar ratio is more preferably 0.01 or more, even more preferably 0.1 or more, and more preferably 0.8 or less, and even more preferably 0.5 or less. If the molar ratio is too large, the amount of the nucleophilic functional group-containing compounds increases relatively, and the amount of unreacted nucleophilic functional group-containing compounds increases, while if the molar ratio is too small, the amount of unreacted C 1-4 The amount of halogenated hydrocarbons increases, and there is a risk that carbonyl halides may be released outside the reaction system. 1-4 When the halogenated hydrocarbon is a liquid at room temperature and pressure and can be used as a solvent, 1-4 The ratio of the diol compound to the halogenated hydrocarbon may be 1 mg / mL or more and 500 mg / mL or less.

[0085] Among the above-mentioned optional structural units (Z), structural units derived from diols having an aromatic ring are preferred, as they tend to increase the refractive index of the thermoplastic resin. From the viewpoint of the reactivity of the monomer in the polymerization reaction, structural units derived from aliphatic hydroxyl groups (e.g., -CH ２ For the above reasons, a structural unit derived from a diol having an aromatic ring and an aliphatic hydroxyl group, such as a diol having the general formula (I), is preferred. １ ) ~ (I 3 ) １ ) ~ (I 3 It is preferable to provide a structural unit (Z) derived from

[0086] The thermoplastic resin may be a random copolymer or a block copolymer containing silane structural units, ester structural units, and diol structural units. The thermoplastic resin may also be a random copolymer or a block copolymer containing silane structural units, ester structural units, diols, and any other structural units. From the viewpoint of the properties of the thermoplastic resin and simplification of the manufacturing process, the thermoplastic resin is preferably a random copolymer. It is also preferable that the number of bonds between dinaphthalene structural units (N) via silane structural units and the number of bonds between fluorene structural units (F) via silane structural units are as small as possible, and that many dinaphthalene structural units (N) and fluorene structural units (F) are alternately bonded via silane structural units.

[0087] In the thermoplastic resin, it is preferred that the silane structural unit (S) and the diol structural unit (A) are bonded via a (silyl) ether bond, and more preferably, substantially all of the silane structural units (S) and the diol structural units (A) in the thermoplastic resin are bonded via an ether bond. Also, it is preferred that the ester structural unit (I) and the diol structural unit (A) in the thermoplastic resin are bonded via an ester bond, and more preferably, substantially all of the ester structural units (I) and the diol structural units (A) in the thermoplastic resin are bonded via an ester bond. However, the thermoplastic resin may further contain a carbonate bond, and the thermoplastic resin may be a polyester resin or a polyester carbonate resin, and is preferably a polyester resin.

[0088] <I-2. Ratio of Structural Units> In a thermoplastic resin, the content of the silane structural unit (S) is preferably 2 to 50 mol% or 5 to 50 mol%, based on the total number of moles of all structural units. The content of the silane structural unit (S) in a thermoplastic resin is more preferably 10 to 45 mol%, more preferably 15 to 40 mol%. In a thermoplastic resin, the content of the ester structural unit (I) is preferably 3 to 45 mol%, based on the total number of moles of all structural units. The content of the ester structural unit (I) in a thermoplastic resin is more preferably 5 to 40 mol%, more preferably 10 to 35 mol%. Furthermore, in a thermoplastic resin, the content of the diol structural unit (A) is preferably 30 to 70 mol%, based on the total number of moles of all structural units. The content of the diol structural unit (A) in a thermoplastic resin is more preferably 35 to 65 mol%, more preferably 40 to 60 mol%.

[0089] In a thermoplastic resin, the silane structural units (S) and the ester structural units (I) are bonded to the terminals of the diol structural units (A). For the following reasons, it is preferable that the total number of moles of the silane structural units (S) and the ester structural units (I) in the thermoplastic resin be approximately equal to the total number of moles of the diol structural units (A). The silane structural units (S) are formed by eliminating an alkoxy group or monoaryloxy group in the silane compound during a polymerization reaction between the above-mentioned silane compound and the hydroxyl group of the diol compound. The ester structural units (I) are formed by an esterification reaction in which alcohol or water is eliminated during a polymerization reaction between the above-mentioned carboxylic acid, ester compound, or the like and the hydroxyl group of the diol compound. For this reason, in a thermoplastic resin, the total number of moles of the silane structural units (S) and the ester structural units (I) is usually equal to the total number of moles of the diol structural units (A). However, when silane structural units (S) or ester structural units (I) are positioned at both ends of the diol-derived diol structural units (A), the total number of moles of the silane structural units (S) and the ester structural units (I) may be slightly in excess of the total number of moles of the diol structural units (A), and for example, the total number of moles of the silane structural units (S) and the ester structural units (I) may be about 1.01 times the total number of moles of the diol structural units (A). Thus, the total number of moles of the silane structural units (S) and the ester structural units (I) in the thermoplastic resin is, for example, 1.00 to 1.05 times, preferably 1.00 to 1.03 times, and more preferably 1.00 to 1.01 times the total number of moles of the diol structural units (A).

[0090] In the thermoplastic resin, the proportion of the optional structural unit (Z) in all structural units is preferably 30 mol% or less, more preferably 20 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less, and the optional structural unit (Z) may not be contained. In addition, in the thermoplastic resin, the total proportion of the silane structural unit, the ester structural unit, and the diol structural unit in all structural units is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more. In addition, the thermoplastic resin may be composed only of the silane structural unit, the ester structural unit, and the diol structural unit (A).

[0091] <I-3. Properties of Thermoplastic Resin> The weight-average molecular weight of the thermoplastic resin is, for example, 5,000 to 100,000, preferably 5,000 to 50,000, and more preferably 6,000 to 30,000. The weight-average molecular weight of the thermoplastic resin is further preferably 10,000 to 25,000, more preferably 12,000 to 22,000, and particularly preferably 15,000 to 20,000. In some embodiments of the thermoplastic resin, the weight-average molecular weight is preferably 12,000 to 40,000, more preferably 14,000 to 36,000, and particularly preferably 16,000 to 35,000.

[0092] The thermoplastic resin has a glass transition temperature (Tg) according to JIS K 7121 of, for example, 105 to 170°C, 120 to 170°C, or 137 to 170°C, preferably 110 to 165°C, and more preferably 115 to 160°C. The Tg range of the thermoplastic resin is preferably 120 to 160°C, and more preferably 130 to 158°C.

[0093] The refractive index (nD) of the thermoplastic resin is preferably 1.670 to 1.720, more preferably 1.675 to 1.710, and even more preferably 1.680 to 1.705, 1.681 to 1.720, etc. Typically, a high refractive index (nD) value is preferred for thermoplastic resins that can be used in optical applications, so the lower limit is important, and the thermoplastic resin in one embodiment of the present invention has a refractive index (nD) value of 1.650 or greater. The refractive index (nD) value of the thermoplastic resin is preferably 1.675 or greater, more preferably 1.680 or greater, and even more preferably 1.681 or greater or 1.685 or greater. While the upper limit of the refractive index (nD) of the thermoplastic resin is not particularly important, the thermoplastic resin in one embodiment of the present invention has a refractive index (nD) value of 1.710 or less.

[0094] The Abbe number (νd) of the thermoplastic resin is, for example, 15.0 to 19.6. The Abbe number (νd) of the thermoplastic resin is preferably 16.0 to 24.0, more preferably 16.5 to 23.0, 17.0 to 22.0, or 17.5 to 21.0, even more preferably 18.0 to 20.0, and even more preferably 18.5 to 19.5. Thermoplastic resins, particularly those used for optical applications, preferably have a high refractive index, and high refractive index thermoplastic resins usually tend to have small Abbe number (νd) values. However, optical thermoplastic resins with high Abbe number (νd) values ​​can also be useful. The thermoplastic resin in one embodiment of the present invention has an Abbe number (νd) of 17.0 or greater. The Abbe number (νd) of the thermoplastic resin is preferably 17.5 or greater, more preferably 18.0 or greater, and even more preferably 18.4 or greater.

[0095] In the case of a thermoplastic resin, the value of θgF is preferably 0.850 or less, more preferably 0.750 or less, even more preferably 0.700 or less, and particularly preferably 0.685 or less or 0.680 or less. In the case of a thermoplastic resin, the value of θhF is preferably 1.500 or less, more preferably 1.450 or less, even more preferably 1.400 or less or 1.360 or less, and particularly preferably 1.340 or less or 1.320 or less. Here, θgF and θhF represent the wavelength dispersion of the refractive index, and the smaller the value, the smaller the wavelength dispersion. If the wavelength dispersion becomes large, especially in the g-line and h-line in the short wavelength region, it may become difficult to correct chromatic aberration, so usually, the smaller the values ​​of θgF and θhF are preferred.

[0096] In the thermoplastic resin, the proportion of the total weight of silicon atoms (total Si amount) based on the total weight of the thermoplastic resin is, for example, 0.4 to 10.0 mass%, preferably 1.0 to 10.0 mass%, more preferably 1.2 to 8.0 mass%, even more preferably 1.5 to 7.0 mass%, and particularly preferably 2.0 to 6.5 mass%, for example, 2.0 to 4.0 mass%.

[0097] In the polymer chain of the thermoplastic resin, the proportion of carbonate-derived Ph end groups, i.e., —OC(O)O—Ph end groups, is preferably 0.1 to 20 μeq / g, more preferably 0.5 to 18 μeq / g, even more preferably 1.0 to 16 μeq / g, and particularly preferably 1.5 to 12 μeq / g. The proportion of carbonate-derived Ph end groups is preferably 1 to 20 mol%, more preferably 2 to 18 mol%, even more preferably 3 to 15 mol%, and particularly preferably 4 to 12 mol%, based on the total number of end groups in the polymer chain of the thermoplastic resin.

[0098] In the polymer chain of the thermoplastic resin, the silyl ether-derived Ph end group, i.e., —OSiRs １ Rs ２ The terminal group of -OPh (Rs １ and Rs. ２is defined separately) is preferably 5 to 200 μeq / g, more preferably 10 to 150 μeq / g, even more preferably 15 to 120 μeq / g, and particularly preferably 20 to 100 μeq / g. The proportion of silyl ether-derived Ph terminal groups is preferably 30 to 99 mol%, more preferably 40 to 95 mol%, even more preferably 50 to 90 mol%, and particularly preferably 60 to 85 mol%, based on the total number of terminal groups in the polymer chain of the thermoplastic resin. Furthermore, in the polymer chain of the thermoplastic resin, alkoxy terminal groups such as silyl ether-derived OMe terminal groups, for example, —OSiRs １ Rs ２ -OMe end group (Rs １ and Rs. ２ is defined separately) is preferably 5 to 300 μeq / g, more preferably 20 to 250 μeq / g, even more preferably 40 to 200 μeq / g, and particularly preferably 60 to 150 μeq / g. The proportion of alkoxy terminal groups such as silyl ether-derived Me terminal groups is preferably 10 to 99 mol %, more preferably 20 to 90 mol %, even more preferably 30 to 80 mol %, and particularly preferably 40 to 70 mol %, based on the total number of terminal groups in the polymer chain of the thermoplastic resin.

[0099] Thermoplastic resin polymers may contain some impurities. For example, thermoplastic resin polymers may contain impurities derived from raw materials such as formic acid and organic phosphorus compounds in an amount of, for example, 5 ppm to 100 ppm by weight, 10 ppm to 70 ppm by weight, or 20 ppm to 50 ppm by weight, based on the total weight of the polymer. Furthermore, the thermoplastic resin may contain a small amount of catalyst used in the polymerization reaction for production. For example, the remaining catalyst may be present in an amount of, for example, 5 μmol to 100 μmol, 15 μmol to 80 μmol, 25 μmol to 60 μmol, or 30 μmol to 50 μmol, calculated as metal, per mole of all dihydroxy compounds used in the production of the thermoplastic resin polymer.

[0100] [II. Composition (Thermoplastic Resin Composition)] The thermoplastic resin composition of the present invention preferably contains the above-mentioned polysilyl ether resin as a thermoplastic resin as a main component. The thermoplastic resin composition of the present invention may contain the following components in addition to the thermoplastic resin.

[0101] <II-1. Resins Other than the Resins Described Above> The thermoplastic resin composition of the present invention may contain a thermoplastic resin other than the polysilyl ether resin described above, such as a polycarbonate resin. The type of polycarbonate resin is not particularly limited, as long as it contains an —[O-R-OCO]— unit containing a carbonate bond in the molecular main chain (where R is an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and further has a linear or branched structure). The thermoplastic resin composition may also contain a polycarbonate resin, polyester carbonate resin, or polyester resin other than the polysilyl ether resin described above. Similarly, the polyester carbonate resin and polyester resin are not particularly limited, as long as they contain an —[O-R-OC]— unit (where R is as described above) containing a carbonate bond in the molecular main chain.

[0102] Resins that do not fall under the category of polysilyl ether resins but are included in the thermoplastic resin composition, such as polycarbonate resins, polyester carbonate resins, and polyester resins, preferably have a weight average molecular weight of 10,000 to 100,000, more preferably 13,000 to 80,000, and even more preferably 15,000 to 60,000.

[0103] The composition of the present invention may contain a resin other than the polysilyl ether resin, preferably a thermoplastic resin. The type of thermoplastic resin as such a secondary component is not particularly limited, but examples thereof include polycarbonate resins and polyester carbonate resins, as well as various resins such as acrylic resins such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polyimide (PI), cycloolefin copolymers (COC), norbornene-containing resins, polyethersulfone, cellophane, and aromatic polyamides.

[0104] In the composition, the proportion of the total weight of silicon atoms (total Si amount) based on the total weight of the composition is preferably 0.1 to 20 mass%, more preferably 0.2 to 15 mass%, and particularly preferably 0.3 to 10 mass%.

[0105] A composition with excellent characteristics can be produced by using a thermoplastic resin with a high Si content. By mixing a thermoplastic resin having a Si content of, for example, 0.1 mass % or more with a resin that is substantially free of silyl ether structural units, preferably a polycarbonate resin, the resulting composition can have both excellent impact resistance and flowability.

[0106] Compositions containing thermoplastic resins may contain phenolic compounds that may be produced as by-products of the polymerization reaction, as well as unreacted silane compounds, carbonate compounds, and diol compounds. Because impurities such as phenolic compounds and diphenyl carbonate can reduce the strength of molded articles and cause odors, it is preferable to minimize their content. Therefore, the content of phenolic compounds, silane compounds, carbonate compounds, and diol compounds may be reduced to an undetectable level, but from the perspective of productivity, they may be included in the composition to the extent that the effect is not impaired. Furthermore, by including a predetermined amount of residual monomer, for example, 1 to 1,000 ppm by weight, preferably 10 to 900 ppm, and more preferably 20 to 800 ppm, based on the total weight of the composition, improved fluidity during molding can be achieved, resulting in good plasticity when the resin is molten. The composition of the present invention may also contain, for example, more than 300 ppm by mass or more, more than 500 ppm by mass or more, or more than 700 ppm by mass or more of an aromatic monohydroxy compound, such as aryl alcohols such as phenol.

[0107] <II-2. Additives> The thermoplastic resin composition of the present invention may contain additives. Examples of additives include antioxidants. As the antioxidant, phosphite-based antioxidants are preferred. Furthermore, the thermoplastic resin composition preferably contains the antioxidant used in the polymerization reaction for producing the polyether resin.

[0108] The proportion of the antioxidant added to the thermoplastic resin composition is preferably 0.001 parts by mass or more (approximately 10 ppm by mass or more), more preferably 0.01 parts by mass or more (approximately 100 ppm by mass or more), and even more preferably 0.1 parts by mass or more (approximately 1000 ppm by mass or more), per 100 parts by mass of the total weight of the composition. The proportion of the antioxidant added to the thermoplastic resin composition is preferably 2.0 parts by mass or less, more preferably 1.0 part by mass or less, even more preferably 0.7 parts by mass or less (approximately 7,000 ppm by mass or less), and particularly preferably 0.5 parts by mass or less (approximately 5,000 ppm by mass or less), per 100 parts by mass of the total weight of the composition. The antioxidant may be used alone or in combination with two or more different antioxidants. When two or more different antioxidants are used, the total amount is preferably within the above range.

[0109] The thermoplastic resin composition of the present invention may contain the following additives as secondary components. Deactivator: After the polymerization reaction is complete, the catalyst may be removed or deactivated from the thermoplastic resin of the present invention in order to maintain thermal stability. A method of deactivating the catalyst by adding a known acidic substance can be preferably carried out. Specific examples of the acidic substance include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate, phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid, phosphites such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, and monooctyl phosphite, and the like. Suitable catalysts include phosphate esters such as diphenylphosphonic acid, dioctylphosphonic acid, and monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; phosphonic acid esters such as diethyl phenylphosphonate; phosphines such as triphenylphosphine and bis(diphenylphosphino)ethane; boric acids such as boric acid and phenylboric acid; aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate; organic halides such as stearic acid chloride, benzoyl chloride, and p-toluenesulfonic acid chloride; alkyl sulfates such as dimethyl sulfate; and organic halides such as benzyl chloride. Furthermore, alkyl acid phosphate metal salts such as distearyl acid phosphate zinc salt and monostearyl acid phosphate zinc salt may also be used as a deactivator for deactivating the catalyst. The above-mentioned deactivators may be used in an amount of, for example, 0.001 to 50 times, preferably 0.01 to 30 times the molar amount of the catalyst.

[0110] A stabilizer may be added to the thermoplastic resin of the present invention. Examples of stabilizers include heat stabilizers and the above-mentioned antioxidants. When blended, the stabilizer is added in an amount of preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.02 parts by mass or more, per 100 parts by mass of the thermoplastic resin, and preferably 2 parts by mass or less, more preferably 1.4 parts by mass or less, and even more preferably 1.0 part by mass or less. Only one type of stabilizer may be contained, or two or more types may be contained. When two or more types are contained, the total amount is preferably within the above range.

[0111] Examples of the heat stabilizer include phenol-based, phosphorus-based, and sulfur-based heat stabilizers. Specific examples include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; metal acid pyrophosphates such as sodium acid pyrophosphate, potassium acid pyrophosphate, and calcium acid pyrophosphate; phosphates of Group 1 or Group 10 metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds. Also included are at least one compound selected from the group consisting of (a) a phosphite ester compound in which at least one ester in the molecule is esterified with phenol and / or a phenol having at least one alkyl group having 1 to 25 carbon atoms, (b) phosphorous acid, and (c) tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene-di-phosphonite.Specific examples of the phosphite ester compound (a) include trioctyl phosphite, trioctadecyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, triphenyl phosphite, tris(mononylphenyl)phosphite, tris(mononyl / dinonylphenyl)phosphite, trisnonylphenyl phosphite, tris(octylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, trinonyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, and bis(2,4-di-tert-butylphenyl)pentaerythritol. Examples of suitable diphosphite include bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol phosphite, monooctyldiphenyl phosphite, distearylpentaerythritol diphosphite, tricyclohexyl phosphite, diphenylpentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite. These may be used alone or in combination of two or more. Examples of the organic phosphite compound include "ADK STAB 1178 (product name, the same applies hereinafter)," "ADK STAB 2112," and "ADK STAB HP-10" manufactured by Adeka Corporation; "JP-351," "JP-360," and "JP-3CP" manufactured by Johoku Chemical Industry Co., Ltd.; and "IRGAFOS 168" manufactured by BASF.Examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris(nonylphenyl)phosphate, and 2-ethylphenyldiphenyl phosphate. When incorporated, the amount of the heat stabilizer added is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.03 parts by mass or more, relative to 100 parts by mass of the thermoplastic resin. It is also preferably 1 part by mass or less, more preferably 0.7 parts by mass or less, and even more preferably 0.5 parts by mass or less. Only one type of heat stabilizer may be contained, or two or more types may be contained. When two or more types are contained, it is preferable that the total amount is within the above range.

[0112] Flame Retardant The thermoplastic resin of the present invention may contain various additives within the scope of the present invention. Examples of flame retardants that may be used in the present invention include organometallic salt flame retardants, phosphorus-based flame retardants, and silicone-based flame retardants. Flame retardants that can be used in the present invention include the flame retardants (flame retardant compositions) described in paragraphs 0085 to 0093 of JP 2016-183422 A, the contents of which are incorporated herein by reference.

[0113] Examples of the ultraviolet absorber include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide, as well as organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic acid ester compounds, hindered amine compounds, and phenyl salicylate compounds. Of these, benzotriazole-based and benzophenone-based organic ultraviolet absorbers are preferred.In particular, specific examples of benzotriazole compounds include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-5-chlorobenzotriazole. Chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amyl)-benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol], 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]phenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylmethyl)phenol, 2-[5-chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol, 2,2'-(1,4-phenylene)bis[4H-3,1-benzoxazin-4-one], [(4-methoxyphenyl)-methylene]-propanediol acid dimethyl ester, 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylmethyl)phenol, 2-[5-chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol phenol, 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetrabutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetrabutyl)phenol], [methyl-3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate-polyethylene glycol] condensate, and the like can be mentioned.Among the above, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole and 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol] are preferred. Specific examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and 2,2',4,4'-tetrahydroxybenzophenone. Specific examples of phenyl salicylate-based UV absorbers include phenyl salicylate and 4-tert-butylphenyl salicylate. Specific examples of triazine-based UV absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]phenol and 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol. Specific examples of hindered amine-based UV absorbers include bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate. When incorporated, the UV absorber is preferably added in an amount of at least 0.01 parts by mass, more preferably at least 0.1 parts by mass, and preferably at most 3 parts by mass, more preferably at most 1 part by mass, per 100 parts by mass of the thermoplastic resin. The ultraviolet absorber may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.

[0114] Mold Release Agents Examples of mold release agents include carboxylic acid esters, polysiloxane compounds, and paraffin wax (polyolefin-based). Specific examples include at least one compound selected from the group consisting of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds with a number-average molecular weight of 200 to 15,000, and polysiloxane-based silicone oils. Examples of aliphatic carboxylic acids include saturated or unsaturated aliphatic mono-, di-, or tri-carboxylic acids. Aliphatic carboxylic acids also include alicyclic carboxylic acids. Among these, preferred aliphatic carboxylic acids are mono- or di-carboxylic acids having 6 to 36 carbon atoms, with saturated aliphatic mono-carboxylic acids having 6 to 36 carbon atoms being even more preferred. Specific examples of aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetraacontanoic acid, montanic acid, glutaric acid, adipic acid, and azelaic acid. The same aliphatic carboxylic acids as those described above can be used as the aliphatic carboxylic acids in the esters of aliphatic carboxylic acids and alcohols. On the other hand, examples of alcohols include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferred, and aliphatic saturated monohydric or polyhydric alcohols having 30 or less carbon atoms are more preferred. Here, aliphatic compounds also include alicyclic compounds. Specific examples of alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, etc. The above-mentioned ester compounds may contain aliphatic carboxylic acids and / or alcohols as impurities, or may be a mixture of multiple compounds.Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture primarily composed of myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate. Aliphatic hydrocarbons having a number-average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomers having 3 to 12 carbon atoms. Aliphatic hydrocarbons also include alicyclic hydrocarbons. These hydrocarbon compounds may also be partially oxidized. Among these, paraffin wax, polyethylene wax, or partially oxidized polyethylene wax are preferred, with paraffin wax and polyethylene wax being more preferred. The number average molecular weight is preferably 200 to 5,000. These aliphatic hydrocarbons may be a single substance or a mixture of substances with various constituent components and molecular weights, as long as the main component is within the above-mentioned range. Examples of polysiloxane-based silicone oils include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone. Two or more of these may be used in combination. When blended, the addition ratio of the release agent is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 2 parts by mass or less, more preferably 1 part by mass or less, per 100 parts by mass of the thermoplastic resin. Only one type of release agent may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount be within the above-mentioned range.

[0115] Colorant The colorant may be either a dye or a pigment, and examples thereof include inorganic pigments, organic pigments, organic dyes, etc. Examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine; oxide pigments such as titanium oxide, zinc white, red iron oxide, chromium oxide, iron black, titanium yellow, zinc-iron brown, titanium-cobalt green, cobalt green, cobalt blue, copper-chromium black, and copper-iron black; chromate pigments such as yellow lead and molybdate orange; and ferrocyanide pigments such as iron blue. Examples of organic pigments and dyes used as colorants include phthalocyanine dyes and pigments such as copper phthalocyanine blue and copper phthalocyanine green (dyes and pigments are referred to as dyes and pigments, hereinafter); azo dyes and pigments such as nickel azo yellow; condensed polycyclic dyes and pigments such as thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone, and quinophthalone; and quinoline, anthraquinone, heterocyclic, and methyl dyes and pigments. Among these, titanium oxide, carbon black, cyanine, quinoline, anthraquinone, and phthalocyanine dyes and pigments are preferred from the viewpoint of thermal stability. Furthermore, colorants may be used in the form of masterbatches with polystyrene resins, polycarbonate resins, or acrylic resins to improve handling during extrusion and dispersibility in the resin composition. When blended, the colorant is preferably added in an amount of 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less, and 0.1 parts by mass or more, relative to 100 parts by mass of the thermoplastic resin. Only one colorant may be used, or two or more colorants may be used. When two or more colorants are used, the total amount is preferably within the above range.

[0116] [III. Molded Article] Next, a molded article according to the present invention containing the thermoplastic resin or thermoplastic resin composition of the present invention will be described. The molded article according to the present invention contains the above-mentioned thermoplastic resin or thermoplastic resin composition. The molded article is obtained by molding the thermoplastic resin or thermoplastic resin composition. The molding method for the molded article is not particularly limited, and examples of the molded article include injection molded articles, press molded articles, blow molded articles, extrusion molded articles, vacuum molded articles, and pressure molded articles.

[0117] The molded article of the present invention is, for example, an optical lens, an optical film, etc. The thermoplastic resin of the present invention is suitable for optical applications, and the optical lens and the optical film have particularly excellent properties. Furthermore, the optical lens that can be included in the molded article of the present invention has a refractive index, an Abbe number, etc. within an appropriate range.

[0118] [IV. Method for Producing Thermoplastic Resin] <IV-1. Overview of the Production Method> The method for producing a thermoplastic resin includes at least a step of polymerizing the above-mentioned silane compound as a linking agent, the above-mentioned carboxylic acid or ester, and a diol compound (fluorene ring-containing dihydroxy compound (component A) or dinaphthalene-containing dihydroxy compound (component B)). The silane compound functions as a source of silane bonding sites, the carboxylic acid or ester functions as a source of ester bonding sites, and components A and B function as sources of the corresponding structural units. In addition, when a carbonate compound, such as diphenyl carbonate (DPC), is used, carbonate bonding sites can be formed in the main chain of the produced thermoplastic resin.

[0119] The above-mentioned polymerization reaction can be schematically illustrated as follows. For example, when dimethyldiphenoxysilane is used as the silane compound and BINOL-DC is used as the carboxylic acid, the silane compound reacts with the terminal hydroxyl groups of the diol compound to form a main chain of a thermoplastic resin, and phenol (PhOH), water, and the like are generated as by-products. Therefore, in the polymerization step, it is preferable to carry out the polymerization reaction under reduced pressure while removing by-products such as alcohols (e.g., aryl alcohols such as phenol), water, and the like in a molten state.

[0120] <II-2. Monomer Ratio> In the polymerization process for producing a thermoplastic resin, the ratios of the monomers, silane compound, carboxylic acid or ester compound, and diol compound components A and B are appropriately adjusted to achieve the preferred ratios of the structural units described above. For example, the molar ratio of component A to component B ((A):(B)) is preferably (A):(B) = 30 / 70 to 95 / 5. The molar ratio of component A to component B is more preferably 40 / 60 to 92 / 8, even more preferably 50 / 50 to 90 / 10, and particularly preferably 50 / 50 to 80 / 20.

[0121] The silane structural unit (S) and the ester structural unit (I) are bonded to the terminals of the diol structural unit (A), and the total number of moles of the silane structural unit (S) and the ester structural unit (I) is approximately equal to the total number of moles of the alcohol structural unit (A). However, it is preferable to use a slight excess of the silane compound and the carboxylic acid or ester compound in the polymerization step. For example, the total number of moles of the silane compound and the carboxylic acid or ester compound to be polymerized is 1.0 to 1.2 times, preferably 1.01 to 1.1 times, and more preferably 1.02 to 1.06 times the total number of moles of the diol compound (e.g., component A and component B).

[0122] In this way, if the amount (number of moles) of the silane compound is slightly in excess relative to the total amount (number of moles) of the fluorene ring-containing dihydroxy compound (component A) and the dinaphthalene-containing dihydroxy compound (component B) in the polymerization step, the excess silane compound, carboxylic acid, or ester compound is not used in the polymerization reaction and is removed from the reaction system, while a shortage of the silane structural units (S) and the ester structural units (I) in the thermoplastic resin obtained after polymerization is prevented, and the total number of moles of the silane structural units (S) and the ester structural units (I) can be reliably adjusted to be equal to the total number of moles of the diol structural units (A).

[0123] <II-3. Optional Monomer> In the polymerization step for producing a thermoplastic resin, a monomer other than a silane compound, a carboxylic acid or ester compound, and a diol compound may be used. For example, this is a monomer for forming the optional structural unit (Z) described above.

[0124] <II-4. Catalyst> Known polymerization catalysts can be used in the polymerization step. For example, antimony compounds, titanium compounds, germanium compounds, tin compounds, or aluminum compounds are preferred. Compounds used as polymerization catalysts include, for example, oxides of antimony, titanium, germanium, tin, and aluminum; acetates such as zinc acetate and lead acetate; carboxylates; hydrides; alcoholates; halides; carbonates; and sulfates. Two or more of these compounds may be used in combination as a polymerization catalyst. Among these compounds, tin, titanium, and germanium compounds are preferred from the viewpoint of the melt stability and color of the thermoplastic resin. For example, alkyl titanate compounds such as tetrabutyl orthotitanate are preferred. Known transesterification catalysts can also be used in the polymerization step. For example, compounds containing manganese, magnesium, titanium, zinc, aluminum, calcium, cobalt, sodium, lithium, or lead can be used. Specific examples include oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates, and sulfates containing these elements. Among these compounds, oxides, acetates, alcoholates, etc. of manganese, magnesium, zinc, titanium, and cobalt are preferred from the viewpoints of the melt stability, color, and small amount of insoluble foreign matter in the polymer of the thermoplastic resin. Manganese, magnesium, and titanium compounds are more preferred. Two or more of these compounds may be used in combination as a polymerization catalyst.

[0125] In the polymerization step, a catalyst containing a basic compound may be used. Examples of basic compound catalysts include those containing alkali metal compounds, alkaline earth metal compounds, etc. Examples of such compounds include organic acid salts of alkali metals and alkaline earth metal compounds, inorganic salts such as carbonates, oxides, hydroxides, hydrides, and alkoxides. Alternatively, quaternary ammonium hydroxides and their salts, amines, etc. may be used as basic compound catalysts. These compounds may be used alone or in combination.

[0126] Among the above-mentioned basic compound catalysts, those containing alkali metal carbonates or alkali metal hydroxides are more preferred. Specific examples of more preferred catalysts include metal carbonates such as cesium carbonate, potassium carbonate, sodium carbonate, and sodium bicarbonate; and metal hydroxides such as cesium hydroxide, potassium hydroxide, and sodium hydroxide. Furthermore, as a catalyst for the polymerization step, metal acetates and metal salts such as zinc acetate, lead acetate, manganese acetate, cobalt acetate, aluminum acetate, calcium acetate, potassium acetate, lithium acetate, magnesium acetate, sodium acetate, tin acetate, zirconium acetate, and zirconium acetylacetonate (Zr(acac)) can also be used. Specific examples of preferred metal salts include zinc acetate, lead acetate, manganese acetate, and cobalt acetate.

[0127] Furthermore, a phosphonium salt or the like can be used as a catalyst, and a quaternary phosphonium salt is preferred. Specific examples of the phosphonium salt as a polymerization catalyst include alkylphosphonium salts such as tetra-n-butylphosphonium bromide and tetra-n-butylphosphonium chloride; arylphosphonium salts such as tetraphenylphosphonium bromide, tetraphenylphosphonium chloride and tetraphenylphosphonium phenoxide (TPPP); and alkylarylphosphonium salts.

[0128] Further specific examples of catalysts for the polymerization reaction include the following: Examples of alkali metal compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, sodium phenylborohydride, and phenylborohydride. Examples of the phenylboronate include potassium boron phenylate, lithium boron phenylate, cesium phenylate, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium hydrogen phosphate, dipotassium phenylphosphate, dilithium phenylphosphate, disodium phenylphosphate, dipotassium phenylphosphate, dilithium phenylphosphate, discesium phenylphosphate; alcoholates and phenolates of sodium, potassium, lithium, and cesium; and disodium salt, dipotassium salt, dilithium salt, and dicesium salt of bisphenol A.

[0129] Examples of alkaline earth metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate. Specific examples of basic boron compounds that can be used as a catalyst in the polymerization step include sodium salts, potassium salts, lithium salts, calcium salts, barium salts, magnesium salts, and strontium salts of tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethylphenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl boron, tributylbenzyl boron, tributylphenyl boron, tetraphenyl boron, benzyltriphenyl boron, methyltriphenyl boron, and butyltriphenyl boron.

[0130] Examples of basic phosphorus compounds that can be used as catalysts in the polymerization step include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.

[0131] Examples of basic ammonium compounds that can be used as a catalyst in the polymerization step include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, and butyltriphenylammonium hydroxide.

[0132] Examples of amine compounds that can be used as catalysts in the polymerization step include 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, and aminoquinoline.

[0133] In addition, known polymerization catalysts can also be used, and preferred examples include antimony compounds, titanium compounds, germanium compounds, tin compounds, and aluminum compounds. Examples of such compounds include oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates, and sulfates of antimony, titanium, germanium, tin, and aluminum. These compounds can also be used in combination of two or more. Among these, tin, titanium, and germanium compounds are preferred from the viewpoint of the melt stability and color of the thermoplastic resin.

[0134] As described above, known catalysts can be used as catalysts for the polymerization reaction. For example, compounds containing manganese, magnesium, titanium, zinc, aluminum, calcium, cobalt, sodium, lithium, or lead can be used. Specific examples include oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates, and sulfates containing these elements. Among these, oxides, acetates, alcoholates, and other compounds of manganese, magnesium, zinc, titanium, and cobalt are preferred from the viewpoints of the melt stability, color, and small amount of insoluble foreign matter in the polymer of the thermoplastic resin. Manganese, magnesium, and titanium compounds are more preferred. These compounds can be used in combination of two or more.

[0135] As catalysts for the polymerization step, zinc, tin, zirconium, and lead salts are preferably used, and these can be used alone or in combination, and can also be used in combination with the above-mentioned alkali metal compounds and alkaline earth metal compounds.

[0136] Specific examples of catalysts that can be used in the polymerization step include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin(II) chloride, tin(IV) chloride, tin(II) acetate, tin(IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead(II) acetate, lead(IV) acetate, zirconium acetate, and titanium tetrabutoxide. Of these, zinc acetate, zirconium acetate, and titanium tetrabutoxide are preferred, with titanium tetrabutoxide being more preferred.

[0137] The catalyst can be prepared by a known method, or a commercially available catalyst may be used. In addition, it is preferable to substantially completely remove catalysts, such as alkali metal compound catalysts and alkaline earth metal compound catalysts, from the thermoplastic resin and the thermoplastic resin composition described in detail below.

[0138] <II-5. Additives> In the polymerization reaction for producing a thermoplastic resin, additives may be used, and antioxidants are preferably used. In the polymerization step, the order of mixing does not matter, but it is preferable to mix not only the silane compound, component A, and component B as monomer compounds, but also the antioxidant with the monomer compounds before starting the polymerization reaction. In the polymerization reaction, it is preferable to polymerize the monomer compounds in the presence of the above-mentioned catalyst.

[0139] Examples of antioxidants include phosphite additives, phenolic antioxidants, hindered phenolic antioxidants, bisphenolic antioxidants, polyphenolic antioxidants, and sulfur-based antioxidants, with phosphite additives being preferred. Specific examples of phosphite antioxidants include organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds. Examples of the antioxidant include at least one selected from the group consisting of (a) a phosphite ester compound in which at least one ester in the molecule is esterified with phenol and / or a phenol having at least one alkyl group having 1 to 25 carbon atoms, (b) phosphorous acid, and (c) tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene-di-phosphonite.Specific examples of the phosphite ester compound (a) include trioctyl phosphite, trioctadecyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, triphenyl phosphite, tris(mononylphenyl)phosphite, tris(mononyl / dinonylphenyl)phosphite, trisnonylphenyl phosphite, tris(octylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, trinonyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, and bis(2,4-di-tert-butylphenyl)pentaerythritol. Examples of suitable diphosphite include bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol phosphite, monooctyldiphenyl phosphite, distearylpentaerythritol diphosphite, tricyclohexyl phosphite, diphenylpentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite. These may be used alone or in combination of two or more. Examples of the organic phosphite compound include "ADK STAB 1178 (product name, the same applies hereinafter)," "ADK STAB 2112," and "ADK STAB HP-10" manufactured by Adeka Corporation; "JP-351," "JP-360," and "JP-3CP" manufactured by Johoku Chemical Industry Co., Ltd.; and "IRGAFOS 168" manufactured by BASF.Examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris(nonylphenyl)phosphate, and 2-ethylphenyldiphenyl phosphate.

[0140] Examples of phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 4,4'-butylidenebis-(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3- (3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis( oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, and the like.Examples of phenol-based antioxidants include "Irganox 1010" (registered trademark, hereinafter the same) and "Irganox 1076" manufactured by BASF, and "ADK STAB AO-50" and "ADK STAB AO-60" manufactured by Adeka Corporation. When blended, the antioxidant is added in an amount of preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.05 parts by mass or more, relative to 100 parts by mass of the total monomer compounds of the thermoplastic resin. It is also preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, even more preferably 0.3 parts by mass or less, or 0.1 parts by mass or less. The phosphorus content in the thermoplastic resin resulting from phosphite-based antioxidants is also, for example, 1 part by mass or less, more preferably 0.5 parts by mass or less, and even more preferably 0.1 parts by mass or less. Only one type of antioxidant may be included, or two or more types may be included. When two or more types are included, it is preferable that the total amount is within the above range.

[0141] It is also possible to produce a thermoplastic resin composition containing an antioxidant by adding an antioxidant to a thermoplastic resin produced by a polymerization reaction. Conventionally, additives have often been added after the production of a resin to prevent thermal history of the additive itself that occurs during the polymerization reaction or to enable adjustment of the amount added depending on the intended use. However, the method for producing a thermoplastic resin of the present invention, in which an antioxidant is added to a monomer compound before the polymerization reaction, has a significant effect of improving the color of the produced thermoplastic resin.

[0142] <II-6. Polymerization Reaction Conditions> In the polymerization reaction for polymerizing the above-described monomer compounds, the mixture of the above-described components is melted, and in the molten state, alcohols derived from the carbonate compound as by-products, such as aryl alcohols such as phenol, methanol, etc., are removed under reduced pressure. By setting the reaction conditions in this manner, the polymerization reaction can proceed efficiently.

[0143] In the polymerization step, it is preferable to allow the polymerization reaction to proceed under a pressure of 400 Pa or less. That is, the pressure in the polymerization reaction is preferably within the range of 400 Pa or less. In the polymerization step, it is preferable to maintain a normal pressure state without reducing the pressure or a state where the pressure is not significantly reduced for a certain period of time, and then reduce the pressure in the system to further allow the polymerization reaction to proceed. For example, in the polymerization step, it is preferable to gradually reduce the reaction pressure from the initial atmospheric pressure to 400 Pa or 200 Pa or less, such as 60,000 Pa, 40,000 Pa, 27,000 Pa, 24,000 Pa, 20,000 Pa, 16,000 Pa, 10,000 Pa, 8,000 Pa, 5,000 Pa, 4,000 Pa, 2,000 Pa, 400 Pa, 400 Pa or less, or 200 Pa or less. For example, in the polymerization step, the pressure may be reduced stepwise from the initial atmospheric pressure to 60,000 Pa, 40,000 Pa, 20,000 Pa, 10,000 Pa, 5,000 Pa, and 200 Pa or less. This depressurization step in which the pressure in the reaction system is reduced stepwise and the degree of depressurization is increased halfway through is preferred because it allows efficient removal of the by-product alcohol while suppressing distillation of raw materials.

[0144] The time for the polymerization step is determined appropriately taking into consideration the type of the target thermoplastic resin, pressure, temperature, and other conditions, but for example, the total time for the polymerization step is within 5 to 10 hours. More specifically, the reaction time before decompression in the reaction system is 0.5 to 3 hours, preferably 1 to 2 hours, and the reaction time after decompression is 1 to 5 hours, preferably 2 to 4 hours.

[0145] In the polymerization step, the temperature in the polymerization reaction is preferably within a range of 150 to 300° C. More preferably, the temperature in the polymerization reaction is 160 to 280° C., even more preferably 170 to 270° C., and particularly preferably 180 to 260° C. Furthermore, the temperature range in the polymerization reaction may be 190 to 290° C., 210 to 280° C., 230 to 270° C., or 240 to 260° C.

[0146] In the polymerization step, the ratio of the molar amount of the catalyst to the total molar amount of the monomer compounds (molar ratio: i.e., molar amount of the catalyst / molar amount of the monomer compounds) is 1.0×10 －７ ~1.0 x 10 －２ (mol / mol: 0.1 to 10,000 μmol / mol, or 1.0 × 10 －４ The molar ratio is preferably 1.0 × 10 to 10 mmol / mol. －７ ~2.0 x 10 －５ mol / mol (or 0.1 to 20 μmol / mol).

[0147] <II-7. Method of Adding Each Component in the Polymerization Reaction> In the polymerization process for producing a thermoplastic resin, the monomer compounds and catalyst serving as raw materials may be mixed together in advance before the polymerization reaction is initiated. Adding the raw materials and catalyst all at once in this manner allows the polymerization reaction to proceed in a simple procedure. Alternatively, a monomer compound other than the silane compound described above, i.e., a dicarboxylic acid, monocarboxylic acid monoester, or carboxylic acid diester represented by any of the above formulas (1) to (6) for forming the ester structural unit (I); and a monomer represented by the above formula (7) and / or a monomer represented by the above formula (8) (a monomer represented by any of the formulas (7) to (10)) for forming the diol structural unit (A), may be mixed in advance to proceed with the first-stage polymerization reaction. In this case, a silane compound and a catalyst for forming the silane structural unit (S) are post-added to the reaction system obtained in the first-stage polymerization reaction (post-addition step a), and the second-stage polymerization reaction is carried out. Alternatively, the first-stage polymerization reaction may be carried out by mixing only a monomer compound other than a silane compound or a monomer compound other than a silane compound with a catalyst, and then a silane compound for forming the silane structural unit (S) may be post-added to the resulting reaction system (post-addition step b) to carry out the second-stage polymerization reaction.

[0148] In the first-stage polymerization reaction described above, a dehydration reaction accompanies the polymerization. In the first-stage polymerization reaction, the amount of dehydration by the end of the reaction is preferably 50 mol% or more, more preferably 60 mol% or more, and even more preferably 70 mol% or more. However, increasing the dehydration rate may extend the reaction time of the first-stage polymerization, potentially worsening the color tone of the resulting resin. Therefore, the dehydration rate in the first-stage polymerization reaction may be, for example, 50 mol% or more and 70 mol% or less, or 50 mol% or more and less than 70 mol%. The limit value of the dehydration rate described above is a value that sets the theoretical amount of dehydration to 100% of the reference value when all monomers are completely dehydrated in the first-stage polymerization reaction. The reaction conditions for the first-stage polymerization reaction are set taking into consideration, for example, the melting points of the monomers, and are not particularly limited. However, to ensure rapid progress of the dehydration reaction, the reaction temperature is preferably 200°C or higher. More preferably, the reaction temperature in the first-stage polymerization reaction is 210°C or 220°C or higher, and even more preferably 230°C or higher. The pressure of the reaction system in the first-stage polymerization reaction is preferably adjusted to a reduced pressure range of 20 to 200 hPa, more preferably 30 to 150 hPa, and even more preferably 50 to 100 hPa. The duration of the first-stage polymerization reaction is, for example, 3 minutes to 1 hour, more preferably 5 to 50 minutes, even more preferably 10 to 40 minutes, and particularly preferably 15 to 30 minutes. In the second-stage polymerization reaction, it is preferable to adopt the reaction conditions described in the above section <II-6. Polymerization reaction conditions>.

[0149] In this way, by post-adding only the silane compound for forming the silane structural unit (S), or the silane compound and the catalyst, it is possible to suppress the amount of low molecular weight compounds (low molecular weight materials) generated and also to improve the color of the resulting thermoplastic resin (reduce the YI value). Note that a catalyst does not have to be used, and in particular in the polymerization reaction employing the above-mentioned post-addition step a or b, particularly the post-addition step b, the polymerization reaction can proceed smoothly without a catalyst.

[0150] <Measurement of polystyrene-equivalent weight average molecular weight (Mw)> Using GPC (gel permeation chromatography), a calibration curve was prepared using standard polystyrene (Shodex STANDARD, SM-105) of known molecular weight (molecular weight distribution = 1) with chloroform as the developing solvent. The elution time and molecular weight value of each peak from the measured standard polystyrene were plotted, and a calibration curve was prepared by cubic approximation. Based on the obtained calibration curve, the weight average molecular weight (Mw) was calculated as a polystyrene-equivalent value using the following formula: [Calculation formula] Mw = Σ(Wi × Mi) / Σ(Wi) (In the above formula, i represents the i-th division point when dividing the molecular weight M, Wi represents the i-th weight, and Mi represents the i-th molecular weight. Furthermore, the molecular weight M represents the molecular weight in polystyrene terms at the same elution time on the calibration curve.)

[0151] [Measurement conditions] Apparatus: Labsolutions manufactured by Shimadzu Corporation Columns: Guard column (Shodex GPC K-G 4A) x 1, analytical column (Shodex GPC K-805L) x 2 Solvent: Chloroform (HPLC grade) Injection volume: 10 μL Sample concentration: 2000 ppm Solvent flow rate: 1 mL / min Measurement temperature: 40° C. Detector: RI

[0152] <Measurement of Glass Transition Temperature (Tg)> A measurement sample was prepared by weighing 5 to 12 mg of test piece into an AI autosampler sample container (RDC aluminum pan, a cylindrical container with a diameter of 6.8 mm and a height of 2.5 mm), and sealing the top of the sample container with an AI autosampler cover. Measurements were performed using a differential scanning calorimeter (DSC) under a nitrogen atmosphere (nitrogen flow rate: 50 ml / min), and 10.0 mg of sapphire was used as a standard substance in the reference cell. The measurement sample adjusted to 30°C was then heated to 280°C at 20°C / min, and then cooled to 30°C at 20°C / min. The temperature was then raised to 280°C at 10°C / min, and the measurement was performed. Measurement device: differential scanning calorimeter (DSC) (product name "DSC-7020", manufactured by Hitachi High-Tech Science Corporation)

[0153] <Method for Measuring Refractive Index (nd)> A 3 mm thick rectangular piece made of the polyester copolymer produced in the Examples and Comparative Examples described in detail below was measured using an Abbe refractometer according to the method of JIS-K-7142.

[0154] <Methods for Calculating Abbe Number (νd), θgF, and θhF> For 3 mm thick right-angled pieces made of polyester resin produced in the Examples and Comparative Examples described in detail below, the refractive index (nd) values ​​at wavelengths of 405 nm, 436 nm, 486 nm, 589 nm, and 656 nm at 20°C were measured using an Abbe refractometer according to the method of JIS-K-7142, and the Abbe number, θgF, and θhF were calculated using the following formulas: νd=(nd-1) / (nF-nC) θgF=(ng-nF) / (nF-nC) θhF=(nh-nF) / (nF-nC) nd: refractive index at wavelength 589 nm nC: refractive index at wavelength 656 nm nF: refractive index at wavelength 486 nm ng: refractive index at wavelength 436 nm nh: refractive index at wavelength 405 nm

[0155] Example 1 15.09 g (0.0280 mol) of BNEF, 4.49 g (0.0120 mol) of BNE, and 10.53 g (0.0102 mol) of BINOL-DC (2,2'-([1,1'-binaphthalene]-2,2'-diylbis(oxy))acetoacetic acid) were placed in a 300 ml four-neck flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated and melted at 60 hPa and 230°C, and the reaction was allowed to proceed for 20 minutes while condensing and removing water distilled from the reaction system using a cooling tube. The pressure was then reduced to less than 1 hPa, and the reaction was allowed to continue for 20 minutes. Thereafter, nitrogen pressure was restored, and 10.53 g (0.0306 mol) of DNDMS (dinaphthyldimethoxysilane) and 100 μmol / mol (the catalyst amount is the relative molar amount to BNEF and BNE) of tetrabutyl orthotitanate (tetrabutyl orthotitanate) as a catalyst were added to the system, and the pressure was reduced again. Methanol and water distilled from the reaction system at 200 hPa and 230 ° C. were condensed with a cooling tube and removed for 30 minutes, while the reaction was allowed to proceed. Thereafter, the temperature was raised to 245 ° C. for 20 minutes, then the pressure was reduced to 100 hPa for 10 minutes, reduced to 50 hPa, and the temperature was raised to 260 ° C. for 10 minutes, reduced to less than 1 hPa, and the reaction was carried out for 70 minutes. The resulting polysilyl ether resin had an Mw of 25,378, a refractive index (nd) of 1.695, an Abbe number (vd) of 18.2, θgF of 0.668, θhF of 1.317, and a glass transition temperature (Tg) of 151° C. These properties are shown in Table 2 below.

[0156] Example 2 BNEF 15.09 g (0.0280 mol), BNE 4.49 g (0.0120 mol), BINOL-DC 8.21 g (0.0204 mol) were placed in a 300 ml four-neck flask equipped with a stirrer, and the system was replaced with a nitrogen atmosphere. The raw materials were heated and melted at 60 hPa and 230 ° C., and the water distilled from the reaction system was condensed with a cooling tube and removed while the reaction proceeded for 30 minutes, after which the pressure was reduced to less than 1 hPa, and the reaction was carried out for 20 minutes. Thereafter, the nitrogen pressure was restored, and 7.02 g (0.0204 mol) of DNDMS and 100 μmol / mol of tetrabutyl orthotitanate as a catalyst (the catalyst amount is the relative molar amount to BNEF and BNE) were added to the system, and the pressure was reduced again. Methanol and water distilled from the reaction system at 200 hPa and 230 ° C. were condensed in a cooling tube and removed, while the reaction proceeded for 30 minutes. Thereafter, the temperature was raised to 245 ° C. for 20 minutes, then reduced pressure to 100 hPa for 10 minutes, reduced pressure to 50 hPa, heated to 260 ° C. for 10 minutes, reduced pressure to less than 1 hPa, and the reaction was carried out for 60 minutes. The Mw of the obtained polysilyl ether resin was 18,076, the refractive index (nd) was 1.693, the Abbe number (vd) was 18.3, θgF was 0.671, θhF was 1.326, and the glass transition temperature (Tg) was 151 ° C. These properties are shown in Table 2 below.

[0157] Example 3 BNEF 15.09 g (0.0280 mol), BNE 4.49 g (0.0120 mol), BINOL-DC 12.32 g (0.0306 mol) were placed in a 300 ml four-neck flask equipped with a stirrer, and the system was replaced with a nitrogen atmosphere. The raw materials were heated and melted at 60 hPa and 230 ° C., and the water distilled from the reaction system was condensed with a cooling tube and removed, and the reaction was allowed to proceed for 30 minutes, after which the pressure was reduced to less than 1 hPa, and the reaction was carried out for 20 minutes. Thereafter, the nitrogen pressure was restored, and 3.51 g (0.0102 mol) of DNDMS and 100 μmol / mol of tetrabutyl orthotitanate as a catalyst (the catalyst amount is the relative molar amount to BNEF and BNE) were added to the system, and the pressure was reduced again. Methanol and water distilled from the reaction system at 200 hPa and 230 ° C. were condensed in a cooling tube and removed, while the reaction proceeded for 30 minutes. Thereafter, the temperature was raised to 245 ° C. for 20 minutes, then reduced pressure to 100 hPa for 10 minutes, reduced pressure to 50 hPa, heated to 260 ° C. for 10 minutes, reduced pressure to less than 1 hPa, and the reaction was carried out for 60 minutes. The Mw of the obtained polysilyl ether resin was 21,042, the refractive index (nd) was 1.690, the Abbe number (vd) was 18.2, θgF was 0.674, θhF was 1.333, and the glass transition temperature (Tg) was 153 ° C. These properties are shown in Table 2 below.

[0158] Example 4 BNEF 15.09g (0.0280mol), BNE 4.49g (0.0120mol), BINOL-DP 5.66g (0.0102mol), DNDMS 10.53g (0.0306mol), and tetrabutyl orthotitanate 100μmol / mol (catalyst amount is the relative molar amount to BNEF and BNE) as a catalyst was placed in a 300ml four-necked flask equipped with a stirrer, and the system was replaced under a nitrogen atmosphere. 300hPa, 210 ° C. raw materials were heated and melted, after 30 minutes of reaction, the temperature was raised to 230 ° C. and the pressure was reduced to 200hPa for 30 minutes, and the reaction was carried out, and the methanol and phenol distilled from the reaction system were condensed with a cooling tube, and the reaction was allowed to proceed while being removed. Next, the temperature was raised to 245 ° C. for 20 minutes, the pressure was reduced to 100 hPa for 10 minutes, the temperature was raised to 260 ° C., the pressure was reduced to 50 hPa for 10 minutes, and the pressure was reduced to less than 1 hPa for 60 minutes. The Mw of the obtained polysilyl ether resin was 22,614, the refractive index (nd) was 1.695, the Abbe number (vd) was 18.2, the θgF was 0.668, the θhF was 1.317, and the glass transition temperature (Tg) was 151 ° C. These properties are shown in Table 2 below.

[0159] Example 5 BNEF 15.09g (0.0280mol), BNE 4.49g (0.0120mol), BINOL-DP 11.31g (0.0204mol), DNDMS 7.02g (0.0204mol), and tetrabutyl orthotitanate 100μmol / mol (catalyst amount is the relative molar amount to BNEF and BNE) as a catalyst was placed in a 300ml four-necked flask equipped with a stirrer, and the system was replaced under a nitrogen atmosphere. 300hPa, 210 ° C. raw materials were heated and melted, after 30 minutes of reaction, the temperature was raised to 230 ° C. and the pressure was reduced to 200hPa for 30 minutes, and the reaction was carried out, and the methanol and phenol distilled from the reaction system were condensed with a cooling tube, and the reaction was allowed to proceed while being removed. Next, the temperature was raised to 245 ° C. for 20 minutes, the pressure was reduced to 100 hPa for 10 minutes, the temperature was raised to 260 ° C., the pressure was reduced to 50 hPa for 10 minutes, and the pressure was reduced to less than 1 hPa for 50 minutes, and the reaction was carried out. The Mw of the obtained polysilyl ether resin was 18,000, the refractive index (nd) was 1.693, the Abbe number (vd) was 18.3, the θgF was 0.671, the θhF was 1.326, and the glass transition temperature (Tg) was 150 ° C. These properties are shown in Table 2 below.

[0160] Example 6 15.08 g (0.0280 mol) of BNEF, 4.49 g (0.0120 mol) of BNE, 16.97 g (0.0306 mol) of BINOL-DP, 3.51 g (0.0102 mol) of DNDMS, and 100 μmol / mol of tetrabutyl orthotitanate and 50 μmol / mol of zinc acetate (II) dihydrate as catalysts (the catalytic amount is the number of moles relative to the BNEF and BNE) were placed in a 300 ml four-neck flask equipped with a stirrer, and the inside of the system was purged with a nitrogen atmosphere. The raw materials were heated and melted at 300 hPa and 210 ° C., and after 30 minutes of reaction, the temperature was raised to 230 ° C., the pressure was reduced to 200 hPa, and the reaction was continued for 30 minutes. The methanol and phenol distilled from the reaction system were condensed with a cooling tube and removed while the reaction proceeded. Next, the temperature was raised to 245 ° C., the pressure was reduced to 100 hPa, and the reaction proceeded for 20 minutes, the pressure was reduced to 50 hPa, and the reaction proceeded for 10 minutes. The temperature was raised to 260 ° C., the pressure was reduced to less than 1 hPa, and the reaction proceeded for 30 minutes. The Mw of the obtained polysilyl ether resin was 22,303, the refractive index (nd) was 1.690, the Abbe number (vd) was 18.2, the θgF was 0.668, the θhF was 1.317, and the glass transition temperature (Tg) was 154 ° C. These properties are shown in Table 2 below.

[0161] Example 7 15.09 g (0.0280 mol) of BNEF, 4.49 g (0.0120 mol) of BNE, 4.39 g (0.0102 mol) of BINOL-DM (2,2'-([1,1'-binaphthalene]-2,2'-diylbis(oxy))methyl acetoacetate), 10.53 g (0.0306 mol) of DNDMS, and 100 μmol / mol of tetrabutyl orthotitanate as a catalyst (the catalyst amount is the number of moles relative to BNEF and BNE) were placed in a 300 ml four-neck flask equipped with a stirrer, and the inside of the system was purged with a nitrogen atmosphere. The raw materials were heated and melted at 300 hPa and 210 ° C., and after 30 minutes of reaction, the temperature was raised to 230 ° C., the pressure was reduced to 200 hPa, and the reaction was continued for 30 minutes. The methanol distilled from the reaction system was condensed using a cooling tube and removed while the reaction proceeded. Next, the temperature was raised to 245 ° C. for 20 minutes, the pressure was reduced to 100 hPa for 10 minutes, the temperature was raised to 260 ° C., the pressure was reduced to 50 hPa for 10 minutes, and the pressure was reduced to less than 1 hPa for 60 minutes. The Mw of the obtained polysilyl ether resin was 22,701, the refractive index (nd) was 1.695, the Abbe number (vd) was 18.2, θgF was 0.668, θhF was 1.317, and the glass transition temperature (Tg) was 151 ° C. These properties are shown in Table 2 below.

[0162] Example 8 BNEF 15.09g (0.0280mol), BNE 4.49g (0.0120mol), BINOL-DM 8.78g (0.0204mol), DNDMS 7.02g (0.0204mol), and tetrabutyl orthotitanate 100μmol / mol (catalyst amount is the relative molar amount to BNEF and BNE) as a catalyst was placed in a 300ml four-necked flask equipped with a stirrer, and the system was replaced under a nitrogen atmosphere. 300hPa, 210 ° C. raw materials were heated and melted, after 30 minutes of reaction, the temperature was raised to 230 ° C. and the pressure was reduced to 200hPa for 30 minutes, and the reaction was allowed to proceed, with the methanol distilled from the reaction system condensed in a cooling tube, and the reaction was allowed to proceed while removing. Next, the temperature was raised to 245 ° C. for 20 minutes, the pressure was reduced to 100 hPa for 10 minutes, the temperature was raised to 260 ° C., the pressure was reduced to 50 hPa for 10 minutes, and the pressure was reduced to less than 1 hPa for 50 minutes, and the reaction was carried out. The Mw of the obtained polysilyl ether resin was 17,509, the refractive index (nd) was 1.693, the Abbe number (vd) was 18.3, θgF was 0.671, θhF was 1.326, and the glass transition temperature (Tg) was 150 ° C. These properties are shown in Table 2 below.

[0163] Example 9 15.08 g (0.0280 mol) of BNEF, 4.49 g (0.0120 mol) of BNE, 13.17 g (0.0306 mol) of BINOL-DM, 3.51 g (0.0102 mol) of DNDMS, and 100 μmol / mol of tetrabutyl orthotitanate and 50 μmol / mol of zinc acetate (II) dihydrate as catalysts (the catalytic amount is the number of moles relative to the BNEF and BNE) were placed in a 300 ml four-neck flask equipped with a stirrer, and the inside of the system was purged with a nitrogen atmosphere. The raw materials were heated and melted at 300 hPa and 210 ° C., and after 30 minutes of reaction, the temperature was raised to 230 ° C., the pressure was reduced to 200 hPa, and the reaction was continued for 30 minutes. The methanol distilled from the reaction system was condensed using a cooling tube and removed while the reaction proceeded. Next, the temperature was raised to 245 ° C., the pressure was reduced to 100 hPa, and the reaction proceeded for 20 minutes, the pressure was reduced to 50 hPa, and the reaction proceeded for 10 minutes. The temperature was raised to 260 ° C., the pressure was reduced to less than 1 hPa, and the reaction proceeded for 30 minutes. The Mw of the obtained polysilyl ether resin was 21,524, the refractive index (nd) was 1.690, the Abbe number (vd) was 18.2, the θgF was 0.674, the θhF was 1.333, and the glass transition temperature (Tg) was 153 ° C. These properties are shown in Table 2 below.

[0164] Example 10 BNEF 15.09g (0.0280mol), BNE 4.49g (0.0120mol), FDPM (9,9-fluorene-methyl dipropionate) 3.23g (0.0095mol), DNDMS 10.73g (0.0312mol), and lead (II) acetate trihydrate 50μmol / mol (catalyst amount is the relative molar amount to BNEF and BNE) as a catalyst were placed in a 300ml four-necked flask equipped with a stirrer, and the system was substituted under a nitrogen atmosphere. The raw materials were heated and melted at 400hPa and 210 ° C., reacted for 30 minutes, then heated to 230 ° C. and reacted for 20 minutes, and the reaction was allowed to proceed while condensing and removing the methanol distilled from the reaction system with a cooling tube. Next, the temperature was raised to 245 ° C, the pressure was reduced to 200 hPa for 20 minutes, the pressure was reduced to 100 hPa for 10 minutes, the temperature was raised to 255 ° C, the pressure was reduced to 50 hPa for 10 minutes, and the pressure was reduced to less than 1 hPa for 150 minutes, and the reaction was carried out. The Mw of the obtained polysilyl ether resin was 25,305, the refractive index (nd) was 1.692, the Abbe number (vd) was 18.5, θgF was 0.668, θhF was 1.311, and the glass transition temperature (Tg) was 147 ° C. These properties are shown in Table 2 below.

[0165] Example 11 15.09 g (0.0280 mol) of BNEF, 6.32 g (0.0120 mol) of DPBN (2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene), 3.23 g (0.0095 mol) of FDPM, 10.73 g (0.0312 mol) of DNDMS, and 50 μmol / mol of lead (II) acetate trihydrate as a catalyst (the catalytic amount is the number of moles relative to BNEF and DPBN) were placed in a 300 ml four-neck flask equipped with a stirrer, and the inside of the system was purged with a nitrogen atmosphere. The raw materials were heated and melted at 400 hPa and 210 ° C., and after 30 minutes of reaction, the temperature was raised to 230 ° C. and the reaction was continued for 20 minutes. The methanol distilled from the reaction system was condensed using a cooling tube and the reaction was allowed to proceed while being removed. Next, the temperature was raised to 245 ° C., the pressure was reduced to 200 hPa for 20 minutes, the pressure was reduced to 100 hPa for 10 minutes, the temperature was raised to 255 ° C., the pressure was reduced to 50 hPa for 10 minutes, and the pressure was reduced to less than 1 hPa for 240 minutes. These properties are shown in Table 2 below. The Mw of the obtained polysilyl ether resin was 29,949, the refractive index (nd) was 1.697, the Abbe number (vd) was 17.7, θgF was 0.680, θhF was 1.341, and the glass transition temperature (Tg) was 157 ° C.

[0166] Example 12 36.63 g (0.0680 mol) of BNEF, 2.43 g (0.0120 mol) of 1,12-dodecanediol, 21.05 g (0.0612 mol) of DNDMS, 6.90 g (0.0204 mol) of FDPM, and catalysts consisting of 20 μmol / mol of tetrabutyl orthotitanate, 400 μmol / mol of zinc (II) acetate dihydrate, and 50 μmol / mol of lead (II) acetate trihydrate (the catalyst amounts are the number of moles relative to BNEF and BNE) were placed in a 300 ml four-neck flask equipped with a stirrer, and the inside of the system was purged with a nitrogen atmosphere. The raw materials were heated and melted at 400 hPa and 230 ° C., and the reaction was allowed to proceed for 60 minutes while the methanol distilling from the reaction system was condensed and removed using a cooling tube. The pressure was reduced to 200 hPa and the reaction was allowed to proceed for 30 minutes, and then the temperature was raised to 245 ° C. and the pressure was reduced to 100 hPa for 20 minutes, then the pressure was reduced to 50 hPa for 10 minutes, and the temperature was raised to 260 ° C. and the pressure was reduced to less than 1 hPa for 40 minutes. The Mw of the obtained polysilyl ether resin was 65,341, the refractive index (nd) was 1.684, the Abbe number (vd) was 19.0, θgF was 0.661, θhF was 1.297, and the glass transition temperature (Tg) was 149 ° C. These properties are shown in Table 2 below.

[0167] Example 13 BNEF 30.16g (0.0560mol), DPBN 12.64g (0.0240mol), FDPM 6.97g (0.0206mol), DPDMS (diphenyldimethoxysilane) 5.03g (0.0206mol), DNDMS 14.17g (0.0412mol), and zinc acetate (II) dihydrate 200μmol / mol (catalyst amount is the relative molar amount to BNEF and DPBN) was placed in a 300ml four-necked flask equipped with a stirrer, and the system was replaced under a nitrogen atmosphere. The raw materials were heated and melted at 400hPa and 210 ° C., and after 45 minutes of reaction, the temperature was raised to 230 ° C. and reacted for 45 minutes, and the methanol distilled from the reaction system was condensed with a cooling tube, and the reaction was allowed to proceed while removing. Next, the pressure was reduced to 200 hPa for 20 minutes, reduced to 100 hPa and heated to 240 ° C for 10 minutes, reduced to 50 hPa for 10 minutes, heated to 255 ° C, and then reduced to less than 1 hPa for 215 minutes, and the reaction was carried out. The Mw of the obtained polysilyl ether resin was 29,305, the refractive index (nd) was 1.690, the Abbe number (vd) was 18.2, θgF was 0.679, θhF was 1.342, and the glass transition temperature (Tg) was 152 ° C. These properties are shown in Table 2 below.

[0168] Example 14 BNEF 30.16g (0.0560mol), DPBN 12.64g (0.0240mol), FDPM 8.37g (0.0247mol), DPDMS 6.03g (0.0247mol), DNDMS 11.34g (0.0330mol), and zinc acetate (II) dihydrate 300μmol / mol (catalyst amount is the relative molar amount to BNEF and DPBN) as a catalyst was placed in a 300ml four-necked flask equipped with a stirrer, and the system was replaced under a nitrogen atmosphere. The raw materials were heated and melted at 400hPa and 210 ° C., and after 45 minutes of reaction, the temperature was raised to 230 ° C. and reacted for 45 minutes, and the methanol distilled from the reaction system was condensed with a cooling tube, and the reaction was allowed to proceed while removing. Next, the pressure was reduced to 200 hPa for 20 minutes, reduced to 100 hPa and heated to 240 ° C for 10 minutes, reduced to 50 hPa for 10 minutes, heated to 255 ° C, and then reduced to less than 1 hPa for 240 minutes, and the reaction was carried out. The Mw of the obtained polysilyl ether resin was 23,330, the refractive index (nd) was 1.687, the Abbe number (vd) was 18.3, θgF was 0.674, θhF was 1.336, and the glass transition temperature (Tg) was 150 ° C. These properties are shown in Table 2 below.

[0169] Example 15 BNEF 10.78g (0.0200mol), DPBN 10.53g (0.0200mol), DMT (dimethyl terephthalate) 1.58g (0.0082mol), DNDMS 11.23g (0.0326mol), and tetrabutyl orthotitanate 200μmol / mol (catalyst amount is the relative molar amount to BNEF and DPBN) as a catalyst was placed in a 300ml four-necked flask equipped with a stirrer, and the system was replaced under a nitrogen atmosphere. 400hPa, 210 ° C. raw materials were heated and melted, after 30 minutes of reaction, the temperature was raised to 230 ° C., the pressure was reduced to 200hPa, and the reaction was carried out for 20 minutes, and the methanol distilled from the reaction system was condensed with a cooling tube, and the reaction was allowed to proceed while removing. Next, the temperature was raised to 245 ° C, the pressure was reduced to 100 hPa for 20 minutes, the pressure was reduced to 50 hPa for 10 minutes, the temperature was raised to 255 ° C, and the pressure was reduced to less than 1 hPa for 80 minutes, and the reaction was carried out. The Mw of the obtained polysilyl ether resin was 21,539, the refractive index (nd) was 1.702, the Abbe number (vd) was 17.1, the θgF was 0.682, the θhF was 1.292, and the glass transition temperature (Tg) was 159 ° C. These properties are shown in Table 2 below.

[0170] Example 16 18.87 g (0.0350 mol) of BNEF, 2.63 g (0.0050 mol) of DPBN, 3.74 g (0.0100 mol) of BNE (2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene), 5.05 g (0.0260 mol) of DMT, 8.94 g (0.0260 mol) of DNDMS, and 200 μmol / mol of tetrabutyl orthotitanate as a catalyst (the catalytic amount is the number of moles relative to BNEF, DPBN, and BNE) were placed in a 300 ml four-neck flask equipped with a stirrer, and the inside of the system was purged with a nitrogen atmosphere. The raw materials were heated and melted at 400 hPa and 210 ° C., and after 30 minutes of reaction, the temperature was raised to 230 ° C., the pressure was reduced to 200 hPa, and the reaction was continued for 20 minutes. The methanol distilled from the reaction system was condensed using a cooling tube and removed while the reaction proceeded. Next, the temperature was raised to 245 ° C., the pressure was reduced to 100 hPa for 20 minutes, the pressure was reduced to 50 hPa for 10 minutes, and the temperature was raised to 255 ° C., and the pressure was reduced to less than 1 hPa for 120 minutes. The resulting polysilyl ether resin had an Mw of 21,706, a refractive index (nd) of 1.690, an Abbe number (vd) of 18.1, θgF of 0.670, θhF of 1.322, and a glass transition temperature (Tg) of 161 ° C. These properties are shown in Table 2 below.

[0171] Example 17 10.78 g (0.0200 mol) of BNEF, 10.53 g (0.0200 mol) of DPBN, 1.99 g (0.0082 mol) of 2,6-DMNDC (2,6-naphthalenedicarboxylic acid dimethyl ester), 11.23 g (0.0326 mol) of DNDMS, and 200 μmol / mol of tetrabutyl orthotitanate and 200 μmol / mol of zinc acetate (II) dihydrate as catalysts (the catalytic amount is the number of moles relative to BNEF and DPBN) were placed in a 300 ml four-neck flask equipped with a stirrer, and the inside of the system was purged with a nitrogen atmosphere. The raw materials were heated and melted at 400 hPa and 210 ° C., and after 30 minutes of reaction, the temperature was raised to 230 ° C., the pressure was reduced to 200 hPa, and the reaction was continued for 20 minutes. The methanol distilled from the reaction system was condensed using a cooling tube and removed while the reaction proceeded. Next, the temperature was raised to 245 ° C., the pressure was reduced to 100 hPa for 20 minutes, the pressure was reduced to 50 hPa for 10 minutes, and the temperature was raised to 255 ° C., and the pressure was reduced to less than 1 hPa for 60 minutes. The Mw of the obtained polysilyl ether resin was 17,881, the refractive index (nd) was 1.704, the Abbe number (vd) was 17.0, θgF was 0.685, θhF was 1.371, and the glass transition temperature (Tg) was 163 ° C. These properties are shown in Table 2 below.

[0172] Example 18 i) Synthesis of BIPOL-DMB (methyl 10,10'-([9,9'-biphenanthrene]-10,10'-diylbis(oxy))acetobutyrate) 80.4 g (0.21 mol) of 9,9'-biphenanthrene-10,10'-diol, 123 g of N-methylpyrrolidone, 60.5 g of potassium carbonate, and 4.0 g of potassium iodide were charged into a four-neck flask and purged with nitrogen. The temperature was then raised to 90°C, and 70.9 g (0.52 mol) of methyl chlorobutyrate was added dropwise over 1 hour while maintaining the temperature of the reaction solution at 90°C. The mixture was then stirred while maintaining the temperature inside the flask at 90°C. The reaction was completed after 18 hours of post-stirring. HPLC analysis of the reaction solution after the reaction showed that the reaction selectivity for the target compound, BIPOL-DMB, was 99.7%. Thereafter, 240 g of water was added, and the mixture was cooled and stirred overnight at 25°C, after which the precipitated solid was filtered off. 157.0 g of the obtained solid and 367 g of methyl isobutyl ketone were charged into a four-neck flask, and after nitrogen substitution, the mixture was heated to dissolve. 249 g of water was then added, and the mixture was washed with water at 80°C, and the aqueous layer was removed. This operation was repeated four times. 141 g of methyl isobutyl ketone and water were then distilled off. The liquid was then cooled and stirred overnight while maintaining the temperature at 25°C, and the precipitated solid was then filtered off. The solid matter collected by filtration was dried at 80°C under reduced pressure to obtain 108.4 g of methyl 10,10'-([9,9'-biphenanthrene]-10,10'-diylbis(oxy))acetobutyrate (BIPOL-DMB or 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthryl) (yield: 90.7%). The compound obtained was analyzed by liquid chromatography mass spectrometry and １ H-NMR and １３ C-NMR analysis revealed that the product was BIPOL-DMB. Liquid chromatography mass spectrometry (mass spectrometry / electrospray ionization): mass 609.23 [M+Na] 　１H-NMR analysis (400MHz, solvent: deuterated chloroform) δ <ppm>: 8.81-8.83 (d, 2H), 8.75-8.77 (d, 2H), 8.29-8.31 (dd, 2H), 7.69-7.79 (dt, 2H), 7.69-7.73 (dt , 2H), 7.55-7.59 (m, 2H), 7.31-7.33 (d, 4H), 3.88-3.93 (m, 2H), 3.54-3.58 (m, 2H), 3.36 (s, 6H), 1.88-1.94 (m, 2H), 1.58-1.74 (m, 6H). 　１３ C-NMR (400 MHz, solvent: deuterated chloroform) δ <ppm>: 173.42, 151.70, 132.75, 131.84, 128.22, 128.14, 127.16, 126.94, 126.88, 126.86, 125.54, 123.43, 122.93, 122.66, 122.32, 72.33, 51.21, 29.95, 25.25. The purity of the obtained biphenanthrene dicarboxylic acid compound as measured by high performance liquid chromatography was 99.5%, and the hue of a 10% THF solution obtained by the above analytical method was APHA20. The PXRD measurement chart of the obtained solid biphenanthrene dicarboxylic acid compound is shown in Figure 1. The peak pattern revealed that the solid of the target compound obtained was crystalline. The diffraction angles 2θ (°) of the diffraction peaks that appeared, the relative integrated intensities based on the peak with the strongest integrated intensity, and the relative intensities based on the peak with the strongest intensity are shown in Table 1, with peaks having a relative integrated intensity of 5 or more being selected. The melting point of the obtained biphenanthrenedicarboxylic acid compound crystals was measured by the above analytical method and found to be 134° C. The differential scanning calorimetry chart is shown in FIG.

[0173] ii) Synthesis of Thermoplastic Resin 25.85 g (0.0480 mol) of BNEF, 5.74 g (0.0098 mol) of BIPOL-DMB (methyl 10,10'-([9,9'-biphenanthrene]-10,10'-diylbis(oxy))acetobutyrate) obtained by the method described in section i) above, 13.47 g (0.0392 mol) of DNDMS, and 10 μmol / mol of tetrabutyl orthotitanate and 50 μmol / mol of lead acetate (II) trihydrate as catalysts (all catalyst amounts are expressed in terms of moles relative to BNEF) were placed in a 300 ml four-neck flask equipped with a stirrer, and the inside of the system was purged with a nitrogen atmosphere. The raw materials were heated and melted at 400 hPa and 210 ° C., and after 30 minutes of reaction, the temperature was raised to 230 ° C., the pressure was reduced to 200 hPa, and the reaction was continued for 30 minutes. The methanol distilled from the reaction system was condensed with a cooling tube and removed while the reaction proceeded. Next, the temperature was raised to 245 ° C., the pressure was reduced to 100 hPa for 20 minutes, the pressure was reduced to 50 hPa for 10 minutes, and the temperature was raised to 260 ° C., and the pressure was reduced to less than 1 hPa for 63 minutes. The Mw of the obtained polysilyl ether resin was 23,898, the refractive index (nd) was 1.698, the Abbe number (vd) was 17.8, θgF was 0.664, θhF was 1.307, and the glass transition temperature (Tg) was 164 ° C. These properties are shown in Table 2 below.

[0174] Example 19 34.47 g (0.0640 mol) of BNEF, 8.43 g (0.0160 mol) of DPBN, 6.85 g (0.0124 mol) of BINOL-DP (2,2′-([1,1′-binaphthalene]-2,2′-diylbis(oxy))phenyl acetoacetate), 8.37 g (0.0247 mol) of FDPM, 11.34 g (0.0330 mol) of DNDMS, 3.02 g (0.0124 mol) of DPDMS, and 20 μmol / mol of tetrabutyl orthotitanate and 50 μmol / mol of zinc acetate (II) dihydrate as catalysts (the amounts of the catalysts are expressed in terms of moles relative to BNEF and DPBN) were added to a 300 ml flask equipped with a stirrer. The mixture was placed in a four-neck flask and the system was substituted with a nitrogen atmosphere. The raw materials were heated and melted at 400 hPa and 230 ° C., and after 30 minutes of reaction, the pressure was reduced to 200 hPa and the reaction was continued for 30 minutes. The methanol and phenol distilled from the reaction system were condensed using a cooling tube and the reaction was allowed to proceed while being removed. The mixture was then heated to 245 ° C., reduced to 100 hPa for 30 minutes, reduced to 50 hPa for 10 minutes, and heated to 260 ° C., and then reduced to less than 1 hPa for 72 minutes. The resulting polysilyl ether resin had an Mw of 31,420, a refractive index (nd) of 1.688, an Abbe number (vd) of 18.3, θgF of 0.672, θhF of 1.327, and a glass transition temperature (Tg) of 154 ° C. These properties are shown in Table 2 below.

[0175] Example 20 34.47 g (0.0640 mol) of BNEF, 8.43 g (0.0160 mol) of DPBN, 11.42 g (0.0206 mol) of BINOL-DP, 8.37 g (0.0247 mol) of FDPM, 11.34 g (0.0330 mol) of DNDMS, 1.01 g (0.0041 mol) of DPDMS, and 20 μmol / mol of tetrabutyl orthotitanate and 50 μmol / mol of zinc acetate (II) dihydrate as catalysts (catalyst amounts are all relative molar amounts to BNEF and DPBN) were placed in a 300 ml four-neck flask equipped with a stirrer, and the inside of the system was purged with a nitrogen atmosphere. The raw materials were heated and melted at 400 hPa and 230 ° C., and after 30 minutes of reaction, the pressure was reduced to 200 hPa and the reaction was continued for 30 minutes. The methanol and phenol distilled from the reaction system were condensed using a cooling tube and the reaction was continued while being removed. The temperature was then raised to 245 ° C., the pressure was reduced to 100 hPa for 30 minutes, the pressure was reduced to 50 hPa for 10 minutes, the temperature was raised to 260 ° C., and the pressure was reduced to less than 1 hPa for 95 minutes. The resulting polysilyl ether resin had an Mw of 31,764, a refractive index (nd) of 1.689, an Abbe number (vd) of 18.2, θgF of 0.674, θhF of 1.333, and a glass transition temperature (Tg) of 158 ° C. These properties are shown in Table 2 below.

[0176] Comparative Example 1 BNEF 70.00g (0.130mol), DPDMS 34.25g (0.140mol), and zinc (II) acetate dihydrate 6μmol / mol (catalyst amount is the relative molar amount to BNEF) as a catalyst were placed in a 300ml four-necked flask equipped with a stirrer, and the system was replaced under a nitrogen atmosphere. After heating and melting the raw materials at 210 ° C. and 600hPa and reacting for 20 minutes, the temperature was raised to 230 ° C. and the pressure was reduced to 400hPa and the reaction was continued for 20 minutes, and the methanol distilled from the reaction system was condensed with a cooling tube and removed while the reaction proceeded. Next, the pressure was reduced to 200hPa for 10 minutes, the temperature was raised to 245 ° C. and the pressure was reduced to 100hPa for 10 minutes, the pressure was reduced to 50hPa for 10 minutes, the temperature was raised to 260 ° C. and the pressure was reduced to less than 1hPa for 120 minutes, and the reaction was carried out. The resulting polysilyl ether resin had an Mw of 33,000, a refractive index (nd) of 1.680, an Abbe number (vd) of 19.7, θgF of 0.658, θhF of 1.284, and a glass transition temperature (Tg) of 136° C. These properties are shown in Table 2 below.

[0177]

[0178] The molecular structures of the monomer compounds used in the above-mentioned Examples and Comparative Examples are as follows:

[0179] The results of the examples and comparative examples confirmed that the thermoplastic resin of this embodiment suppresses chromatic aberration through low θgF and θhF, while achieving a high refractive index (nd) and Abbe number (νd). Thus, thermoplastic resins with favorable properties in terms of chromatic aberration, refractive index, and the like can be suitably used in optical applications. Furthermore, the properties of the resulting thermoplastic resin can also be adjusted and improved by the method for producing the thermoplastic resin. For example, in examples in which a silane compound and a catalyst are added to the reaction system after the start of the polymerization reaction, or in which only a silane compound is added, it is possible to suppress the generation of low-molecular-weight compounds and improve the hue, as indicated by a reduced YI value. These effects of improving the properties of the thermoplastic resin are thought to be due to, for example, the ease with which the generation of cyclized products and colored products resulting from the reaction of a silane compound with a dicarboxylic acid such as BINOL-DC is suppressed.

Claims

1. A thermoplastic resin having a silane structural unit (S), an ester structural unit (I), and a diol structural unit (A), wherein the silane structural unit (S) is derived from any of silane compounds including diaryldialkoxysilane, diaryldiaryloxysilane, and diarylmonoalkoxymonoaryloxysilane, and the ester structural unit (I) is derived from any of dicarboxylic acids, monocarboxylic acid monoesters, and carboxylic acid diesters represented by any of the following general formulas (1) to (6): (In general formula (1), R １ and R ２ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may have a substituent; R ａ represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and m represents an integer of 0 to 4. (In general formula (2), R １ and R ２ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may have a substituent; R ａ and R ｂ each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and m and n each independently represent an integer of 0 to 3. (In general formula (3), R １ and R ２ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may have a substituent; R ａ represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and m represents an integer of 0 to 4. (In general formula (4), R ５ and R ６ each independently represents a halogen atom, an alkyl group which may have a substituent, or an aryl group; a and b each independently represent an integer of 0 to 4; R ７ and R ８ each independently represents a C1-8 alkylene group which may have a substituent; c and d each independently represent an integer of 1 to 5; R ９ and R １０ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent. (In general formula (5), R １１ each independently represents an alkylene group having 1 to 4 carbon atoms; R １２ each independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a halogen atom; each n independently represents 0 or an integer of 1 to 4; R １３ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 4 carbon atoms which may have a substituent. (In general formula (6), R ２１ , R ２２ each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, R ２３ ~R ３０ each independently represents a hydrogen atom, an aliphatic group having 1 to 12 carbon atoms, or an aromatic group having 6 to 20 carbon atoms; a and b each independently represent an integer of 0 or more; R ３１ , R ３２ each independently represents a hydrogen atom, a methyl group, an ethyl group, or a phenyl group which may have a substituent.) A thermoplastic resin, wherein the diol structural unit (A) is derived from any of the diol compounds represented by the following general formulas (7) to (10): In general formula (7), Ra and Rb are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which contains one or more heterocyclic atoms selected from O, N, and S and which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡C-Rh, Rh represents an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more heterocyclic atoms selected from O, N, and S and which may have a substituent, X represents a single bond or a fluorene group which may have a substituent, A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent; m and n each independently represent an integer of 0 to 6; and a and b each independently represent an integer of 0 to 10. (In general formula (8), Rc and Rd are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 20 carbon atoms which may have a substituent; A and B are each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent; p and q are each independently an integer of 0 to 4; a and b are each independently an integer of 0 to 10; Y １ represents a single bond, —O—, —S—, —SO—, —SO ２ represents -, -CO-, or a divalent group represented by any one of formulas (i) to (vi). (In general formula (i), R ８ ~R １７ each independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms; in the general formulae (ii) to (vi), R １８ and R １９ each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms which may have a substituent, or １８ and R １９ are bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms; R ２０ represents an alkylene group having 1 to 9 carbon atoms which may have a substituent, c represents an integer of 0 to 20, and d represents an integer of 1 to 500. A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, p and q each independently represent an integer of 0 to 4, and a and b each independently represent an integer of 0 to 10. (In general formula (9), R ４１ and R ４２ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may have a substituent, and a represents an integer of 2 to 16. (In the general formula (10), R is H, CH ３ or C ２ H ５ Represents.) 2. The thermoplastic resin according to claim 1, wherein the silane structural unit (S) is derived from a diaryldialkoxysilane.

3. The thermoplastic resin according to claim 2, wherein the diaryldialkoxysilane has an optionally substituted C6-20 aryl group and an optionally substituted C1-8 alkoxy group.

4. The thermoplastic resin according to claim 3, wherein the diaryldialkoxysilane is represented by the following formula (11):

5. The thermoplastic resin according to claim 1, wherein the content of the silane structural unit (S) is 2 to 50 mol % based on the total number of moles of all structural units in the thermoplastic resin.

6. The thermoplastic resin according to claim 1, wherein the content of the ester structural unit (I) is 3 to 45 mol % based on the total number of moles of all structural units in the thermoplastic resin.

7. The thermoplastic resin according to claim 1, wherein the content of the diol structural unit (A) is 30 to 70 mol % based on the total number of moles of all structural units in the thermoplastic resin.

8. The thermoplastic resin according to claim 1, wherein the ester structural unit (I) is ester-bonded to the diol structural unit (A).

9. The thermoplastic resin according to claim 1, wherein the thermoplastic resin is either a polyester carbonate resin or a polyester resin.

10. The thermoplastic resin according to claim 1, wherein the silane structural unit (S) is bonded to the diol structural unit (A) via a (silyl) ether bond.

11. The thermoplastic resin according to claim 1, wherein the compound of general formula (7) includes either BNE or DPBN.

12. The thermoplastic resin according to claim 1, wherein the compound of general formula (8) includes either BNEF or BPEF.

13. The thermoplastic resin according to claim 1, wherein the compound of general formula (9) includes 1,12-dodecanediol.

14. The thermoplastic resin of claim 1, wherein the general formula (1) includes dimethyl terephthalate.

15. The thermoplastic resin according to claim 1, wherein the general formula (2) includes dimethyl 2,6-naphthalenedicarboxylate.

16. The thermoplastic resin according to claim 1, wherein the general formula (4) includes FDPM.

17. The thermoplastic resin according to claim 1, wherein the general formula (5) includes the following formula (12):

18. The thermoplastic resin according to claim 1, wherein the general formula (6) includes either of the following formulas (13) and (14):

19. The thermoplastic resin according to claim 1, wherein the θgF of the thermoplastic resin is 0.70 or less, or the θhF of the thermoplastic resin is 1.40 or less.

20. The thermoplastic resin according to claim 1, wherein the weight average molecular weight (Mw) of the thermoplastic resin in terms of polystyrene is 5,000 to 100,000.

21. The thermoplastic resin according to claim 1, wherein the refractive index (nd) of the thermoplastic resin is 1.681 to 1.

720.

22. The thermoplastic resin according to claim 1, wherein the Abbe number (vd) of the thermoplastic resin is 15.0 to 19.

6.

23. The thermoplastic resin according to claim 1, wherein the Tg of the thermoplastic resin is 137 to 170°C.

24. A molded article comprising the thermoplastic resin of claim 1.

25. The molded article according to claim 24, wherein the molded article is an optical lens.

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