Thermoplastic resin, method for producing the same, and use thereof

Abstract

To provide a thermoplastic resin which has a high refractive index and low birefringence, and also exhibits superior moldability or mechanical strength, as well as a method for producing the same and its uses.SOLUTION: A thermoplastic resin is prepared which contains at least a first diol unit (A1) represented by the following formula (1), and in which the absolute value of birefringence in a film uniaxially stretched under stretching conditions including a stretching temperature of (glass transition temperature Tg+10)°C, a stretching speed of 25 mm / min, and a stretching ratio of 3, is 50×10-4 or less at a wavelength of 600 nm. (In the formula, Z1a and Z1b are arene rings, and A1a and A1b are alkylene groups).SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a thermoplastic resin containing diol units derived from specific diol components and having low birefringence, and a method for producing the same and uses thereof, for example, molded articles such as optical members.

Background Art

[0002] Optical resins, particularly thermoplastic resins for optics, have the advantage of being mass-produced by injection molding and are used as camera lenses for electronic device terminals (such as smartphones). In particular, from the perspective of miniaturization or thinning of devices such as smartphones, miniaturization or thinning is also required for camera lenses, and the need for resins with a high refractive index as resins for camera lenses is increasing. This is because when a resin with a high refractive index is used as a resin for a camera lens, the thickness of the lens can be reduced or the curvature of the lens can be relaxed.

[0003] As such high refractive index resins, in Japanese Patent Application Laid-Open No. 2017-179323 (Patent Document 1), International Publication No. 2014 / 073496 (Patent Document 2), and Japanese Patent Application Laid-Open No. 2022-110005 (Patent Document 3), polycarbonate resins into which a fluorene skeleton or a naphthalene skeleton is introduced have been proposed.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] In resins for optical members, in addition to the refractive index, birefringence is also one of the important optical properties. In particular, when optical members such as lenses are miniaturized or thinned, or when they are molded into complex shapes, stress is likely to be applied or molecules are likely to be oriented, so birefringence tends to increase. When a lens is manufactured from a resin with high birefringence, the imaging performance deteriorates due to the deviation of the refractive index, so a resin with low birefringence is required. In addition, with the improvement or multifunctionalization of the functions of imaging systems (image sensors or imaging lens units), the complexity and large aperture of the optical lens shape are progressing, and the need for further reduction of birefringence is increasing.

[0006] As described above, there has been a demand for resins with higher refractive indices and lower birefringence than in the past, but current resins for optical members do not fully meet this demand. One of the factors is that high refractive index and low birefringence are mutually contradictory properties (properties in a trade-off relationship). That is, although it is generally known that introducing a benzene ring skeleton or the like into the chemical structure of a resin can increase the refractive index while maintaining transparency, birefringence also tends to increase as the refractive index increases. Therefore, the more the resin is made to have a higher refractive index, the more difficult it becomes to achieve both low birefringence.

[0007] On the other hand, Patent Document 1 describes that specific polycarbonate resins and polyester carbonate resins can achieve both high refractive index and low birefringence, and Patent Document 2 describes that the obtained polycarbonate resins exhibit physical properties such as high refractive index and low birefringence. However, even the resins described in these patent documents may not have sufficient high refractive index and low birefringence, and there is a need for resins that can achieve both of these properties at an even higher level.

[0008] Although Patent Document 3 discloses that a polycarbonate resin having specific structural units exhibits a very high refractive index, there is no description or suggestion regarding its birefringence. Considering that, as described above, generally the higher the refractive index of a resin, the higher the birefringence tends to be, it is expected that the resin described in Patent Document 3 exhibits very high birefringence.

[0009] In addition, since most of the resins prepared in the examples of Patent Document 3 have a weight average molecular weight Mw of less than 10,000, it is presumed that their mechanical strength is also low. With such resins, it is not possible to mold them into small or thin shapes or complex shapes, or even if they can be molded, they are brittle and prone to cracking and chipping, so the moldability (or productivity) cannot be improved.

[0010] Therefore, an object of the present disclosure is to provide a thermoplastic resin having a high refractive index and low birefringence, as well as good moldability or mechanical strength, and a method for producing and using the same.

Means for Solving the Problems

[0011] As a result of intensive studies to achieve the above problems, the present inventors have found that when polymerization is carried out using a specific diol component in anticipation of an increase in refractive index, as shown in the reference examples described later, the polymerization itself is difficult and a thermoplastic resin cannot be obtained. As a result of further intensive studies by the present inventors, it has been found that even when the specific diol component is used, a relatively high molecular weight thermoplastic resin can be prepared, not only ensuring good mechanical strength or moldability, but also highly achieving both a high refractive index and low birefringence, thus completing the present invention (or the present disclosure). That is, the present disclosure may include the following aspects.

[0012] Aspect [1]: A thermoplastic resin containing a diol component as a polymerization component, wherein the diol unit (A), which is a structural unit derived from the diol component, contains at least a first diol unit (A1) represented by the following formula (1),

[0013]

Chemical formula

[0014] (In the formula, Z 1a and Z 1b each independently represents an arene ring, R 1a and R 1bindependently represents a substituent, m1a and m1b independently represent an integer of 0 or more, k1 and k2 independently represent an integer from 0 to 4, and at least one of k1 and k2 is 1 or more, R 2a and R 2b independently represent a substituent, m2a and m2b independently represent an integer from 0 to 4, k1 + m2a and k2 + m2b are independently 4 or less, A 1a and A 1b independently represent an alkylene group.)

[0015] The absolute value of birefringence in the uniaxially stretched film stretched under the stretching conditions of a stretching temperature (glass transition temperature Tg + 10) °C, a stretching speed of 25 mm / min, and a stretching ratio of 3 times is 50×10 -4 or less, a thermoplastic resin.)

[0016] Aspect [2]: In the formula (1), Z 1a and Z 1b independently represent a C 6-14 arene ring, R 1a and R 1b independently represent a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group or a substituted amino group, m1a and m1b independently represent an integer from 0 to 4, k1 and k2 independently represent an integer from 0 to 2, R 2a and R 2b independently represent an aliphatic hydrocarbon group, a halogen atom or a cyano group, m2a and m2b independently represent an integer from 0 to 2, A 1a and A 1b independently represent a C 1-6 alkylene group, the thermoplastic resin according to Aspect [1].

[0017] Aspect [3]: The diol unit (A) further contains a second diol unit (A2) represented by the following formula (2), the thermoplastic resin according to Aspect [1] or [2].

[0018] [Chemical formula]

[0019] (In the formula, A 2 represents a direct bond or an alkylene group, A 3a and A 3b each independently represent an alkylene group, n3a and n3b each independently represent an integer of 0 or more, R 3a and R 3b each independently represent a substituent, and m3a and m3b each independently represent an integer from 0 to 6.)

[0020] Aspect [4]: In the formula (2), A 2 represents a direct bond or a C 1-4 alkylene group, A 3a and A 3b each independently represent a C 2-6 alkylene group, n3a and n3b each independently represent an integer from 0 to 10, R 3a and R 3b each independently represent a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group or a substituted amino group, and m3a and m3b each independently represent an integer from 0 to 3, the thermoplastic resin according to Aspect [3].

[0021] Aspect [5]: The ratio of the first diol unit (A1) to the second diol unit (A2) is such that the former / latter (molar ratio) = 10 / 90 to 50 / 50, the thermoplastic resin according to Aspect [3] or [4].

[0022] Aspect [6]: The diol unit (A) further contains a third diol unit (A3) represented by the following formula (3), the thermoplastic resin according to any one of Aspects [1] to [5].

[0023] [Chemical formula]

[0024] (In the formula, R 4 represents a substituent, m4 represents an integer from 0 to 8, Z 2a and Z 2b each independently represent an arene ring, R 5a and R 5b each independently represent a substituent, m5a and m5b each independently represent an integer of 0 or more, A 4a and A 4b each independently represent an alkylene group, and n4a and n4b each independently represent an integer of 0 or more.)

[0025] Aspect [7]: In the formula (3), R 4 represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group or a substituted amino group, m4 represents an integer from 0 to 2, Z 2a and Z 2b each independently represent a C 6-14 arene ring, R 5a and R 5b each independently represent a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group or a substituted amino group, m5a and m5b each independently represent an integer from 0 to 2, A 4a and A 4b each independently represent a C 2-6 alkylene group, and n4a and n4b each independently represent an integer from 0 to 10, the thermoplastic resin according to Aspect [6].

[0026] Aspect [8]: In the formula (3), Z 2a and Z 2b each independently represent a condensed polycyclic arene ring or a ring assembly arene ring (preferably a condensed polycyclic arene ring), the thermoplastic resin according to Aspect [6] or [7].

[0027] Aspect [9]: The thermoplastic resin according to any one of Aspects [6] to [8], wherein the ratio of the first diol unit (A1) to the third diol unit (A3) is such that the former / latter (molar ratio) = 10 / 90 to 80 / 20.

[0028] Aspect

[10] : The thermoplastic resin according to any one of Aspects [1] to [9], which is a polyester resin selected from polyester resins, polyester carbonate resins, and polycarbonate resins.

[0029] Aspect

[11] : The weight average molecular weight Mw is 20,000 or more, and the glass transition temperature Tg is 130 to 150°C. The thermoplastic resin according to any one of Aspects [1] to

[10] .

[0030] Aspect

[12] : The refractive index nd is 1.68 or more, and the absolute value of the birefringence is 5×10 -4 or less. The thermoplastic resin according to any one of Aspects [1] to

[11] .

[0031] Aspect

[13] : It is a polycarbonate resin, and the absolute value of the birefringence is 5×10 -4 or less. The thermoplastic resin according to any one of Aspects [1] to

[12] .

[0032] Aspect

[14] : A method for producing a thermoplastic resin according to any one of Aspects [1] to

[13] , including a step of polymerizing a polymerization component containing at least a first diol component corresponding to the first diol unit (A1).

[0033] Aspect

[15] : A molded article containing the thermoplastic resin according to any one of Aspects [1] to

[13] .

[0034] Aspect

[16] : The molded article according to Aspect

[15] , which is an optical member.

[0035] Aspect

[17] : The molded article according to Aspect

[15] or

[16] , which is an optical lens or an optical film.

[0036] Aspect

[18] : An electronic device terminal including the molded body according to any one of Aspects

[15] to

[17] .

[0037] In addition, in the present disclosure, the following secondary objects may be achieved (secondary problems may be solved).

[0038] That is, another object of the present disclosure is to provide a thermoplastic resin having a high refractive index and extremely low birefringence, and a method for producing and using the same.

[0039] Furthermore, still another object of the present disclosure is to provide a thermoplastic resin having a high refractive index and low birefringence, and capable of achieving a good balance between heat resistance and moldability (or productivity), which are in a trade-off relationship with each other, and a method for producing and using the same.

[0040] Also, another object of the present disclosure is to provide a method for easily or efficiently producing a thermoplastic resin having a high refractive index and low birefringence, and good moldability or mechanical strength.

[0041] In the present specification and claims, "diol unit", "structural unit derived from diol component", etc. mean a unit (or divalent group) obtained by removing hydrogen atoms from two hydroxyl groups of the corresponding diol, and "diol component" (including compounds exemplified as diol components) may be used synonymously with the corresponding "diol unit".

[0042] Also, "dicarboxylic acid unit", "structural unit derived from dicarboxylic acid component", etc. mean a unit (or divalent group) obtained by removing OH (hydroxyl group) from two carboxyl groups of the corresponding dicarboxylic acid, and "dicarboxylic acid component" (including compounds exemplified as dicarboxylic acid components) may be used synonymously with the corresponding "dicarboxylic acid unit".

[0043] In addition, the "dicarboxylic acid component" is used in the sense that it includes, in addition to the dicarboxylic acid, derivatives that can be used as polymerization components, such as ester-forming derivatives of dicarboxylic acids, for example, esters of dicarboxylic acids (dicarboxylic acid esters), acid halides (dicarboxylic acid halides), acid anhydrides (dicarboxylic acid anhydrides), etc. The dicarboxylic acid ester may be a monoester (half ester) or a diester, for example, an alkyl ester of a dicarboxylic acid, especially a lower alkyl ester, specifically, a C 1-4 alkyl ester such as an alkyl ester, etc. Examples of the dicarboxylic acid halide include acid chloride, acid bromide, etc.

[0044] Also, in this specification and the claims, "low birefringence" or "low birefringence", etc. means that, unless otherwise specified, the absolute value of the birefringence is small (i.e., close to 0).

[0045] Furthermore, in this specification and the claims, the number of carbon atoms of a substituent may be indicated by C1, C6, C 10 etc. For example, an alkyl group having 1 carbon atom is a "C1 alkyl group", and an aryl group having 6 to 10 carbon atoms is a "C 6-10 aryl group", etc.

[0046] In addition, in this specification and the claims, "independently" means that a plurality of components are each independent components. For example, in the case of A 1a and A 1b , it means that they may be the same alkylene group or different alkylene groups from each other.

[0047] Also, in this specification and the claims, the numerical range indicated by "X~Y" may include the numerical values X and Y.

Advantages of the Invention

[0048] According to the present disclosure, it is possible to provide a thermoplastic resin having a high refractive index and a low birefringence, and having good moldability or mechanical strength, as well as a method for producing the same and uses thereof.

Mode for Carrying Out the Invention

[0049] The thermoplastic resin of the present disclosure (hereinafter, also simply referred to as resin) may be any thermoplastic resin containing at least a diol component [diol component (A)] as a polymerization component (monomer component or resin raw material). Representative thermoplastic resins include, for example, polyester resins such as polyester carbonate resins and polycarbonate resins. Among the polyester resins, polyester carbonate resins and polycarbonate resins are preferred, and polycarbonate resins are more preferred. Since the refractive index and dimensions of an optical resin material change due to moisture absorption, the optical properties become unstable and it cannot be used for precision optical members, so excellent water resistance (or low hygroscopicity) is often required. However, polyester resins are preferable in terms of water resistance (or low hygroscopicity).

[0050] [Diol unit (A)] (A1) First diol unit The diol unit (A), which is a structural unit derived from the diol component (A), contains at least the first diol unit (A1) represented by the following formula (1).

[0051]

Chemical formula

[0052] (In the formula, Z 1a and Z 1b each independently represents an arene ring, R 1a and R 1b each independently represents a substituent, m1a and m1b each independently represent an integer of 0 or more, k1 and k2 each independently represent an integer from 0 to 4, and at least one of k1 and k2 is 1 or more, R 2a and R2b each independently represents a substituent, m2a and m2b each independently represent an integer of 0 to 4, k1 + m2a and k2 + m2b are each independently 4 or less, A 1a and A 1b each independently represents an alkylene group.)

[0053] In the above formula (1), Z 1a , Z 1b Examples of the arene ring (aromatic hydrocarbon ring) represented by include monocyclic arene rings such as benzene rings, and polycyclic arene rings. Examples of the polycyclic arene ring include condensed polycyclic arene rings (condensed polycyclic aromatic hydrocarbon rings), ring-assembled arene rings (ring-assembled aromatic hydrocarbon rings), and the like.

[0054] Examples of the condensed polycyclic arene ring include condensed bicyclic to tetracyclic arene rings such as condensed bicyclic arene rings and condensed tricyclic arene rings. Examples of the condensed bicyclic arene ring include condensed bicyclic C 10-16 arene rings such as naphthalene rings and indene rings. Examples of the condensed tricyclic arene ring include condensed tricyclic C 14-20 arene rings such as anthracene rings and phenanthrene rings. Preferred condensed polycyclic arene rings are condensed polycyclic C 10-14 arene rings such as naphthalene rings.

[0055] Examples of the ring-assembled arene ring include biarene rings such as biphenyl rings, phenylnaphthalene rings, and binaphthyl rings; and terarenes such as terphenyl rings. Preferred ring-assembled arene rings are C 12-18 biarene rings such as biphenyl rings.

[0056] In the present specification and claims, the "ring-aggregated arene ring" means that two or more ring systems (arene ring systems) are directly connected by a single bond or a double bond, and the number of bonds connecting the rings is one less than the number of ring systems. For example, as described above, a phenylnaphthalene ring, a binaphthyl ring, etc. have a condensed polycyclic arene ring skeleton but are classified as ring-aggregated arene rings, and are clearly distinguished from "condensed polycyclic arene rings" such as a naphthalene ring (non-ring-aggregated arene ring).

[0057] Preferred Z 1a , Z 1b Examples of 6-14 the arene ring include C 6-12 arene rings, and more preferably C 6-10 arene rings such as a benzene ring, a naphthalene ring, a biphenyl ring, etc., still more preferably C 1a arene rings such as a benzene ring, a naphthalene ring, etc., and particularly preferably a naphthalene ring. Also, when Z 1b and / or Z

[0058] is a condensed polycyclic arene ring such as a naphthalene ring, it is preferable in terms of easily preparing a resin that well satisfies high refractive index (or low Abbe number) and low birefringence. 1a , Z 1b The types of may be different from each other, but are preferably the same. Also, when the substitution number k1 of the group [-Z 1a -(R 1a ) m1a is 2 or more, the types of two or more rings Z 1a (and the group [-Z 1a -(R 1a ) m1a ) may be the same or different from each other; when the substitution number k2 of the group [-Z 1b -(R 1b ) m1b is 2 or more, the types of two or more rings Z 1b (and the group [-Z 1b -(R 1b ) m1b ) may be the same or different from each other.

[0059] Also, Z1a , Z 1b may be substituted at any position of the 1- to 4-positions and / or 5- to 8-positions of the fluorene skeleton, but the preferred substitution positions (or bonding positions) are the 2-position and / or 7-position, and the 2-position and 7-position (2,7-position) are more preferred.

[0060] In addition, for Z with respect to the fluorene skeleton 1a , Z 1b the bonding position of 1a , Z 1b when Z is a naphthalene ring, it may be either the 1-position or 2-position of the naphthalene ring (i.e., 1-naphthyl or 2-naphthyl), and from the viewpoint of easily preparing a resin that well satisfies high refractive index, low Abbe number, and low birefringence in a well-balanced manner, the 2-position of the naphthalene ring (i.e., 2-naphthyl) is preferred.

[0061] R 1a , R 1b Examples of the substituent (non-reactive group or non-polymerizable group) represented by h are, for example, a halogen atom, a hydrocarbon group (or group [-R h ), group [-OR h (wherein R h represents a hydrocarbon group), group [-SR h (wherein R h represents a hydrocarbon group), an acyl group, a nitro group, a cyano group, a substituted amino group (mono- or di-substituted amino group), and the like.

[0062] In addition, in this specification and the claims, the hydrocarbon group represented by R

[0063] means an independent hydrocarbon group, and they may be the same as or different from each other.

[0064] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. h(]) may be a saturated or unsaturated hydrocarbon group, which may be an aliphatic (including alicyclic) or aromatic hydrocarbon group, and may be a hydrocarbon group having a linear (straight-chain or branched-chain), cyclic, or combined linear and cyclic structure. Representative hydrocarbon group R h Examples thereof include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

[0065] Examples of the alkyl group (linear or branched-chain alkyl group) include C 1-10 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group, preferably C 1-6 alkyl groups, more preferably C 1-4 alkyl groups.

[0066] Examples of the cycloalkyl group include C 5-10 cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group.

[0067] Examples of the aryl group include C 6-12 aryl groups such as a phenyl group, an alkylphenyl group, a biphenylyl group, and a naphthyl group. Examples of the alkylphenyl group include mono- to tri-C 1-4 alkyl-phenyl groups such as a methylphenyl group (or tolyl group) and a dimethylphenyl group (or xylyl group).

[0068] Examples of the aralkyl group include C 6-10 aryl-C 1-4 alkyl groups such as a benzyl group and a phenethyl group.

[0069] In the groups [-OR h and [-SR h , the hydrocarbon group represented by R h includes R 1a , R 1bSimilar hydrocarbon groups including the preferred embodiments and the hydrocarbon groups exemplified above include, for example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and the like.

[0070] Examples of the group [-OR h include, for example, groups corresponding to the examples of the hydrocarbon group R h such as an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group and the like. Examples of the alkoxy group (linear or branched alkoxy group) include C 1-10 alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a t-butoxy group and the like. Examples of the cycloalkyloxy group include C 5-10 cycloalkyloxy groups such as a cyclohexyloxy group and the like. Examples of the aryloxy group include C 6-10 aryloxy groups such as a phenoxy group and the like. Examples of the aralkyloxy group include C 6-10 aryl-C 1-4 alkyloxy groups such as a benzyloxy group and the like.

[0071] Examples of the group [-SR h include, for example, groups corresponding to the examples of the hydrocarbon group R h such as an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group and the like. Examples of the alkylthio group include C 1-10 alkylthio groups such as a methylthio group, an ethylthio group, a propylthio group, an n-butylthio group, a t-butylthio group and the like. Examples of the cycloalkylthio group include C 5-10 cycloalkylthio groups such as a cyclohexylthio group and the like. Examples of the arylthio group include C 6-10 arylthio groups such as a thiophenoxy group and the like. Examples of the aralkylthio group include C 6-10 aryl-C 1-4 alkylthio groups such as a benzylthio group and the like.

[0072] Examples of the acyl group include C 1-6 alkyl-carbonyl groups such as an acetyl group.

[0073] Examples of the mono- or di-substituted amino group include, for example, a dialkylamino group, a bis(alkylcarbonyl)amino group, etc. Examples of the dialkylamino group include diC 1-4 alkylamino groups such as a dimethylamino group. Examples of the bis(alkylcarbonyl)amino group include bis(C 1-4 alkyl-carbonyl)amino groups such as a diacetylamino group.

[0074] Among these R 1a , R 1b , typically, a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, a substituted amino group, etc. are mentioned. Preferred R 1a , R 1b include an alkyl group and an alkoxy group. Specifically, C 1-6 alkyl groups such as a methyl group and C 1-4 alkoxy groups such as a methoxy group are mentioned. Among them, an alkyl group, particularly a C 1-4 alkyl group such as a methyl group is preferred. The types of R 1a , R 1b may be different from each other, but it is preferred that they are the same. When R 1a is an aryl group, R 1a may form a fused arene ring together with Z 1a ; when R 1b is an aryl group, R 1b may form a fused arene ring together with Z 1b .

[0075] R 1a , R 1b The substitution numbers m1a and m1b of represent integers of 0 or more, and Z 1a , Z 1bIt may be selected according to the type, and each can be selected from integers of about 0 to 7, preferably, stepwise, integers of 0 to 6, integers of 0 to 5, integers of 0 to 4, integers of 0 to 3, integers of 0 to 2, more preferably 0 or 1, and particularly 0. When m1a is 2 or more, the same ring Z 1a Two or more groups R 1a substituting it may be the same as or different from each other; when m1b is 2 or more, the same ring Z 1b Two or more groups R 1b substituting it may be the same as or different from each other. The substitution position of R 1a , R 1b is not particularly limited and may be selected according to the type of Z 1a , Z 1b .

[0076] The groups [-Z 1a -(R 1a ) m1a , [-Z 1b -(R 1b ) m1b (hereinafter, also simply referred to as Z 1 -containing groups) have substitution numbers k1 and k2 each indicating an integer of 0 to 4, preferably, stepwise, an integer of 0 to 3, an integer of 0 to 2, more preferably 0 or 1, and particularly 1. When k1 and / or k2 is 2 or more, the types of two or more Z 1 -containing groups may be the same as or different from each other. It is sufficient that at least one of k1 and k2 is 1 or more, for example, at least one of them is 1 or 2, preferably at least one of them is 1, and more preferably both k1 and k2 are 1.

[0077] The substituents (non-reactive groups or non-polymerizable groups) represented by R 2a , R 2b may be substituents other than the Z 1 -containing groups and may be non-aromatic substituents. Representative R 2a , R 2b include hydrocarbon groups (such as non-aromatic hydrocarbon groups), halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms, and cyano groups.

[0078] Examples of the hydrocarbon group include, for example, the above R 1a , R 1b and the hydrocarbon groups exemplified as such. Examples of the non-aromatic hydrocarbon group include non-aromatic groups among the hydrocarbon groups exemplified as the above R 1a , R 1b and specifically include aliphatic hydrocarbon groups such as alkyl groups and cycloalkyl groups. Preferred R 2a , R 2b include aliphatic hydrocarbon groups such as alkyl groups, halogen atoms, and cyano groups, and more preferably alkyl groups such as C 1-6 alkyl groups, particularly C 1-4 alkyl groups such as methyl group, ethyl group, and t-butyl group. Further, the types of R 2a and R 2b may be the same as or different from each other, and are preferably the same.

[0079] R 2a , R 2b The substitution numbers m2a and m2b of R 2a , R 2b may each be, for example, an integer of about 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0. m2a and m2b may be different from each other, but are preferably the same. When m2a is 2 or more, the types of two or more R 2a , R 2b may be the same as or different from each other; when m2b is 2 or more, the types of two or more R 2a , R 2b may be the same as or different from each other. Further, the substitution positions of R 1 are not particularly limited as long as they are any of the 1- to 8-positions of the fluorene skeleton, and R 2a , R 2b may be substituted at positions other than the substitution position of the Z 1 -containing group.

[0080] k1 + m2a and k2 + m2b are each, for example, an integer of 0 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1. k1 + m2a and k2 + m2b may be the same as or different from each other.

[0081] A 1a , A 1b Examples of the alkylene group (linear or branched alkylene group) represented by are, for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, a 1,2-butanediyl group, a 2-methylpropane-1,3-diyl group, etc., C 1-8 alkylene groups. Preferred alkylene groups include C 1-6 alkylene groups, more preferably C 1-4 alkylene groups, still more preferably C 2-4 alkylene groups. Among them, C 2-3 alkylene groups such as an ethylene group, a trimethylene group, and a propylene group are preferred, and in particular, a C3 alkylene group such as a trimethylene group is preferred. Note that A 1a and A 1b may be different from each other, and it is preferred that they are the same.

[0082] As a typical first diol unit (A1), in the above formula (1), Z 1a and Z 1b independently represent a C 6-14 arene ring, R 1a and R 1b independently represent a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, or a substituted amino group, m1a and m1b independently represent an integer of 0 to 4, k1 and k2 independently represent an integer of 0 to 2, R 2a and R 2b independently represent an aliphatic hydrocarbon group, a halogen atom, or a cyano group, m2a and m2b independently represent an integer of 0 to 2, A 1a and A 1b independently represent a diol unit showing a C 1-6 alkylene group;

[0083] Preferably, in the formula (1), Z 1a and Z 1b each independently represents a C 6-12 arene ring such as a benzene ring, a naphthalene ring, or a biphenyl ring, R 1a and R 1b each independently represents a hydrocarbon group, and m1a and m1b each independently represent an integer from 0 to 2, k1 and k2 each independently represent 0 or 1, R 2a and R 2b each independently represents an aliphatic hydrocarbon group, and m2a and m2b each independently represent 0 or 1, A 1a and A 1b each independently represent a diol unit having a C 1-4 alkylene group;

[0084] More preferably, in the formula (1), Z 1a and Z 1b each independently represents a C 6-10 arene ring, R 1a and R 1b each independently represents an alkyl group or a cycloalkyl group, m1a and m1b each independently represent an integer from 0 to 2, k1 and k2 each independently represent 0 or 1, R 2a and R 2b each independently represents an alkyl group or a cycloalkyl group, m2a and m2b each independently represent 0 or 1, A 1a and A 1b each independently represent a diol unit having a C 2-4 alkylene group;

[0085] Particularly preferably, in the formula (1), Z 1a and Z 1b each independently represents a naphthalene ring (particularly, a naphthalene ring bonded to the 2-position with respect to the fluorene skeleton), R1a and R 1b each independently represents a C 1-4 alkyl group such as an alkyl group, and m1a and m1b each independently represent an integer of 0 to 2, k1 and k2 each independently represent 0 or 1 (particularly, 1), R 2a and R 2b each independently represents a C 1-4 alkyl group such as an alkyl group, and m2a and m2b each independently represent 0 or 1, A 1a and A 1b each independently represents a C 2-3 alkylene group (particularly, a C3 alkylene group such as a trimethylene group), which is a diol unit.

[0086] As a specific first diol component (A1) for forming the first diol unit (A1), for example, 9,9-bis(hydroxyalkyl)-mono or diarylfluorene, more specifically, 9,9-bis(3-hydroxypropyl)-1-phenylfluorene, 9,9-bis(3-hydroxypropyl)-2-phenylfluorene, 9,9-bis(3-hydroxypropyl)-3-phenylfluorene, 9,9-bis(3-hydroxypropyl)-4-phenylfluorene, 9,9-bis(3-hydroxypropyl)-1-(1-naphthyl)fluorene, 9,9-bis(3-hydroxypropyl)-2-(1-naphthyl)fluorene, 9,9-bis(3-hydroxypropyl)-3-(1-naphthyl)fluorene, 9,9-bis(3-hydroxypropyl)-4-(1-naphthyl)fluorene, 9,9-bis(3-hydroxypropyl)-1-(2-naphthyl)fluorene, 9,9-bis(3-hydroxypropyl)-2-(2-naphthyl)fluorene, 9,9-bis(3-hydroxypropyl)-3-(2-naphthyl)fluorene, 9,9-bis(3-hydroxypropyl)-4-(2-naphthyl)fluorene, 9,9-bis(3-hydroxypropyl)-1,8-diphenylfluorene, 9,9-bis(3-hydroxypropyl)-2,7-diphenylfluorene, 9,9-bis(3-hydroxypropyl)-3,6-diphenylfluorene, 9,9-bis(3-hydroxypropyl)-4,5-diphenylfluorene, 9,9-bis(3-hydroxypropyl)-1,8-di(1-naphthyl)fluorene, 9,9-bis(3-hydroxypropyl)-2,7-di(1-naphthyl)fluorene, 9,9-bis(3-hydroxypropyl)-3,6-di(1-naphthyl)fluorene, 9,9-bis(3-hydroxypropyl)-4,5-di(1-naphthyl)fluorene, 9,9-bis(3-hydroxypropyl)-1,8-di(2-naphthyl)fluorene, 9,9-bis(3-hydroxypropyl)-2,7-di(2-naphthyl)fluorene, 9,9-bis(3-hydroxypropyl)-3,6-di(2-naphthyl)fluorene, 9,9-bis(3-hydroxypropyl)-4,5-di(2-naphthyl)fluorene, 9,9-bis(2-hydroxyethyl)-2-phenylfluorene, 9,9-bis(2-hydroxyethyl)-2-(1-naphthyl)fluorene, 9,9-bis(2-hydroxyethyl)-2-(2-naphthyl)fluorene, 9,9-bis(2-hydroxyethyl)-2,7-diphenylfluorene, 9,9-bis(2-hydroxyethyl)-2,7-di(1-naphthyl)fluorene, 9,9-bis(2-hydroxyethyl)-2,7-di(2-naphthyl)fluorene, etc., 9,9-bis(hydroxyC 2-4 alkyl)-mono- or di(C 6-12 aryl)fluorene, etc.

[0087] The first diol unit (A1) may be used alone or in combination of two or more. Among the first diol units (A1), a diol unit corresponding to 9,9-bis(hydroxyalkyl)-diarylfluorene such as 9,9-bis(hydroxyC 2-3 alkyl)-di(C 6-10 aryl)fluorene is preferred, and more preferably a diol unit corresponding to 9,9-bis(hydroxyalkyl)-dinaphthylfluorene such as 9,9-bis(3-hydroxypropyl)-2,7-di(2-naphthyl)fluorene, etc., 9,9-bis(hydroxyC 2-3 alkyl)-dinaphthylfluorene.

[0088] (A2) The second diol unit In addition to the first diol unit (A1), the diol unit (A) may further contain at least one (preferably both) diol unit selected from the second diol unit (A2) represented by the following formula (2) and the third diol unit (A3) represented by the formula (3) described later, or may not contain it.

[0089] The preferred diol unit (A) may contain at least a second diol unit (A2) represented by the following formula (2). When the thermoplastic resin of the present disclosure contains the second diol unit (A2), the polymerization reaction tends to proceed, and it is easy to prepare a resin excellent in the balance between a high refractive index and low birefringence. Further, when the thermoplastic resin of the present disclosure contains the second diol unit (A2), it is possible to suppress a decrease in the refractive index and an excessive increase in the glass transition temperature.

[0090]

Chemical formula

[0091] (In the formula, A 2 represents a direct bond or an alkylene group, A 3a and A 3b each independently represent an alkylene group, n3a and n3b each independently represent an integer of 0 or more, R 3a and R 3b each independently represent a substituent, and m3a and m3b each independently represent an integer of 0 to 6.)

[0092] In the formula (2), examples of the alkylene group (linear or branched alkylene group) in A 2 include a C 1-6 alkylene group such as a methylene group and an ethylene group, preferably a C 1-4 alkylene group, more preferably a C 1-2 alkylene group.

[0093] Preferred A 2 includes a direct bond (single bond) or a C 1-2 alkylene group, more preferably a direct bond (single bond) or a methylene group, particularly preferably a direct bond (single bond).

[0094] A 3a , A 3bExamples of the alkylene group (linear or branched alkylene group) represented by include ethylene group, propylene group (1,2-propanediyl group), trimethylene group, 1,2-butanediyl group, tetramethylene group, etc. C 2-6 alkylene groups and the like, preferably C 2-4 alkylene group, more preferably C 2-3 alkylene group, especially ethylene group is preferred. Also, A 3a and A 3b The types of may be the same as or different from each other, but are preferably the same.

[0095] The repeating numbers (number of moles added) n3a and n3b of the alkyleneoxy group [-(A 3a O)-] and [-(A 3b O)-] only need to be 0 or more respectively. For example, they may be selected from integers of about 0 to 15, preferably, step by step, integers of 0 to 10, integers of 0 to 8, integers of 0 to 6, integers of 0 to 4, integers of 0 to 2, and more preferably 0 or 1. Also, when the repeating numbers n3a and n3b are each 1 or more, the polymerization reactivity is likely to be improved. For example, they may be selected from integers of about 1 to 15, preferably, step by step, integers of 1 to 10, integers of 1 to 8, integers of 1 to 6, integers of 1 to 4, integers of 1 to 3, and more preferably 1 or 2, and particularly 1 is preferred. In the present specification and claims, the "repeating number (number of moles added)" may be an average value (arithmetic average value, additive average value) or an average number of moles added. Therefore, n3a and n3b may be selected from the range of about 0 to 15, preferably, step by step, 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, 0 to 1, or may be selected from about 1 to 15, preferably, step by step, 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, 1 to 2. When n3a and n3b are in a moderate range where they are not too large, the refractive index and heat resistance tend not to decrease.

[0096] Also, n3a and n3b may be the same as or different from each other. When n3a is 2 or more, two or more alkyleneoxy groups [-(A 3aThe types of [-O-(A 3b O)-] may be different from each other, but are preferably the same. When there are two or more n3b, two or more alkyleneoxy groups [-(A

[0097] The group [-O-(A 3a O) n3a -], [-O-(A 3b O) n3b -] (that is, the divalent group (or ether bond) forming the main chain of the thermoplastic resin) is not particularly limited in its bonding position (substitution position) with respect to the naphthalene ring, but when the bonding position between the naphthalene ring and A 2 is taken as the 1-position, the 2-position is preferred.

[0098] R 3a , R 3b Examples of the substituent (non-reactive group or non-polymerizable group) represented by are, for example, the same groups including the preferred embodiments as the groups exemplified as R 1a , R 1b in the above formula (1). Therefore, typical R 3a , R 3b include a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, a substituted amino group, etc. Preferred R 3a , R 3b include an alkyl group and an alkoxy group. Specifically, a C 1-6 alkyl group such as a methyl group, and a C 1-4 alkoxy group such as a methoxy group. Among them, an alkyl group, particularly a C 1-4 alkyl group such as a methyl group is preferred. The types of R 3a and R 3b may be the same as or different from each other.

[0099] R 3a , R 3bThe substitution numbers m3a and m3b may each be an integer of about 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, still more preferably 0 or 1, and particularly 0. m3a and m3b may be different from each other, but are preferably the same. When m3a is 2 or more, the two or more R 3a may be the same as or different from each other; when m3b is 2 or more, the two or more R 3b may be the same as or different from each other. Also, the R 3a , R 3b substitution positions are not particularly limited, and may be substituted at positions other than the bonding positions with the naphthalene ring and A 2 and the groups [-O-(A 3a O) n3a -], [-O-(A 3b O) n3b -].

[0100] As a typical second diol unit (A2), in the above formula (2), A 2 represents a direct bond or a C 1-4 alkylene group, A 3a and A 3b independently represent a C 2-6 alkylene group, n3a and n3b independently represent an integer of 0 to 10, R 3a and R 3b independently represent a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group or a substituted amino group, and units in which m3a and m3b independently represent an integer of 0 to 3, etc. can be mentioned;

[0101] Preferably, in the above formula (2), A 2 represents a direct bond or a C 1-2 alkylene group, A 3a and A 3b independently represent a C 2-4 alkylene group, n3a and n3b independently represent an integer of 0 to 4, R 3a and R3b independently represents a hydrocarbon group, and units such as m3a and m3b independently represent integers from 0 to 2;

[0102] More preferably, in the formula (2), A 2 represents a direct bond or a methylene group, A 3a and A 3b independently represent a C 2-3 alkylene group, n3a and n3b independently represent integers from 0 to 2, R 3a and R 3b independently represent an alkyl group, and units such as m3a and m3b independently represent integers from 0 to 2;

[0103] Particularly preferably, in the formula (2), A 2 represents a direct bond, A 3a and A 3b independently represent a C 2-3 alkylene group, n3a and n3b independently represent 0 or 1, R 3a and R 3b independently represent a C 1-4 alkyl group, and structural units such as m3a and m3b independently represent 0 or 1 are exemplified.

[0104] Specific second diol components (A2) that form the second diol unit (A2) include, for example, 1,1'-binaphthyls (or 1,1'-binaphthalenes) in which A 2 is a direct bond. Examples of 1,1'-binaphthyls include dihydroxy-1,1'-binaphthyl such as 2,2'-dihydroxy-1,1'-binaphthyl; bis[hydroxy(poly)alkoxy]-1,1'-binaphthyl and the like.

[0105] Examples of the bis[hydroxy(poly)alkoxy]-1,1'-binaphthyl include 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxypropoxy)-1,1'-binaphthyl, 2,2'-bis[2-(2-hydroxyethoxy)ethoxy]-1,1'-binaphthyl, and other 2,2'-bis[hydroxy(mono to deca)C 2-4 alkoxy]-1,1'-binaphthyl.

[0106] These second diol units (A2) may be used alone or in combination of two or more. Preferred second diol units (A2) include dihydroxy-1,1'-binaphthyls such as bis[hydroxy(poly)alkoxy]-1,1'-binaphthyl, more preferably 2,2'-bis[hydroxy(mono or di)C 2-4 alkoxy]-1,1'-binaphthyl, particularly 2,2'-bis[hydroxyC 2-3 alkoxy]-1,1'-binaphthyl-derived structural units are preferred.

[0107] (A3) Third diol unit In addition to the first diol unit (A1), the diol unit (A) may or may not further contain a third diol unit (A3) represented by the following formula (3) as necessary. Preferred diol units (A) may at least contain both the second diol unit (A2) and the third diol unit (A3). When the thermoplastic resin of the present disclosure contains the third diol unit (A3), the polymerization reaction tends to proceed, the heat resistance (glass transition temperature) tends to be improved without significantly reducing the refractive index, and it is easy to achieve both high refractive index and low birefringence.

[0108] [Chemical formula]

[0109] (In the formula, R 4represents a substituent, m4 represents an integer from 0 to 8, Z 2a and Z 2b each independently represents an arene ring, R 5a and R 5b each independently represents a substituent, m5a and m5b each independently represent an integer of 0 or more, A 4a and A 4b each independently represents an alkylene group, and n4a and n4b each independently represent an integer of 0 or more.)

[0110] In the above formula (3), the substituent (non-reactive group or non-polymerizable group) represented by R 4 is, for example, the same as the groups exemplified as R 1a , R 1b in the above formula (1). Representative examples of R 4 include a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, a substituted amino group, etc. Preferably, it is a halogen atom, a hydrocarbon group, or a cyano group, and more preferably a hydrocarbon group such as an alkyl group or an aryl group. Examples of the alkyl group (linear or branched alkyl group) include a C 1-6 alkyl group such as a methyl group, an ethyl group, a t-butyl group, etc., and a C 1-4 alkyl group such as a methyl group is preferred. Examples of the aryl group include a C 6-10 aryl group such as a phenyl group, etc.

[0111] As the substitution number m4 of R 4 , for example, an integer of about 0 to 6, preferably, in a stepwise manner, an integer of 0 to 4, an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0. When m4 is 2 or more, the types of two or more R 4 may be the same as or different from each other. Also, when R 4 is substituted on both benzene rings forming the fluorene skeleton, the type of R 4 on one benzene ring and the type of R 4The types may be the same as or different from each other, and are preferably the same. Also, R 4 The substitution position of is not particularly limited, and may be, for example, the 2-position, 3-position, 2,7-position, etc.

[0112] Z 2a , Z 2b Examples of the arene ring represented by include, for example, the arene ring exemplified as Z 1a , Z 1b in the above formula (1), and the same rings as those. Preferred Z 2a , Z 2b is a C 6-14 arene ring, more preferably a C arene ring such as a benzene ring, naphthalene ring, biphenyl ring, etc. 6-12 arene ring, still more preferably a C 6-10 arene ring such as a benzene ring, naphthalene ring, etc., or a polycyclic arene ring (C 10-12 polycyclic arene ring, etc.), especially a naphthalene ring. Z 2a and / or Z 2b being a polycyclic arene ring (for example, a condensed polycyclic arene ring such as a naphthalene ring, a ring-assembled arene ring such as a biphenyl ring, etc.) is preferable in terms of easily preparing a resin that well satisfies high refractive index (or low Abbe number) and low birefringence. Z 2a and Z 2b The types may be the same as or different from each other, and are preferably the same.

[0113] In addition, the substitution positions of Z 2a and Z 2b bonded to the 9-position of the fluorene ring are not particularly limited. For example, when Z 2a , Z 2b is a benzene ring, it may be at any position. When Z 2a , Z 2b is a naphthalene ring, it may be at either the 1-position (1-naphthyl) or 2-position (2-naphthyl), preferably the 2-position. When Z 2a , Z 2b is a biphenyl ring, it may be at any of the 2-position, 3-position, 4-position, preferably the 3-position.

[0114] R 5a ,R 5b Examples of the substituent (non-reactive group or non-polymerizable group) represented by [,R] include, for example, R in the above formula (1) 1a ,R 1b Examples include the same groups including preferred embodiments as the groups exemplified as [,R]. Representative R 5a ,R 5b Examples of [,R] include a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, a substituted amino group, etc. Preferred are hydrocarbon groups such as an alkyl group (linear or branched alkyl group), a cycloalkyl group, an aryl group, an aralkyl group, and an alkoxy group (linear or branched alkoxy group) [-OR h , etc. More preferred are C 1-6 alkyl groups such as a methyl group, C 5-8 cycloalkyl groups such as a cyclohexyl group, C 6-14 aryl groups such as a phenyl group, and C 1-4 alkoxy groups such as a methoxy group. Among them, an alkyl group and an aryl group are preferred, and in particular, C 1-4 alkyl groups such as a methyl group and C 6-10 aryl groups such as a phenyl group are preferred. Also, the types of R 5a and R 5b may be the same as or different from each other. When R 5a is an aryl group, R 5a may form a fused arene ring together with Z 2a ; when R 5b is an aryl group, R 5b may form a fused arene ring together with Z 2b .

[0115] R 5a ,R 5b The substitution numbers m5a and m5b of [,R] may each be an integer of 0 or more, and Z 2a ,Z 2bcan be appropriately selected according to the type, for example, it may be an integer of about 0 to 6, preferably an integer of 0 to 4, more preferably an integer of 0 to 2, still more preferably 0 or 1, and particularly preferably 0. m5a and m5b may be different from each other, but are preferably the same. Further, when m5a is 2 or more, two or more R 5a types may be the same as or different from each other; when m5b is 2 or more, two or more R 5b types may be the same as or different from each other.

[0116] R 5a ,R 5b The substitution position is not particularly limited, and in Z 2a ,Z 2b , it may be substituted at a position other than the bonding position with the 9-position of the fluorene ring and the group [-O-(A 4a O) n4a -], [-O-(A 4b O) n4b -] (that is, the ether bond (-O-) forming the main chain). For example, it may be substituted at the ortho position (the carbon atom adjacent to the bonding position of the ether bond) with respect to the ether bond (-O-) in Z 2a ,Z 2b .

[0117] A 4a ,A 4b Examples of the alkylene group (linear or branched alkylene group) represented by include the same groups as those exemplified as A 3a ,A 3b in the above formula (2), including preferred embodiments. Further, the types of A 4a and A 4b may be the same as or different from each other, but are preferably the same.

[0118] Alkyleneoxy group [-(A 4a O)-], [-(A 4bThe number of repetitions (added mole number) n4a and n4b of [-O-] may each be 0 or more, for example, may be selected from integers of about 0 to 15, preferably, stepwise as follows, integers of 0 to 10, integers of 0 to 8, integers of 0 to 6, integers of 0 to 4, integers of 0 to 2, and more preferably 0 or 1. Further, when each of the number of repetitions n4a and n4b is 1 or more, the polymerization reactivity is likely to be improved, for example, may be selected from integers of about 1 to 15, preferably, stepwise as follows, integers of 1 to 10, integers of 1 to 8, integers of 1 to 6, integers of 1 to 4, integers of 1 to 3, and more preferably 1 or 2, and particularly 1 is preferable. In the present specification and claims, the "number of repetitions (added mole number)" may be an average value (arithmetic average value, additive average value) or an average added mole number. Therefore, n4a and n4b may be selected from the range of about 0 to 15, preferably, stepwise as follows, may be 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, 0 to 1, and may also be selected from integers of about 1 to 15, preferably, stepwise as follows, may be 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, 1 to 2. When n4a and n4b are in an appropriate range where they are not too large, the refractive index and heat resistance tend not to decrease.

[0119] Further, n4a and n4b may be the same as or different from each other. When n4a is 2 or more, the types of two or more alkyleneoxy groups [-(A 4a O)-] may be different from each other, but are preferably the same; when n4b is 2 or more, the types of two or more alkyleneoxy groups [-(A 4b O)-] may be different from each other, but are preferably the same.

[0120] The group [-O-(A 4a O) n4a -], [-O-(A 4b O) n4b -] (that is, the ether bond forming the main chain) to the rings Z 2a , Z 2b The substitution positions are not particularly limited, and may be substituted at appropriate positions of Z 2a , Z 2b respectively. The group [-O-(A 4a O) n4a-], [-O-(A 4b O) n4b -] ring Z 2a , Z 2b The substitution position for is Z 2a , Z 2b When Z is a benzene ring, it is preferably substituted at any of the 2-, 3-, or 4-positions of the phenyl group bonded to the 9-position of the fluorene ring, and among them, at the 3- or 4-position, particularly at the 4-position. Also, Z 2a , Z 2b When Z is a naphthalene ring, it is often substituted at any of the 5- to 8-positions of the naphthyl group bonded to the 9-position of the fluorene ring. For example, the 1- or 2-position of the naphthalene ring is substituted with respect to the 9-position of the fluorene ring (substituted in the relationship of 1-naphthyl or 2-naphthyl), and with respect to this substitution position, it is preferably substituted in the relationship of 1,5-position, 2,6-position, particularly 2,6-position. Also, Z 2a , Z 2b When Z is a ring assembly arene ring, the substitution position of the group [-O-(A 4a O) n4a -], [-O-(A 4b O) n4b -] is not particularly limited. For example, it may be substituted on the arene ring bonded to the 9-position of fluorene or the arene ring adjacent to this arene ring. For example, Z 2a , Z 2b When is a biphenyl ring (or Z 2a , Z 2b is a benzene ring, m5a, m5b are 1, R 5a , R 5b is a phenyl group), the 3-position of the biphenyl ring is preferably bonded to the 9-position of fluorene, and the 6-position of the biphenyl ring is preferably bonded to the group [-O-(A 4a O) n4a -], [-O-(A 4b O) n4b -].

[0121] As a typical third diol unit (A3), in the above formula (3), R 4represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group or a substituted amino group, m4 represents an integer of 0 to 2, Z 2a and Z 2b each independently represents a C 6-14 arene ring, R 5a and R 5b each independently represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group or a substituted amino group, m5a and m5b each independently represent an integer of 0 to 2, A 4a and A 4b each independently represents a C 2-6 alkylene group, and n4a and n4b each independently represent units such as an integer of 0 to 10;

[0122] Preferably, in the formula (3), R 4 represents a hydrocarbon group, m4 represents an integer of 0 to 2, Z 2a and Z 2b each independently represents a C 6-12 arene ring such as a benzene ring, a naphthalene ring, a biphenyl ring, R 5a and R 5b each independently represents a hydrocarbon group, m5a and m5b each independently represent an integer of 0 to 2, A 4a and A 4b each independently represents a C 2-4 alkylene group, and n4a and n4b each independently represent units such as an integer of 0 to 6;

[0123] More preferably, in the formula (3), R 4 represents an alkyl group such as a C 1-6 alkyl group or a C 6-10 aryl group such as an aryl group, m4 represents an integer of 0 to 2, Z 2a and Z 2b each independently represents a C 6-10represents an arene ring or a polycyclic arene ring, R 5a and R 5b independently represent an alkyl group such as a C 1-6 alkyl group or a C 6-12 aryl group such as an aryl group, m5a and m5b independently represent an integer from 0 to 2, A 4a and A 4b independently represent a C 2-3 alkylene group, and units such as n4a and n4b independently represent an integer from 0 to 2;

[0124] Particularly preferably, in the above formula (3), R 4 represents a C 1-4 alkyl group, m4 represents an integer from 0 to 2, Z 2a and Z 2b independently represent a C such as a benzene ring or a naphthalene ring 6-10 arene ring or a C such as a naphthalene ring or a biphenyl ring 10-12 polycyclic arene ring (particularly, a naphthalene ring), R 5a and R 5b independently represent a C such as a methyl group 1-4 alkyl group such as an alkyl group or a phenyl group, m5a and m5b independently represent an integer from 0 to 2, A 4a and A 4b independently represent an ethylene group or a propylene group, and units such as n4a and n4b independently represent 0 or 1.

[0125] Specific third diol components (A3) that form the third diol unit (A3) include, for example, in the above formula (3), 9,9-bis(hydroxyaryl)fluorenes where n4a and n4b are 0; 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes where n4a and n4b are 1 or more, for example, about 1 to 10.

[0126] In the present specification and claims, unless otherwise specified, the term "(poly)alkoxy" is used to mean including both alkoxy groups and polyalkoxy groups.

[0127] Examples of 9,9-bis(hydroxyaryl)fluorenes include 9,9-bis(hydroxyphenyl)fluorene, 9,9-bis(alkyl-hydroxyphenyl)fluorene, 9,9-bis(aryl-hydroxyphenyl)fluorene, 9,9-bis(hydroxynaphthyl)fluorene, and the like.

[0128] Examples of 9,9-bis(hydroxyphenyl)fluorene include 9,9-bis(4-hydroxyphenyl)fluorene, and the like.

[0129] Examples of 9,9-bis(alkyl-hydroxyphenyl)fluorene include 9,9-bis[(mono or di)C 1-4 alkyl-hydroxyphenyl]fluorene such as 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, and the like.

[0130] Examples of 9,9-bis(aryl-hydroxyphenyl)fluorene include 9,9-bis(C 6-10 aryl-hydroxyphenyl)fluorene such as 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, and the like.

[0131] Examples of 9,9-bis(hydroxynaphthyl)fluorene include 9,9-bis(6-hydroxy-2-naphthyl)fluorene, 9,9-bis(5-hydroxy-1-naphthyl)fluorene, and the like.

[0132] Examples of 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorenes include 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorene, 9,9-bis[alkyl-hydroxy(poly)alkoxyphenyl]fluorene, 9,9-bis[aryl-hydroxy(poly)alkoxyphenyl]fluorene, 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorene, and the like.

[0133] Examples of 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxypropoxy)phenyl]fluorene, and 9,9-bis[hydroxy(mono to deca)C 2-4 alkoxy-phenyl]fluorene, and the like.

[0134] Examples of 9,9-bis[alkyl-hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene, 9,9-bis[4-(2-hydroxypropoxy)-3-methylphenyl]fluorene, and 9,9-bis[(mono or di)C 1-4 alkyl-hydroxy(mono to deca)C 2-4 alkoxy-phenyl]fluorene, and the like.

[0135] Examples of 9,9-bis[aryl-hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxypropoxy)-3-phenylphenyl)fluorene, and 9,9-bis[C 6-10 aryl-hydroxy(mono to deca)C 2-4 alkoxy-phenyl]fluorene, and the like.

[0136] Examples of 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorene include 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, 9,9-bis[5-(2-hydroxyethoxy)-1-naphthyl]fluorene, 9,9-bis[6-(2-hydroxypropoxy)-2-naphthyl]fluorene, etc., and 9,9-bis[hydroxy(mono to deca)C 2-4 alkoxy-naphthyl]fluorene, etc.

[0137] These third diol units (A3) may be used alone or in combination of two or more. Preferred third diol units (A3) include 9,9-bis[hydroxy(mono to penta)C 2-4 alkoxyC 6-12 aryl]fluorenes such as 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes; more preferably 9,9-bis[hydroxyC 2-4 alkoxyC 6-12 aryl]fluorenes such as 9,9-bis(hydroxyalkoxyaryl)fluorenes; even more preferably 9,9-bis(hydroxyC 2-4 alkoxy-C 10-12 aryl)fluorenes, specifically 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene and other 9,9-bis(hydroxyC 2-4 alkoxy-naphthyl)fluorenes, and 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene and other 9,9-bis(hydroxyC 2-4 alkoxy-phenylphenyl)fluorenes, which are structural units derived therefrom.

[0138] (A4) Fourth diol unit Note that the diol unit (A) may or may not contain a fourth diol unit (A4) that is different from the first diol unit (A1), the second diol unit (A2), and the third diol unit (A3) [not belonging to the category of the first to third diol units (A1) to (A3)] as required.

[0139] Examples of the fourth diol unit (A4) include a constituent unit derived from an aliphatic diol component, an alicyclic diol component, an aromatic diol component, and an alkylene oxide (or alkylene carbonate, haloalkanol) adduct of these diol components.

[0140] Examples of the aliphatic diol component include alkanediol (or alkylene glycol), polyalkane diol (or polyalkylene glycol), and the like.

[0141] Examples of the alkylene glycol include linear or branched alkylene glycols. Specifically, C such as ethylene glycol, propylene glycol, trimethylene glycol, 1,2 - butanediol, 1,3 - butanediol, tetramethylene glycol (or 1,4 - butanediol), 1,5 - pentanediol, neopentyl glycol, 1,6 - hexanediol, 1,8 - octanediol, 1,10 - decanediol, 2-12 and alkylene glycols and the like.

[0142] Examples of the polyalkylene glycol include poly linear or branched alkylene glycols having 2 or more, preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 to 4 alkylene glycol units. Specifically, di - to deca C such as diethylene glycol, dipropylene glycol, triethylene glycol, 2-12 and alkylene glycols and the like.

[0143] Examples of the alicyclic diol component include cycloalkanediols such as cyclohexanediol; bis(hydroxyalkyl)cycloalkanes such as cyclohexanedimethanol; and hydrogenated products of the following aromatic diol components such as the hydrogenated product of bisphenol A.

[0144] Examples of the aromatic diol component (excluding the first to third diol components (A1) to (A3)) include dihydroxyarenes such as hydroquinone and resorcinol; aromatic aliphatic diols such as benzenedimethanol; bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol C, bisphenol G, and bisphenol S; and biphenols such as p,p'-biphenol.

[0145] Examples of the alkylene oxide (corresponding alkylene carbonate or haloalkanol) adducts of these diol components include C 2-4 alkylene oxide adducts, preferably ethylene oxide adducts, propylene oxide adducts, etc. of C 2-3 alkylene oxide adducts, and the number of moles added is not particularly limited. Specifically, examples include adducts obtained by adding about 2 to 10 moles of ethylene oxide per mole of bisphenol A.

[0146] These fourth diol units (A4) may be included alone or in combination of two or more.

[0147] The proportion of the fourth diol unit (A4) is, for example, 50 mol% or less, preferably 30 mol% or less, more preferably 10 mol% or less, based on the total diol units (A), and may be, for example, about 0.1 to 5 mol%, and it is particularly preferable to substantially not contain the fourth diol unit (A4).

[0148] The ratio of the first diol unit (A1) to the whole diol unit (A) (also referred to as A1 / A) may be, for example, about 5 to 75 mol%, preferably 10 to 72 mol%. Further, A1 / A is preferably, stepwise as follows, less than 40 mol%, 20 to 39 mol%, 25 to 38 mol%, 30 to 37 mol%, 33 to 36 mol%, and this range may also be the range of the resin (P1) described later. A1 / A is preferably, stepwise as follows, more than 30 mol% and less than 75 mol%, 40 to 73 mol%, 45 to 72.5 mol%, 50 to 72 mol%, 60 to 71.5 mol%, 65 to 71 mol%, and this range may also be the range of the resin (P2) described later. When the ratio of the first diol unit (A1) is in an appropriate range where it is not too small, it tends to be easy to suppress a decrease in polymerization reactivity [a decrease in molecular weight, mechanical strength, and / or moldability (productivity)], or to easily achieve both a high refractive index and low birefringence; when it is in an appropriate range where it is not too large, it tends to be easy to suppress a decrease in polymerization reactivity [a decrease in molecular weight, mechanical strength, and / or moldability (productivity)], or to easily achieve both a high refractive index and low birefringence.

[0149] The ratio of the second diol unit (A2) to the whole diol unit (A) (also referred to as A2 / A) may be, for example, about 0 to 90 mol%, preferably, stepwise as follows, 20 to 80 mol%, 25 to 70 mol%, 30 to 60 mol%, 35 to 55 mol%, 40 to 50 mol%, 43.0 to 48 mol%. The said ratio may also be the range of the resin (P1) described later. When the ratio of the second diol unit (A2) is in an appropriate range where it is not too small, it tends to be easy to suppress a decrease in polymerization reactivity [a decrease in molecular weight, mechanical strength, and / or moldability (productivity)], or to easily suppress an excessive increase in the glass transition temperature Tg; when it is in an appropriate range where it is not too large, it tends to be easy to suppress a decrease in refractive index and heat resistance.

[0150] The ratio of the third diol unit (A3) to the whole diol unit (A) (also referred to as A3 / A) is, for example, about 0 to 90 mol%, preferably 10 to 80 mol%. A3 / A is preferably, in a stepwise manner, 3 to 50 mol%, 5 to 40 mol%, 10 to 30 mol%, 15 to 25 mol%, and this range may also be the range of the resin (P1) described later. Further, A3 / A is preferably, in a stepwise manner, more than 25 mol% and less than 70 mol%, 27 to 60 mol%, 27.5 to 55 mol%, 28 to 50 mol%, 28.5 to 40 mol%, 29 to 35 mol%, and this range may also be the range of the resin (P2) described later. When the ratio of the third diol unit (A3) is within an appropriate range where it is not too small, it tends to be easy to suppress a decrease in refractive index and heat resistance; when it is within an appropriate range where it is not too large, it tends to be easy to suppress an excessive increase in glass transition temperature Tg and birefringence.

[0151] The ratio of the total amount of the first diol unit (A1) and the second diol unit (A2) to the whole diol unit (A) (also referred to as A1,2 / A) may be, for example, about 10 to 100 mol%, preferably, in a stepwise manner, 30 to 98 mol%, 50 to 97 mol%, 60 to 95 mol%, 70 to 90 mol%, 75 to 85 mol%. This range may also be the range of the resin (P1) described later.

[0152] The ratio of the total amount of the first diol unit (A1) and the third diol unit (A3) to the whole diol unit (A) (also referred to as A1,3 / A) is, for example, 10 mol% or more, specifically about 20 to 100 mol%. A1,3 / A is preferably, in a stepwise manner, 10 to 75 mol%, 20 to 70 mol%, 30 to 65 mol%, 40 to 60 mol%, 45 to 58 mol%, 50 to 57 mol%. This range may also be the range of the resin (P1) described later. Further, A1,3 / A is preferably, in a stepwise manner, 50 mol% or more, 70 mol% or more, 90 mol% or more, substantially 100 mol%, and this range may also be the range of the resin (P2) described later.

[0153] The ratio of the total amount of the first diol unit (A1), the second diol unit (A2), and the third diol unit (A3) to the whole diol unit (A) (also referred to as A1,2,3 / A) may be 30 mol% or more, specifically about 40 to 100 mol%, preferably, stepwise as follows, 50 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, and particularly substantially 100 mol%.

[0154] The ratio of the first diol unit (A1) to the second diol unit (A2) (also referred to as A1 / A2) may be selected from the range of former / latter (molar ratio) = about 5 / 95 to 100 / 0, preferably about 10 / 90 to 50 / 50. Further, A1 / A2 is preferably, stepwise as follows, 20 / 80 to 50 / 50, 30 / 70 to 48 / 52, 35 / 75 to 47 / 53, 40 / 60 to 46 / 54, 42 / 58 to 45 / 55. This range may also be the range of the resin (P1) described later. When the ratio of the first diol unit (A1) is within an appropriate range where it is not too small, there is a tendency to easily suppress a decrease in refractive index and heat resistance, or to easily adjust to low birefringence; when the ratio of the second diol unit (A2) is within an appropriate range where it is not too small, there is a tendency to easily suppress a decrease in polymerization reactivity (decrease in molecular weight, mechanical strength, and / or moldability (productivity)).

[0155] The ratio of the first diol unit (A1) to the third diol unit (A3) (also referred to as A1 / A3) may be, for example, about the former / latter (molar ratio) = 10 / 90 to 80 / 20, preferably 15 / 85 to 75 / 25. Also, A1 / A3 is preferably, stepwise as follows, 15 / 85 to 80 / 20, 25 / 75 to 75 / 25, 30 / 70 to 70 / 30, 50 / 50 to 69 / 31, 53 / 47 to 68 / 32, 60 / 40 to 67 / 33, 61 / 39 to 66 / 34, 62 / 38 to 65.0 / 35.0, and this range may also be the range of the resin (P1) described later. Also, A1 / A3 is preferably, stepwise as follows, 31 / 69 to 74 / 26, 40 / 60 to 73 / 27, 45 / 55 to 72.5 / 27.5, 50 / 50 to 72 / 28, 60 / 40 to 71.5 / 28.5, 65 / 35 to 71 / 29, and this range may also be the range of the resin (P2) described later. When the ratio of the first diol unit (A1) is within an appropriate range where it is not too small, it tends to be easy to prepare low birefringence, it is easy to suppress an excessive increase in the glass transition temperature Tg, and it is easy to suppress a decrease in polymerization reactivity [a decrease in molecular weight, mechanical strength, and / or moldability (productivity)]. When the ratio of the third diol unit (A3) is within an appropriate range where it is not too small, there is a tendency that it is easy to improve heat resistance and it is easy to suppress a decrease in polymerization reactivity [a decrease in molecular weight, mechanical strength, and / or moldability (productivity)].

[0156] The ratio of the second diol unit (A2) to the third diol unit (A3) (also referred to as A2 / A3) can be selected from the range of former / latter (molar ratio) = 0 / 100 to 100 / 0. For example, it may be about 10 / 90 to 100 / 0, preferably stepwise as follows: 30 / 70 to 90 / 10, 50 / 50 to 85 / 15, 55 / 45 to 80 / 20, 60 / 40 to 75 / 25, 65 / 35 to 73 / 27, 67 / 33 to 71 / 29. This range may also be the range of the resin (P1) described later. When the ratio of the second diol unit (A2) is within an appropriate range and not too small, it tends to be easy to suppress the decrease in polymerization reactivity [decrease in molecular weight, mechanical strength, and / or moldability (productivity)], easy to prepare a low birefringence, and easy to suppress an excessive increase in the glass transition temperature Tg. When the ratio of the third diol unit (A3) is within an appropriate range and not too small, it tends to be easy to suppress a decrease in refractive index and heat resistance.

[0157] In addition, the ratio of the total amount of the first to fourth diol units (A1) to (A4) may be 100 mol% with respect to the entire diol unit (A). Also, the ratio of the diol unit (A) [total amount of the first to fourth diol units (A1) to (A4)] may be, for example, 10 mol% or more with respect to the entire constituent units of the resin (total amount of constituent units derived from all polymerization components constituting the resin), preferably stepwise as follows: 20 to 50 mol%, 30 to 50 mol%, 40 to 50 mol%.

[0158] (Dicarboxylic acid unit (B)) The thermoplastic resin may be a polyester-based resin (such as a polyester resin or a polyester carbonate resin) containing a dicarboxylic acid unit (B), which is a constituent unit derived from a dicarboxylic acid component (B) as a polymerization component, in addition to the diol unit (A). The thermoplastic resin may not contain the dicarboxylic acid unit (B). For example, it may be a polycarbonate resin that does not contain the dicarboxylic acid unit (B).

[0159] Examples of the dicarboxylic acid unit (B) include constitutional units derived from, for example, an aromatic dicarboxylic acid component, an alicyclic dicarboxylic acid component, an aliphatic dicarboxylic acid component, and the like.

[0160] Examples of the aromatic dicarboxylic acid component include, for example, monocyclic aromatic dicarboxylic acids, polycyclic aromatic dicarboxylic acids, and ester-forming derivatives thereof. Examples of the monocyclic aromatic dicarboxylic acid include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, and isophthalic acid; alkylbenzenedicarboxylic acids, specifically, C 1-4 alkyl-benzenedicarboxylic acids such as 4-methylisophthalic acid, and the like.

[0161] Examples of the polycyclic aromatic dicarboxylic acid include, for example, condensed polycyclic aromatic dicarboxylic acids, specifically, condensed polycyclic C 10-24 arene-dicarboxylic acids such as naphthalenedicarboxylic acid, anthracenedicarboxylic acid, and phenanthrenedicarboxylic acid, preferably condensed polycyclic C 10-14 arene-dicarboxylic acids and the like; biaryldicarboxylic acids, specifically, 2,2'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, and the like; diarylalkanedicarboxylic acids, specifically, diC 6-10 arylC 1-6 alkane-dicarboxylic acids such as 4,4'-diphenylmethanedicarboxylic acid, and the like; diarylketonedicarboxylic acids, specifically, di(C 6-10 aryl)ketone-dicarboxylic acids such as 4,4'-diphenylketonedicarboxylic acid, and the like; diaryletherdicarboxylic acids, specifically, di(C 6-10 aryl)ether-dicarboxylic acids such as 4,4'-diphenyletherdicarboxylic acid, and the like; diarylsulfonedicarboxylic acids, specifically, di(C 6-10 aryl)sulfone-dicarboxylic acids such as 4,4'-diphenylsulfonedicarboxylic acid, and the like.

[0162] Examples of the naphthalenedicarboxylic acid include 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and the like.

[0163] Examples of the alicyclic dicarboxylic acid component include cycloalkanedicarboxylic acids, specifically C such as 1,4-cyclohexanedicarboxylic acid 5-10 cycloalkane-dicarboxylic acids and the like; bridged cyclic cycloalkanedicarboxylic acids, specifically bicyclic or tricyclic cycloalkanedicarboxylic acids such as decahydrophthalic acid, norbornanedicarboxylic acid, adamantanecarboxylic acid, tricyclodecanedicarboxylic acid, and the like; cycloalkenedicarboxylic acids, specifically C such as cyclohexenedicarboxylic acid 5-10 cycloalkene-dicarboxylic acids and the like; bridged cyclic cycloalkenedicarboxylic acids, specifically bicyclic or tricyclic cycloalkenedicarboxylic acids such as norbornenedicarboxylic acid; and ester-forming derivatives thereof and the like.

[0164] Examples of the aliphatic dicarboxylic acid component include linear or branched alkane-dicarboxylic acids, specifically C such as succinic acid, adipic acid, suberic acid, sebacic acid, decanedicarboxylic acid, and the like 2-12 alkane-dicarboxylic acids and the like; linear or branched unsaturated aliphatic dicarboxylic acids, specifically C such as maleic acid, fumaric acid, itaconic acid, and the like 2-10 alkene-dicarboxylic acids; and ester-forming derivatives thereof and the like.

[0165] The dicarboxylic acid unit (B) may be contained alone or in combination of two or more.

[0166] The ratio of the diol unit (A) to the dicarboxylic acid unit (B) in the thermoplastic resin (also referred to as A / B) may be, for example, A / B (molar ratio) = 1 / 0.8 to 1 / 1.2, preferably about 1 / 0.9 to 1 / 1.1, but it does not necessarily have to be within this range. For example, A / B (molar ratio) = 1 / 0 to 1 / 0.5, preferably in the following steps: 1 / 0 to 1 / 0.3, 1 / 0 to 1 / 0.2, 1 / 0 to 1 / 0.1, and it is particularly preferred that the dicarboxylic acid unit (B) is substantially not contained.

[0167] (Carbonate unit (C)) The thermoplastic resin may, if necessary, further contain a carbonate unit (C) to form a polyester carbonate resin or a polycarbonate resin.

[0168] In the present specification and claims, the "carbonate unit" refers to a structural unit derived from a carbonate bond-forming component capable of forming a carbonate bond [-O-C(=O)-O-] by reaction with a diol component or the like, that is, a carbonyl group [-C(=O)-]. In other words, a carbonate bond can be formed together with the terminal oxygen atoms of two diol units bonded adjacent to the carbonate unit (carbonyl group).

[0169] Therefore, as the carbonate bond-forming component (C), any compound capable of forming a carbonate bond by reaction with the diol component (A) may be used. Representative carbonate bond-forming components (C) include, for example, phosgene such as phosgene and triphosgene, and carbonic acid diesters such as diphenyl carbonate.

[0170] These carbonate bond-forming components (C) can be used alone or in combination of two or more. Among these carbonate bond-forming components (C), carbonic acid diesters such as diphenyl carbonate are preferred from the viewpoints of safety and the like.

[0171] The ratio of the total amount of dicarboxylic acid units (B) and carbonate units (C) to diol units (A) in the thermoplastic resin is such that the former / latter (molar ratio) = 1 / 0.8 to 1 / 1.2, preferably 1 / 0.9 to 1 / 1.1, more preferably 1 / 1 to 1 / 1.1, and may be substantially equimolar. Also, the ratio of dicarboxylic acid units (B) to carbonate units (C) (also referred to as B / C) may be selected from the range of the former / latter (molar ratio) = 0 / 100 to 100 / 0, for example, about 0 / 100 to 50 / 50, preferably in the following steps: 0 / 100 to 30 / 70, 0 / 100 to 20 / 80, 0 / 100 to 10 / 90, 0 / 100 to 5 / 95, and it is particularly preferred that it substantially does not contain dicarboxylic acid units (B).

[0172] (Other constitutional units (D)) Note that the thermoplastic resin may not contain other constitutional units (D) different from diol units (A), dicarboxylic acid units (B), and carbonate units (C), but may contain them as necessary within a range that does not impair the effects of the present disclosure.

[0173] As other constitutional units (D), depending on the type of resin, etc., for example, constitutional units derived from polymerization components such as diisocyanate components may be used. In the case of a polyester-based resin, for example, constitutional units derived from hydroxycarboxylic acid components, corresponding lactone components, polyfunctional polymerization components having three or more polymerizable groups (carboxyl groups and / or hydroxyl groups), etc. may be mentioned.

[0174] Examples of the hydroxycarboxylic acid component include aromatic hydroxycarboxylic acids such as hydroxybenzoic acid; aliphatic hydroxycarboxylic acids (hydroxyalkanoic acids) such as lactic acid, 3-hydroxybutyric acid, and 6-hydroxyhexanoic acid; and ester-forming derivatives thereof. Examples of the corresponding lactone component include lactones corresponding to hydroxyalkanoic acids such as ε-caprolactone.

[0175] Examples of the polyfunctional polymer component having three or more polymerizable groups (carboxyl group and / or hydroxyl group) include polyvalent carboxylic acids having a valence of three or more such as trimellitic acid and pyromellitic acid; polyhydric alcohols having a valence of three or more such as glycerin and pentaerythritol, and the like.

[0176] The proportion of such other structural units (D) is, for example, 50 mol% or less, preferably in the following steps, 0 to 30 mol%, 0 to 10 mol%, 0.01 to 5 mol% with respect to the total amount of all structural units (the total amount of diol units (A), dicarboxylic acid units (B), carbonate units (C) and other structural units (D)), and it is preferable that other structural units (D) are not substantially contained.

[0177] (Representative resin) Examples of the typical polyester resin in the present disclosure include the following resins (P1) and (P2), and the like.

[0178] (P1): A resin in which the diol unit (A) contains at least a first diol unit (A1), a second diol unit (A2) and a third diol unit (A3), and contains a carbonate unit (C).

[0179] (P2): A resin in which the diol unit (A) contains at least a first diol unit (A1) and a third diol unit (A3), and contains a carbonate unit (C).

[0180] Among these resins (P1) and (P2), the resin (P1) is preferable in that it is easy to achieve both a high refractive index and a low birefringence at a high level.

[0181] [Manufacturing method of resin] The manufacturing method of the thermoplastic resin includes a step of polymerizing a polymer component containing at least a first diol component (A1) corresponding to the first diol unit (A1) (polymerization step). Depending on the type of the thermoplastic resin or other polymer components (copolymer components), a conventional method may be used.

[0182] (Method for producing polycarbonate resin) When the thermoplastic resin is a polycarbonate resin, for example, it can be produced by reacting a diol component (A) with a carbonate bond-forming component (C) such as phosgene (solvent method) or transesterification (melt method) through polymerization or condensation. The diol component (A) only needs to contain at least the first diol component (A1), and if necessary, it may further contain the other diol components. Among these methods, the transesterification method is preferred because a solvent is not required.

[0183] In the transesterification method, the proportion of carbonic acid diesters as the carbonate bond-forming component (C) is, for example, 0.8 to 1.5 mol, preferably 0.9 to 1.2 mol, and more preferably 1 to 1.1 mol, per 1 mol of the diol component (A).

[0184] The transesterification reaction may be carried out in the presence of a conventional catalyst. As the catalyst, a base catalyst is usually used, and examples include nitrogen-containing compounds, simple metals, or metal compounds.

[0185] Examples of the nitrogen-containing compounds include quaternary ammonium hydroxides and tertiary amines.

[0186] Examples of the quaternary ammonium hydroxides include tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide; and trialkyl-aralkylammonium hydroxides such as trimethylbenzylammonium hydroxide.

[0187] Examples of the tertiary amines include trialkylamines such as trimethylamine and triethylamine; dialkyl-aralkylamines such as dimethylbenzylamine; and triarylamines such as triphenylamine.

[0188] Examples of the metal contained in the metal alone or the metal compound include alkali metals such as sodium, alkaline earth metals such as magnesium, calcium, and barium, transition metals such as titanium, manganese, and cobalt, Group 12 metals of the periodic table such as zinc and cadmium, Group 13 metals of the periodic table such as aluminum, Group 14 metals of the periodic table such as germanium and lead, and Group 15 metals of the periodic table such as antimony. Examples of the metal compound include alkoxides or phenoxides of the above metals; organic acid salts such as acetates and propionates; inorganic acid salts such as borates, carbonates, or bicarbonates; oxides; hydroxides, and the like.

[0189] These catalysts can be used alone or in combination of two or more. Among these catalysts, carbonates or bicarbonates of alkali metals or alkaline earth metals are preferred, and more preferably carbonates or bicarbonates of alkali metals such as sodium bicarbonate. The amount of the catalyst used is, for example, 0.001×10 -4 ~100×10 -4 mol, preferably in the following steps, 0.01×10 -4 ~40×10 -4 mol, 0.01×10 -4 ~10×10 -4 mol, 0.015×10 -4 ~1×10 -4 mol, 0.02×10 -4 ~0.1×10 -4 mol, 0.025×10 -4 ~0.05×10 -4 mol.

[0190] In addition, the reaction may be carried out in the presence of additives such as stabilizers, if necessary. Examples of the stabilizer include antioxidants and heat stabilizers.

[0191] The reaction can usually be carried out in an atmosphere of an inert gas, for example, nitrogen gas; noble gases such as helium and argon. The reaction can also be carried out under reduced pressure, for example, 1×10 2 ~10×10 2 Pa or so, preferably in the following steps, 5×102 below Pa, 2×10 2 below Pa, 1.3×10 2 It can also be carried out under reduced pressure of below Pa. The reaction temperature can be selected according to the polymerization method. For example, in the transesterification method, the reaction temperature is, for example, 150 to 320 °C, preferably 200 to 310 °C, more preferably 250 to 300 °C. In particular, when using diphenyl carbonate as the diesters, it is effective to carry out polycondensation while distilling off phenol under high temperature and reduced pressure.

[0192] After the reaction is completed, the produced thermoplastic resin may be separated and purified by conventional methods, such as separation and purification means such as washing, extraction, concentration, reprecipitation, centrifugation, filtration, column chromatography, adsorption, etc., or means combining these.

[0193] In addition, a polyester carbonate resin may be prepared by using a polyester diol (a polyester resin having hydroxyl groups at both ends) containing a diol unit (A1) as the diol component used in the above method for producing a polycarbonate resin. The polyester diol containing the diol unit (A1) may be prepared by a method for producing a polyester resin described later or the like.

[0194] (Method for producing polyester resin) When the thermoplastic resin is a polyester resin or a polyester carbonate resin, it may be produced (polymerized or polycondensed) by reacting a diol component (A) containing the first diol component (A1), a dicarboxylic acid component (B) corresponding to the dicarboxylic acid unit, and, if necessary, a carbonate bond-forming component (C), etc., and can be prepared by a conventional method, specifically, a melt polymerization method such as a transesterification method or a direct polymerization method, a solution polymerization method, an interfacial polymerization method, etc.

[0195] Depending on the polymerization method, the reaction may be carried out in the presence or absence of a solvent. However, if the solvent remains in the resulting resin, there is a risk of corroding the mold during molding. Also, depending on the polymerization method, if by-products such as salts remain, it may cause cloudiness of the resin (or its molded article), and there is a risk of being defective particularly in applications that require high transparency such as optical members. Therefore, from the viewpoint of improving moldability (productivity) and transparency, a melt polymerization method (or melt polymer) that can effectively suppress the remaining or mixing of solvents, salts, etc. is preferred.

[0196] The charging ratio of the diol component (A) to the dicarboxylic acid component (B) is usually the former / latter (molar ratio) = for example, 1 / 1.2 to 1 / 0.8, preferably 1 / 1.1 to 1 / 0.9. However, it is not necessarily within this range, and at least one component selected from the diol component (A) and the dicarboxylic acid component (B) may be used in excess and reacted with respect to the planned introduction ratio. For example, an aliphatic diol component such as ethylene glycol that can be distilled out from the reaction system may be used in excess of the ratio introduced into the resin (or introduction ratio).

[0197] Also, when using the carbonate bond-forming component (C), the ratio of the total amount of the dicarboxylic acid component (B) and the carbonate bond-forming component (C) to the diol component (A) is, for example, the former / latter (molar ratio) = 1 / 1.2 to 1 / 0.8, preferably 1 / 1.1 to 1 / 0.9. The carbonate bond-forming component (C) may be used slightly in excess with respect to the planned introduction ratio in consideration of volatilization and decomposition in the reaction. For example, 0.1 to 5 mol%, preferably 2 to 3 mol% in excess of the total amount of the dicarboxylic acid unit (B) and the carbonate unit (C) (total planned introduction amount into the resin), the carbonate bond-forming component (C) may be used.

[0198] The polymerization reaction may be carried out in the presence of a catalyst. As the catalyst, conventional esterification catalysts such as metal catalysts can be used. As the metal catalyst, for example, alkali metals such as sodium; alkaline earth metals such as magnesium, calcium, and barium; transition metals such as titanium, manganese, and cobalt; Group 12 metals of the periodic table such as zinc and cadmium; Group 13 metals of the periodic table such as aluminum; Group 14 metals of the periodic table such as germanium and lead; Group 15 metals of the periodic table such as antimony, etc. Metal compounds containing these can be used. As the metal compound, for example, alkoxides; organic acid salts such as acetates and propionates; inorganic acid salts such as borates and carbonates; oxides, etc. may be used, and hydrates of these may also be used. Representative metal compounds include, for example, germanium compounds such as germanium dioxide, germanium hydroxide, germanium oxalate, germanium tetraethoxide, and germanium-n-butoxide; antimony compounds such as antimony trioxide, antimony acetate, and antimony ethylene glycolate; titanium compounds such as tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate (or titanium(IV) tetrabutoxide), titanium oxalate, and potassium titanium oxalate; manganese compounds such as manganese acetate tetrahydrate; calcium compounds such as calcium acetate monohydrate, etc.

[0199] These catalysts can be used alone or in combination of two or more. When using a plurality of catalysts, each catalyst can be added according to the progress of the reaction. Among these catalysts, manganese acetate tetrahydrate, calcium acetate monohydrate, germanium dioxide, titanium(IV) tetrabutoxide, etc. are preferred. The amount of the catalyst used is, for example, 0.01×10 -4 ~100×10 -4 mol, preferably 0.1×10 -4 ~40×10 -4 mol.

[0200] The reaction may also be carried out in the presence of stabilizers such as heat stabilizers and antioxidants as necessary. Usually, heat stabilizers are often used. For example, phosphorus compounds such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dibutyl phosphate (or di-n-butyl phosphate), phosphorous acid, trimethyl phosphite, and triethyl phosphite can be mentioned. Among these, dibutyl phosphate is often used. The usage amount of the heat stabilizer is, for example, 0.01×10 -4 ~100×10 -4 mol, preferably 0.1×10 -4 ~40×10 -4 mol.

[0201] The reaction may be carried out in an atmosphere of an inert gas, for example, nitrogen gas; noble gases such as helium and argon. Further, the reaction can also be carried out under reduced pressure, for example, at about 1×10 2 ~1×10 4 Pa. The transesterification reaction may be carried out in an inert gas atmosphere such as nitrogen gas, and the polycondensation reaction may be carried out under reduced pressure. The reaction temperature can be selected according to the polymerization method. For example, the reaction temperature in the melt polymerization method is about 150 to 320°C, preferably 250 to 310°C, and more preferably 270 to 300°C.

[0202] After the reaction is completed, the produced thermoplastic resin may be separated and purified by conventional methods, for example, separation and purification means such as washing, extraction, concentration, reprecipitation, centrifugation, filtration, column chromatography, adsorption, and means combining these.

[0203] [Properties and Uses of Resin] (Properties) The thermoplastic resin may exhibit low birefringence and can well balance high refractive index and low birefringence (absolute value of small birefringence), which are optical properties that are a trade-off with each other. The birefringence of the thermoplastic resin may be evaluated by the birefringence of the stretched film obtained by uniaxially stretching the film formed of the resin alone three times (birefringence at three-fold stretching or three-fold birefringence), as will be described later in the examples. The absolute value of the birefringence at three-fold stretching is, for example, in the range of 0 to 100×10 -4 or so at a measurement temperature of 20°C and a wavelength of 600 nm. When used for applications such as optical lenses, preferably, stepwise, it is 80×10 -4 or less, 50×10 -4 or less, 30×10 -4 or less, 20×10 -4 or less, 10×10 -4 or less, 7×10 -4 or less. From the viewpoint of being more easily used as an optical member even when formed into a small, thin, or complex shape, more preferably, stepwise, it is 5×10 -4 or less, 4.5×10 -4 or less, 4×10 -4 or less, 3.5×10 -4 or less, 3×10 -4 or less, 2.5×10 -4 or less, 2×10 -4 or less, 1.5×10 -4 or less, 1×10 -4 or less, 0.8×10 -4 or less, 0.5×10 -4 or less, 0.3×10 -4 or less. When the birefringence at three-fold stretching is low, even when formed into a small, thin, or complex shape, the decrease in imaging performance can be suppressed, so that it can be effectively used not only as an optical lens but also as an optical film such as a polarizing plate protective film or a retardation film (for example, a retardation film with almost zero retardation) because it is difficult for birefringence or retardation to occur in the plane direction even when thinned by stretching or the like. Note that the lower limit value in the range of the absolute value of the birefringence at three-fold stretching may be 0 or more, but depending on the application, etc., for example, 0.1×10 -4 or more, 1×10 -4 or more, 10×10 -4It may be as described above.

[0204] The thermoplastic resin can exhibit a high refractive index while having low birefringence. The refractive index nd of the resin may be, for example, 1.67 or more at a temperature of 20 °C and a wavelength of 587.6 nm, preferably 1.675 or more, 1.68 or more, 1.685 or more in the following steps, and more preferably 1.69 to 1.715, 1.695 to 1.71 in the following steps.

[0205] The thermoplastic resin can exhibit a low Abbe number. The Abbe number νd of the resin may be, for example, 20 or less at a temperature of 20 °C, preferably 18 or less, 17 or less, 12 to 16, 12.5 to 15.5, 13 to 15, 13.5 to 14.5 in the following steps. The thermoplastic resin can exhibit high anomalous dispersion characteristics. The partial dispersion ratio θgF value of the resin may be, for example, about 0.72 to 0.85, 0.76 to 0.82, 0.78 to 0.81 at a temperature of 20 °C. Also, the difference (ΔθgF value) of the θgF of the reference dispersion glass with the same Abbe number νd may be, for example, about 0.1 to 0.23, 0.15 to 0.2, 0.17 to 0.19. In the present specification and claims, the ΔθgF value is calculated by the following formula θgF = -0.00149×νd + 0.637 (where νd represents the Abbe number νd of the thermoplastic resin) Based on this, the θgF value of the reference dispersion glass with the same Abbe number is calculated, and this value can be calculated by subtracting it from the partial dispersion ratio θgF value of the thermoplastic resin.

[0206] The thermoplastic resin may contain the first diol unit (A1) and still have a relatively high molecular weight. The weight average molecular weight Mw of the resin may be, for example, about 20,000 or more in terms of standard polystyrene conversion, preferably 23,000 to 100,000, 25,000 to 80,000, 27,000 to 60,000, 28,000 to 50,000, 29,000 to 35,000 in the following steps. When the weight average molecular weight Mw is in an appropriate range that is not too low, it tends to be easy to suppress a decrease in moldability (productivity) or mechanical strength, and the applications are also less likely to be restricted.

[0207] The thermoplastic resin can also exhibit a moderately high glass transition temperature Tg, and can well balance heat resistance and moldability (or productivity), which are in a trade-off relationship with each other. The glass transition temperature Tg of the resin may be, for example, about 100 to 200 °C, preferably, in the following steps, 110 to 180 °C, 115 to 170 °C, 120 to 160 °C, 125 to 155 °C, 130 to 150 °C, 135 to 145 °C. When in a moderate range where Tg is not too low, it tends to be easy to suppress discoloration (or coloring) during manufacturing and / or use due to a decrease in heat resistance, or deformation in a high-temperature environment after being molded into a predetermined shape. When in a moderate range where Tg is not too high, it tends to be easy to suppress a decrease in moldability or productivity (especially injection moldability).

[0208] In addition, in this specification and the claims, the birefringence at three-fold stretching, refractive index nd, Abbe number νd, partial dispersion ratio θgF value, weight-average molecular weight Mw, and glass transition temperature Tg can be measured by the methods described in the examples below.

[0209] The thermoplastic resin may be crystalline (crystalline polymer), but from the viewpoint of being easy to reduce birefringence, it is particularly preferably amorphous (amorphous polymer) for applications such as optical members such as optical lenses.

[0210] (Resin composition and its molded article) The resin composition only needs to contain at least the thermoplastic resin of the present disclosure. If necessary, it may or may not contain other components different from the thermoplastic resin of the present disclosure. Examples of other components include, for example, other resins different from the thermoplastic resin (first thermoplastic resin) of the present disclosure, conventional additives, and the like.

[0211] As other resins different from the resin of the present disclosure, conventional curable resins may be used, but thermoplastic resins (second thermoplastic resins) are preferred. Examples of the second thermoplastic resin include, for example, polyolefin resins, specifically, chain olefin resins such as polyethylene resins and polypropylene resins, cyclic olefin resins, etc.; styrene resins, specifically, polystyrene (PS) such as general-purpose polystyrene (GPPS) and syndiotactic polystyrene (SPS), and styrene copolymers, for example, rubber component-containing styrene resins (or rubber-grafted styrene copolymers) such as MS resin, AS resin, impact-resistant polystyrene (HIPS), ABS resin, AAS resin, ACS resin, AES resin, MBS resin, etc.; (meth)acrylic resins, specifically, homopolymers or copolymers of (meth)acrylic monomers such as polymethyl methacrylate (PMMA), etc.; vinyl acetate resins, specifically, polyvinyl acetals such as polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), polyvinyl formal (PVF), polyvinyl butyral (PVB), etc.; vinyl chloride resins, specifically, homopolymers or copolymers of vinyl chloride and / or vinylidene chloride such as polyvinyl chloride (PVC), vinyl chloride-vinyl acetate copolymer, vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-acrylonitrile copolymer, etc.; fluororesins, specifically, polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), etc.; polyester resins different from the first thermoplastic resin of the present disclosure, specifically, polyalkylene arylate resins such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), poly-1,4-cyclohexyl dimethylene terephthalate (PCT), polyethylene naphthalate, etc., polyarylate resins, liquid crystalline polyesters, etc.;Polycarbonate resins (PC) different from the first thermoplastic resin of the present disclosure, specifically, bisphenol-type polycarbonate resins such as bisphenol A type polycarbonate resin; polyamide resins (PA), specifically, aliphatic polyamide resins such as polyamide 6 and polyamide 66, aromatic polyamide resins (aramid resins) such as polyphenylene isophthalamide; polyacetal resins (POM); polyphenylene ether resins (PPE); polyphenylene sulfide resins (PPS); polysulfone resins, specifically, polysulfone resins (PSF), polyethersulfone (PES), etc.; polyether ketone resins, specifically, polyether ketone resins (PEK), polyether ether ketone resins (PEEK), polyether ketone ether ketone ketone (PEKEKK), etc.; phenoxy resins; polyketone resins such as aliphatic polyketone resins; cellulose derivatives, specifically, cellulose esters such as nitrocellulose, cellulose acetate, cellulose acetate propionate, cellulose ethers such as ethyl cellulose; thermoplastic polyimide resins, specifically, polyetherimide (PEI), polyamideimide, etc.; polyether nitrile resins; thermoplastic elastomers (TPE), specifically, polystyrene-based TPE, polyolefin-based TPE (TPO), polydiene-based TPE, chlorine-based TPE, fluorine-based TPE, polyurethane-based TPE (TPU), polyester-based TPE (TPEE), polyamide-based TPE (TPA), etc.

[0212] These other resins may be included alone or in combination of two or more. Further, if necessary, the thermoplastic resin (the first thermoplastic resin) of the present disclosure may form a polymer alloy with other resins. Further, the polymer alloy may contain a compatibilizer.

[0213] The proportion of the thermoplastic resin (the first thermoplastic resin) of the present disclosure may be, for example, about 10% by mass or more, preferably in the following steps, 30% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 100% by mass, based on the total resin components (the total amount of the thermoplastic resin of the present disclosure and other resins) in the resin composition.

[0214] The resin composition may, if necessary, contain various conventional additives, for example, fillers or reinforcing agents, colorants such as dyes and pigments, conductive agents, flame retardants, flame retardant aids, plasticizers, lubricants, stabilizers, mold release agents, antistatic agents, dispersants, compatibilizers, flow regulators, leveling agents, defoaming agents, surface modifiers, low stress agents, carbon materials, and the like. Examples of the stabilizer include antioxidants, ultraviolet absorbers, heat stabilizers, and the like. These additives may be used alone or in combination of two or more.

[0215] The total proportion of these additives is, for example, 50 parts by mass or less, preferably in the following steps, 30 parts by mass or less, 0 to 10 parts by mass, and may be about 0.1 to 5 parts by mass, based on 100 parts by mass of the resin components in the resin composition.

[0216] The resin composition can be prepared by mixing the thermoplastic resin (the first thermoplastic resin) of the present disclosure and, if necessary, other components by a conventional method such as dry mixing or melt kneading, and the resin composition may be in the form of pellets or the like.

[0217] The present disclosure encompasses a molded article comprising at least the thermoplastic resin (or the resin composition of the present disclosure). The shape of the molded article is not particularly limited and may be selected according to the application. For example, it may be in the form of pellets, a one-dimensional structure such as linear (fibrous or thread-like), rod-shaped, a two-dimensional structure such as film-like, sheet-like, plate-like, a lens-like structure such as block-shaped, concave or convex lens-shaped, a three-dimensional structure such as hollow-shaped (tubular or tube-shaped), or a composite shape or complex shape combining these shapes. Since the molded article has excellent optical properties and the like in a well-balanced manner, it can be effectively used as an optical member such as an optical film (optical sheet) or an optical lens, particularly an optical lens.

[0218] The molded article can be molded by a conventional molding method according to the type of the molded article and the like. For example, it can be manufactured using a conventional molding method such as an injection molding method, an injection compression molding method, an extrusion molding method, a transfer molding method, a blow molding method, a compression molding method, a pressure molding method, a casting molding method, a calender process, a foam molding method.

[0219] When molding into a lens shape or the like, for example, it may be molded by a compression molding method, an injection molding method, an injection compression molding method, a transfer molding method, a pressure molding method, or the like.

[0220] When molding into a film shape, the resin composition can be formed (or molded) into a film using a conventional film-forming method, such as a casting method (solvent casting method), a melt extrusion method, a calender method, or the like.

[0221] The average thickness of the film can be selected according to the application from the range of about 1 to 1000 μm, for example, 1 to 200 μm, preferably 5 to 150 μm, and more preferably 10 to 120 μm.

[0222] The film may be an unstretched or stretched film, and even a stretched film can maintain low birefringence. Such a stretched film may be either a uniaxially stretched film or a biaxially stretched film.

[0223] The draw ratio is, for each direction in uniaxial drawing or biaxial drawing, for example, 1.1 to 10 times, preferably 1.2 to 8 times, more preferably 1.5 to 6 times. In the case of biaxial drawing, equal drawing, for example, 1.5 to 5 times drawing in both the longitudinal and transverse directions, may be used, or uneven drawing, for example, 1.1 to 4 times drawing in the longitudinal direction and 2 to 6 times drawing in the transverse direction, may be used. In the case of uniaxial drawing, longitudinal drawing, for example, 2.5 to 8 times drawing in the longitudinal direction, may be used, or transverse drawing, for example, 1.2 to 5 times drawing in the transverse direction, may be used.

[0224] The average thickness of the drawn film is, for example, 1 to 150 μm, preferably 3 to 120 μm, more preferably 5 to 100 μm.

[0225] Such a drawn film can be obtained by subjecting a film after film formation (or an undrawn film) to a drawing treatment. The drawing method is not particularly limited. In the case of uniaxial drawing, either a wet drawing method or a dry drawing method may be used. In the case of biaxial drawing, either a tenter method (flat method) or a tube method may be used, but the tenter method, which is excellent in the uniformity of the drawn thickness, is preferred.

[0226] The molded body may also be a composite molded body including the resin (or resin composition) of the present disclosure and other constituent members. The proportion of the resin composition of the present disclosure in the molded body is not particularly limited, and may be, for example, 10 to 100% by mass, or about 20 to 80% by mass.

Examples

[0227] Hereinafter, the present disclosure will be described in more detail based on examples, but the present disclosure is not limited by these examples. The evaluation items and details of the raw materials are shown below.

[0228] [Evaluation method] ( 1 H-NMR) The sample was dissolved in deuterated chloroform containing tetramethylsilane as an internal standard substance, and using a nuclear magnetic resonance apparatus (「AVANCE III HD」 manufactured by BRUKER), 1The 1H-NMR spectrum was measured.

[0229] (Molecular weight) Using gel permeation chromatography (HLC-8120GPC manufactured by Tosoh Corporation), the sample was dissolved in tetrahydrofuran (THF), and the weight-average molecular weight Mw was measured in terms of standard polystyrene.

[0230] (Glass transition temperature (Tg)) Using a differential scanning calorimeter (EXSTAR6000 DSC6220 ASD-2 manufactured by SII NanoTechnology Inc.), the measurement was carried out under a nitrogen atmosphere at a heating rate of 10 °C / min.

[0231] (Refractive index nd) The sample was hot-pressed at 200 to 240 °C to form a test piece with a thickness of about 1 mm. Using this test piece and a Carl Zeiss precision refractometer (KPR-2000 manufactured by Shimadzu Device Manufacturing Co., Ltd.), the refractive index nd at a measurement temperature of 20 °C was measured using a contact liquid with a refractive index of 1.52 as the contact liquid for the test piece at a wavelength of 587.6 nm (d line).

[0232] (Abbe number νd) Using the test piece for which the refractive index nd at 587.6 nm (d line) was measured, except that the measurement wavelengths were changed to 486.1 nm (F line) and 656.3 nm (C line), the refractive indices nF and nC were measured in the same manner as for the refractive index nd. From the refractive indices nF, nd, and nC at each obtained wavelength, the Abbe number νd was calculated by the following formula.

[0233] νd = (nd - 1) / (nF - nC)

[0234] (Partial dispersion ratio θgF) Using the test piece for which the refractive index nd at 587.6 nm (d line) was measured, except that the measurement wavelengths were changed to 435.8 nm (g line), 486.1 nm (F line), and 656.3 nm (C line), the refractive indices ng, nF, and nC were measured in the same manner as for the refractive index nd. From the refractive indices ng, nF, and nC at each obtained wavelength, the value of the partial dispersion ratio θgF was calculated by the following formula.

[0235] θgF = (ng - nF) / (nF - nC)

[0236] (Birefringence (birefringence or triple birefringence during triple stretching)) A film with a thickness of 200 to 600 μm was formed by hot pressing the sample at 200 to 280°C. This film was cut into strips measuring 60 mm in length and 30 mm in width, and uniaxially stretched (free-end uniaxial stretching) at a rate of 25 mm / min under temperature conditions of the glass transition temperature Tg + 10°C so that the stretching ratio was 3 times. Using a retardation film and optical material inspection device ("RETS-100" manufactured by Otsuka Electronics Co., Ltd.), the retardation was measured by the rotating analyzer method under the conditions of a measurement temperature of 20°C and a measurement wavelength of 600 nm, and the birefringence (or triple birefringence) was calculated by dividing the measured value by the thickness of the measurement site.

[0237] [Polymerization component (monomer or resin raw material)] (Diol component) DNFPO: 2,7-di(2-naphthyl)-9,9-fluorenedipropanol [or, 2,7-di(2-naphthyl)-9,9-bis(3-hydroxypropyl)fluorene], synthesized according to the description in the section of (Preparation of 2,7-dinaphthyl-9,9-fluorenedipropanol) in Example 1 of International Publication No. 2021 / 131942 BINOL-2EO: 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, synthesized according to Synthesis Example 2 described in JP-A No. 2018-59074 BNEF: 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, synthesized according to Synthesis Example 1 described in JP-A No. 2018-59074 BOPPEF: 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, synthesized according to Example 4 described in JP-A No. 2001-206863 (Carbonate bond-forming component) DPC: Diphenyl carbonate The structural formulas of each polymerization component are shown below.

[0238] [Chemical formula]

[0239] [Example 1] To 0.10 mol of DNFPO, 0.50 mol of BINOL-2EO, and 0.40 mol of BNEF as diol components and 1.05 mol of DPC, 3.0×10 -6 moles of sodium hydrogen carbonate were added, and the temperature was raised to 250°C and gradually heated and melted. After raising the temperature to 250°C, while stirring, the temperature was gradually raised and the pressure was reduced to reach 275°C and 0.13 kPa or less, and phenol was removed over about 2 hours. After reaching a predetermined stirring torque, the content was taken out of the reactor to prepare pellets of the polycarbonate resin. The obtained pellets were 1 Analyzed by 1H-NMR, the composition of the diol units of the polycarbonate resin was 10 mol% derived from DNFPO, 50 mol% derived from BINOL-2EO, and 40 mol% derived from BNEF.

[0240] The weight average molecular weight Mw of the obtained polycarbonate resin was 41,800, the glass transition temperature Tg was 148.9°C, the refractive index nd was 1.6833, the Abbe number νd was 17.2, θgF was 0.720, and the birefringence (triple birefringence) was 27.4×10 -4 was.

[0241] [Example 2] Polycarbonate resin pellets were prepared in the same manner as in Example 1 except that 0.10 mol of DNFPO, 0.70 mol of BINOL-2EO, and 0.20 mol of BNEF were used as the diol components. The obtained pellets were 1 Analyzed by 1H-NMR, the composition of the diol units of the polycarbonate resin was 10 mol% derived from DNFPO, 70 mol% derived from BINOL-2EO, and 20 mol% derived from BNEF.

[0242] The weight average molecular weight Mw of the obtained polycarbonate resin was 28,700, the glass transition temperature Tg was 129.1 °C, the refractive index nd was 1.6811, the Abbe number νd was 17.1, θgF was 0.727, and the birefringence (triple birefringence) was 7.2×10 -4 was obtained.

[0243] [Example 3] Polycarbonate resin pellets were prepared in the same manner as in Example 1, except that 0.20 mol of DNFPO, 0.60 mol of BINOL-2EO, and 0.20 mol of BNEF were used as the diol components. The obtained pellets were 1 analyzed by 1H-NMR. As a result, the composition of the diol units in the polycarbonate resin was 20 mol% derived from DNFPO, 60 mol% derived from BINOL-2EO, and 20 mol% derived from BNEF.

[0244] The weight average molecular weight Mw of the obtained polycarbonate resin was 27,400, the glass transition temperature Tg was 133.0 °C, the refractive index nd was 1.6887, the Abbe number νd was 15.7, θgF was 0.763, and the birefringence (triple birefringence) was 7.5×10 -4 was obtained.

[0245] [Reference Example 1] An attempt was made to prepare a polycarbonate resin in the same manner as in Example 1, except that 0.30 mol of DNFPO and 0.70 mol of BNEF were used as the diol components. However, since the viscosity of the reaction mixture did not increase and it could not be taken out at a low viscosity, a polycarbonate resin could not be obtained.

[0246] [Example 4] Polycarbonate resin pellets were prepared in the same manner as in Example 1, except that 0.30 mol of DNFPO, 0.40 mol of BINOL-2EO, and 0.30 mol of BNEF were used as the diol components. The obtained pellets were 1 analyzed by 1H-NMR. As a result, the composition of the diol units in the polycarbonate resin was 30 mol% derived from DNFPO, 40 mol% derived from BINOL-2EO, and 30 mol% derived from BNEF.

[0247] The weight-average molecular weight Mw of the obtained polycarbonate resin was 35,200, the glass transition temperature Tg was 147.7 °C, the refractive index nd was 1.6959, the Abbe number νd was 14.9, θgF was 0.788, and the birefringence (triple birefringence) was 9.1×10 -4 It was as follows.

[0248] [Example 5] Polycarbonate resin pellets were prepared in the same manner as in Example 1, except that 0.30 mol of DNFPO, 0.45 mol of BINOL-2EO, and 0.25 mol of BNEF were used as the diol components. The obtained pellets were 1 Analyzed by 1H-NMR, the composition of the diol units of the polycarbonate resin was 30 mol% derived from DNFPO, 45 mol% derived from BINOL-2EO, and 25 mol% derived from BNEF.

[0249] The weight-average molecular weight Mw of the obtained polycarbonate resin was 46,900, the glass transition temperature Tg was 144.2 °C, the refractive index nd was 1.6953, the Abbe number νd was 14.8, θgF was 0.787, and the birefringence (triple birefringence) was 3.3×10 -4 It was as follows.

[0250] [Example 6] Polycarbonate resin pellets were prepared in the same manner as in Example 1, except that 0.30 mol of DNFPO, 0.50 mol of BINOL-2EO, and 0.20 mol of BNEF were used as the diol components. The obtained pellets were 1 Analyzed by 1H-NMR, the composition of the diol units of the polycarbonate resin was 30 mol% derived from DNFPO, 50 mol% derived from BINOL-2EO, and 20 mol% derived from BNEF.

[0251] The weight-average molecular weight Mw of the obtained polycarbonate resin was 34,600, the glass transition temperature Tg was 136.5 °C, the refractive index nd was 1.6943, the Abbe number νd was 14.7, θgF was 0.788, and the birefringence (triple birefringence) was 3.8×10 -4 It was as follows.

[0252] [Example 7] Polycarbonate resin pellets were prepared in the same manner as in Example 1, except that 0.30 mol of DNFPO, 0.55 mol of BINOL-2EO, and 0.15 mol of BNEF were used as the diol components. The obtained pellets were 1 Analyzed by 1H-NMR, the composition of the diol units of the polycarbonate resin was 30 mol% derived from DNFPO, 55 mol% derived from BINOL-2EO, and 15 mol% derived from BNEF.

[0253] The weight average molecular weight Mw of the obtained polycarbonate resin was 29,100, the glass transition temperature Tg was 132.7 °C, the refractive index nd was 1.6950, the Abbe number νd was 14.7, θgF was 0.793, and the birefringence (triple birefringence) was -0.6×10 -4 .

[0254] [Example 8] Polycarbonate resin pellets were prepared in the same manner as in Example 1, except that 0.35 mol of DNFPO, 0.45 mol of BINOL-2EO, and 0.20 mol of BNEF were used as the diol components. The obtained pellets were 1 Analyzed by 1H-NMR, the composition of the diol units of the polycarbonate resin was 35 mol% derived from DNFPO, 45 mol% derived from BINOL-2EO, and 20 mol% derived from BNEF.

[0255] The weight average molecular weight Mw of the obtained polycarbonate resin was 29,500, the glass transition temperature Tg was 139.9 °C, the refractive index nd was 1.6988, the Abbe number νd was 14.3, θgF was 0.800, and the birefringence (triple birefringence) was -0.2×10 -4 .

[0256] [Example 9] Polycarbonate resin pellets were prepared in the same manner as in Example 1, except that 0.375 mol of DNFPO, 0.425 mol of BINOL-2EO, and 0.20 mol of BNEF were used as the diol components. The obtained pellets were 1Analysis by H-NMR showed that the composition of the diol units of the polycarbonate resin was 37.5 mol% derived from DNFPO, 42.5 mol% derived from BINOL-2EO, and 20 mol% derived from BNEF.

[0257] The weight average molecular weight Mw of the obtained polycarbonate resin was 29,500, the glass transition temperature Tg was 140.2 °C, the refractive index nd was 1.7003, the Abbe number νd was 14.1, θgF was 0.805, and the birefringence (triple birefringence) was -2.5×10 -4 It was.

[0258] [Reference Example 2] Attempts were made to prepare a polycarbonate resin in the same manner as in Example 1 except that 0.40 mol of DNFPO, 0.20 mol of BINOL-2EO, and 0.40 mol of BNEF were used as the diol components. However, the viscosity of the reaction mixture did not increase and it could not be taken out at a low viscosity, so a polycarbonate resin could not be obtained.

[0259] [Reference Example 3] Attempts were made to prepare a polycarbonate resin in the same manner as in Example 1 except that 0.40 mol of DNFPO, 0.40 mol of BINOL-2EO, and 0.20 mol of BNEF were used as the diol components. However, the viscosity of the reaction mixture did not increase and it could not be taken out at a low viscosity, so a polycarbonate resin could not be obtained.

[0260] [Example 10] Polycarbonate resin pellets were prepared in the same manner as in Example 1 except that 0.50 mol of DNFPO and 0.50 mol of BNEF were used as the diol components. The obtained pellets were 1 Analysis by H-NMR showed that the composition of the diol units of the polycarbonate resin was 50 mol% derived from DNFPO and 50 mol% derived from BNEF.

[0261] The weight-average molecular weight Mw of the obtained polycarbonate resin was 46,000, the glass transition temperature Tg was 178.3 °C, the refractive index nd was 1.7073, the Abbe number νd was 13.6, θgF was 0.813, and the birefringence (triple birefringence) was 40.2×10 -4 It was as follows.

[0262] [Example 11] Polycarbonate resin pellets were prepared in the same manner as in Example 1, except that 0.50 mol of DNFPO and 0.50 mol of BOPPEF were used as the diol components. The obtained pellets were 1 Analyzed by 1H-NMR, the composition of the diol units of the polycarbonate resin was 50 mol% derived from DNFPO and 50 mol% derived from BOPPEF.

[0263] The weight-average molecular weight Mw of the obtained polycarbonate resin was 38,300, the glass transition temperature Tg was 150.9 °C, the refractive index nd was 1.6923, the Abbe number νd was 14.3, θgF was 0.814, and the birefringence (triple birefringence) was -32.3×10 -4 It was as follows.

[0264] [Reference Example 4] An attempt was made to prepare a polycarbonate resin in the same manner as in Example 1, except that 0.60 mol of DNFPO, 0.20 mol of BINOL-2EO, and 0.20 mol of BNEF were used as the diol components. However, the viscosity of the reaction mixture did not increase and it could not be taken out at a low viscosity, so a polycarbonate resin could not be obtained.

[0265] [Example 12] Polycarbonate resin pellets were prepared in the same manner as in Example 1, except that 0.70 mol of DNFPO and 0.30 mol of BNEF were used as the diol components. The obtained pellets were 1 Analyzed by 1H-NMR, the composition of the diol units of the polycarbonate resin was 70 mol% derived from DNFPO and 30 mol% derived from BNEF.

[0266] The weight-average molecular weight Mw of the obtained polycarbonate resin was 46,500, the glass transition temperature Tg was 167.2 °C, the refractive index nd was 1.7055, the Abbe number νd was 12.2, θgF was 0.848, and the birefringence (triple birefringence) was 9.4×10 -4 It was as follows.

[0267] [Reference Example 5] A polycarbonate resin was tried to be prepared in the same manner as in Example 1 except that 0.75 mol of DNFPO and 0.25 mol of BNEF were used as the diol component. Although the viscosity of the reaction mixture did not increase sufficiently, the polycarbonate resin could be taken out.

[0268] The weight-average molecular weight Mw of the obtained polycarbonate resin was 18,900, but the molecular weight was too low to prepare a test piece by hot pressing, and the refractive index and triple birefringence could not be measured.

[0269]

Table 1

[0270] As is clear from the results in Table 1, in the reference examples, the resin could not be prepared or the mechanical strength was too low to withstand molding. On the other hand, in the examples, the mechanical strength was good enough to be stretchable, and it had a high refractive index and low birefringence.

[0271] Among the examples, Examples 5 to 9, especially Examples 7 to 8 (particularly Example 8), had extremely low birefringence, and it was shown that they could be suitably applied even to optical members (such as optical lenses and optical films) having a smaller or thinner shape or a complicated shape.

Industrial Applicability

[0272] The thermoplastic resin of the present disclosure can be used in various applications, for example, coating agents or coating films, specifically, paints, inks, protective films for electronic devices and liquid crystal members, etc.; adhesives, pressure-sensitive adhesives; resin fillers; electrical and electronic materials or electrical and electronic components (electrical and electronic devices), specifically, antistatic agents, carrier transport agents, light emitters, organic photoreceptors, heat-sensitive recording materials, photochromic materials, hologram recording materials, antistatic trays, conductive sheets, optical discs, inkjet printers, digital paper, color filters, organic EL elements, organic semiconductor lasers, dye-sensitized solar cells, sensors, EMI shielding films, etc.; mechanical materials or mechanical components (devices), specifically, automotive materials or parts, aerospace-related materials or parts, sliding members, etc.

[0273] The thermoplastic resin of the present disclosure can be particularly effectively used as an optical member. Typical optical members include optical films (optical sheets) such as films for liquid crystals and films for organic ELs; optical lenses such as glasses lenses and camera lenses; prisms, holograms, optical fibers, etc.

[0274] Examples of optical films include, for example, polarizing films, polarizing elements constituting polarizing films and polarizing plate protective films, retardation films, alignment films (orientation films), viewing angle enlargement (compensation) films, diffusion plates (films), prism sheets, light guide plates, brightness enhancement films, near-infrared absorption films, reflection films, antireflection (AR) films, reflection reduction (LR) films, antiglare (AG) films, transparent conductive (ITO) films, anisotropic conductive films (ACF), electromagnetic wave shielding (EMI) films, films for electrode substrates, films for color filter substrates, barrier films, color filter layers, black matrix layers, adhesive layers or release layers between optical films, etc. These optical films can be effectively used as optical films for displays such as liquid crystal displays (LCDs), organic EL displays (OLEDs), plasma displays (PDPs), field emission displays (FEDs), electronic papers, etc. Specific devices or apparatuses (electronic devices such as electronic device terminals) include televisions; personal computers (PCs) such as desktop PCs, notebook PCs or tablet PCs; smartphones, mobile phones; car navigation systems; devices or apparatuses (electronic devices such as electronic device terminals) equipped with flat panel displays (FPDs) such as touch panels, etc.

[0275] Examples of optical lenses include, for example, spectacle lenses, contact lenses, camera lenses, VTR zoom lenses, pickup lenses, Fresnel lenses, solar concentrator lenses, objective lenses, rod lens arrays, etc., and in particular, they may be suitably used for optical lenses such as camera lenses. Representative devices or apparatuses (electronic devices such as electronic device terminals) equipped with such optical lenses include devices having a camera function such as smartphones, mobile phones, digital cameras, tablet terminals, personal computers (PCs) (especially small devices or mobile devices); in-vehicle cameras such as drive recorders, rear cameras, etc.

Claims

1. A thermoplastic resin containing a diol component as a polymerization component, wherein a diol unit (A) which is a structural unit derived from the diol component contains at least a first diol unit (A1) represented by the following formula (1): 【Chemistry 1】 (In the formula, Z １ａ and Z １ｂ each independently represents an arene ring, R １ａ and R １ｂ each independently represents a substituent; m1a and m1b each independently represent an integer of 0 or more; k1 and k2 each independently represent an integer of 0 to 4, and at least one of k1 and k2 is 1 or greater; R ２ａ and R ２ｂ each independently represents a substituent; m2a and m2b each independently represent an integer of 0 to 4; k1+m2a and k2+m2b are independently 4 or less; A １ａ and A １ｂ each independently represents an alkylene group. The absolute value of birefringence of a stretched film uniaxially stretched under the conditions of a stretching temperature (glass transition temperature Tg+10) ° C., a stretching speed of 25 mm / min, and a stretching ratio of 3 times is 50 × 10 at a wavelength of 600 nm. －４ A thermoplastic resin, which is:

2. In the formula (1), Z １ａ and Z １ｂ is independent and C ６－１４ Represents an arene ring; R １ａ and R １ｂ each independently represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, or a substituted amino group; m1a and m1b each independently represent an integer of 0 to 4; k1 and k2 independently represent an integer of 0 to 2; R ２ａ and R ２ｂ each independently represents an aliphatic hydrocarbon group, a halogen atom, or a cyano group; m2a and m2b each independently represent an integer of 0 to 2; A １ａ and A １ｂ is independent and C １－６ The thermoplastic resin of claim 1, which exhibits an alkylene group.

3. The thermoplastic resin according to claim 1 or 2, wherein the diol unit (A) further contains a second diol unit (A2) represented by the following formula (2): 【Chemistry 2】 (In the formula, A ２ represents a direct bond or an alkylene group, A ３ａ and A ３ｂ each independently represents an alkylene group; n3a and n3b ​​each independently represent an integer of 0 or more; R ３ａ and R ３ｂ each independently represents a substituent, and m3a and m3b each independently represent an integer of 0 to 6.

4. In the formula (2), A ２ is a direct bond or C １－４ represents an alkylene group, A ３ａ and A ３ｂ is independent and C ２－６ An alkylene group is represented, and n3a and n3b ​​each independently represent an integer of 0 to 10. R ３ａ and R ３ｂ The thermoplastic resin according to claim 3, wherein m3a and m3b independently represent an integer of 0 to 3.

5. The thermoplastic resin according to claim 3, wherein a ratio of the first diol unit (A1) to the second diol unit (A2) is the former / the latter (molar ratio)=10 / 90 to 50 / 50.

6. The thermoplastic resin according to claim 1 or 2, wherein the diol unit (A) further contains a third diol unit (A3) represented by the following formula (3): 【Chemistry 3】 (In the formula, R ４ represents a substituent, m4 represents an integer of 0 to 8, Z ２ａ and Z ２ｂ each independently represents an arene ring, R ５ａ and R ５ｂ each independently represents a substituent; m5a and m5b each independently represent an integer of 0 or more; A ４ａ and A ４ｂ each independently represents an alkylene group, and n4a and n4b each independently represent an integer of 0 or more.

7. In the formula (3), R ４ represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group or a substituted amino group; m4 represents an integer of 0 to 2; Z ２ａ and Z ２ｂ is independent and C ６－１４ Represents an arene ring; R ５ａ and R ５ｂ each independently represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, or a substituted amino group; m5a and m5b each independently represent an integer of 0 to 2; A ４ａ and A ４ｂ is independent and C ２－６ The thermoplastic resin according to claim 6, wherein n4a and n4b each independently represent an integer of 0 to 10.

8. In the formula (3), Z ２ａ and Z ２ｂ The thermoplastic resin of claim 6 , wherein each independently represents a fused polycyclic arene ring or a ring-assembled arene ring.

9. The thermoplastic resin according to claim 6, wherein a ratio of the first diol unit (A1) to the third diol unit (A3) is the former / the latter (molar ratio)=10 / 90 to 80 / 20.

10. 3. The thermoplastic resin according to claim 1, which is a polyester-based resin selected from the group consisting of polyester resins, polyester carbonate resins and polycarbonate resins.

11. The weight average molecular weight Mw is 20,000 or more, The thermoplastic resin according to claim 1 or 2, having a glass transition temperature Tg of 130 to 150°C.

12. The refractive index nd is 1.68 or more, The absolute value of the birefringence is 5×10 －４ The thermoplastic resin according to claim 1 or 2, wherein:

13. It is a polycarbonate resin, The absolute value of the birefringence is 5×10 －４ The thermoplastic resin according to claim 1 or 2, wherein:

14. 3. The method for producing a thermoplastic resin according to claim 1, further comprising a step of polymerizing a polymerization component containing at least a first diol component corresponding to the first diol unit (A1).

15. A molded article comprising the thermoplastic resin according to claim 1 or 2.

16. The molded article according to claim 15, which is an optical member.

17. The molded article according to claim 15, which is an optical lens or an optical film.

18. An electronic device terminal comprising the molded article according to claim 15.

Images