Fluorene derivatives and resins, and methods of producing and using the same

Abstract

To provide a new diol compound which enables formation of a resin that exhibits a high refractive index and is excellent in moldability (or handleability).SOLUTION: A diol compound is represented by the following formula (1). In the formula, Y1a and Y1b represent monovalent groups represented by formula (Y1), in the formula (Y1), Z1 represents an arene ring, R1 represents a substituent, and m1 represents an integer of 0 or larger; k1a and k1b are integers of 0-4 and at least one thereof is 1 or larger; R2a and R2b represent substituents; m2a and m2b represent integers of 0-4; k1a+m2a and k1b+m2b are 4 or smaller; and Y2a and Y2b represent monovalent groups represented by formula (Y2), in the formula (Y2), A1 and A2 represent alkylene groups, and n2 represents an integer of 0 or larger.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a novel diol compound having a fluorene skeleton, a resin containing this diol compound as a polymerization component, and a production method and use thereof. [Background technology]

[0002] Diol compounds having a fluorene skeleton are often used as optical plastics (or optical resin materials) by taking advantage of their optical properties such as high refractive index. Among them, diol compounds having a 9,9-bisarylfluorene skeleton are known to exhibit particularly excellent optical properties due to their cardo structure, and for example, Patent Documents 1 to 4 disclose polyester resins and polycarbonate resins containing diol compounds having a 9,9-bisarylfluorene skeleton as polymerization components.

[0003] Patent Document 5 discloses that a polyester resin containing a diol compound having a specific fluorene skeleton as a polymerization component, although not a 9,9-bisarylfluorene skeleton, exhibits negative birefringence, and that this polyester resin is used to form a multilayer optical film. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2017-179323 A [Patent Document 2] JP 2018-104691 A [Patent Document 3] JP 2016-69643 A [Patent Document 4] JP 2018-172658 A [Patent Document 5] US Patent Application Publication No. 2012 / 0170118 Summary of the Invention [Problem to be solved by the invention]

[0005] In the examples of Patent Documents 1 and 2, polycarbonate resins are prepared that contain, as polymerization components, diol compounds having a 9,9-bisarylfluorene skeleton, such as 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF), 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF), and 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF).

[0006] In addition, in the Examples of Patent Documents 3 and 4, polyester resins are prepared that contain the above-mentioned BNEF, BPEF, or 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene (BOPPEF) as a polymerization component, as a diol compound having a 9,9-bisarylfluorene skeleton.

[0007] Although the resins obtained in the examples of Patent Documents 1 to 4 exhibit a high refractive index, the demand for optical resin materials with a high refractive index remains high, and depending on the application, they may not be able to be fully met.

[0008] If an attempt is made to form a resin from a monomer having many benzene ring skeletons (or aromatic ring skeletons) in order to achieve an even higher refractive index, the glass transition temperature Tg rises excessively due to the rigidity of the benzene ring skeleton, resulting in a decrease in fluidity (melt fluidity), making injection molding and the like difficult, and a decrease in moldability (handling ease or productivity). In other words, there is a trade-off between a high refractive index and high moldability, and it is not easy to achieve a higher refractive index. Furthermore, since there is a trade-off between a high refractive index and a low birefringence, a resin having many benzene ring structures introduced therein may easily have an increased birefringence.

[0009] In addition, in Example 1c of Patent Document 5, it is described that 9,9-bis[2-(ethoxycarbonyl)ethyl]fluorene was reacted with lithium aluminum hydride to prepare 9,9-bis(3-hydroxypropyl)fluorene, and further in Examples 9, 12, 16 and 18, polyester resins containing this diol compound as a polymerization component were prepared.

[0010] However, since the diol component used in these examples is not a diol compound having a 9,9-bisarylfluorene skeleton, the refractive index of the obtained polyester resin is not very high.

[0011] Therefore, an object of the present invention is to provide a novel diol compound capable of forming a resin which exhibits a high refractive index and is excellent in moldability (handleability or productivity), a resin containing this diol compound as a polymerization component, and a production method and use thereof. [Means for solving the problem]

[0012] Means for Solving the Problems The present inventors conducted extensive research to achieve the above object, and as a result, they discovered that a diol compound having a specific chemical structure in which aryl groups are bonded to positions 1 to 8 of a fluorene skeleton and an alkylene group is bonded to the 9,9-position can unexpectedly form a resin exhibiting a remarkably high refractive index without impairing moldability, despite not having a 9,9-bisarylfluorene skeleton, and thus completed the present invention.

[0013] That is, the diol compound of the present invention is represented by the following formula (1).

[0014] [ka]

[0015] [In the formula, Y 1a and Y 1beach independently represents a monovalent group represented by the following formula (Y1), k1a and k1b each independently represent an integer of 0 to 4, and at least one of k1a and k1b is 1 or more, R 2a and R 2b each independently represents a substituent; m2a and m2b each independently represent an integer of 0 to 4; k1a+m2a and k1b+m2b are each independently 4 or less; Y 2a and Y 2b each independently represents a monovalent group represented by the following formula (Y2).

[0016] [ka]

[0017] (In the formula, Z 1 indicates an arene ring, R 1 represents a substituent, and m1 represents an integer of 0 or 1 or more.

[0018] [ka]

[0019] (In the formula, A 1 and A 2 each independently represents a linear or branched alkylene group, and n2 represents 0 or an integer of 1 or more.

[0020] In the formula (1), Z 1 is C 6-12 may be an arene ring, and k1a and k2b may be integers of about 1 to 2; A 1 is linear or branched C 1-6 may be an alkylene group, A 2 is linear or branched C 2-4 It may be an alkylene group, and n2 may be 0 or an integer of about 1 to 10.

[0021] In addition, in the formula (1), Z 1 may be a benzene ring or a naphthalene ring, k1a and k2b may be 1; A 1 is linear or branched C 1-4 may be an alkylene group, n2 may be 0.

[0022] The present invention encompasses a method for producing the diol compound, which comprises a reduction step of reducing a compound represented by the following formula (I):

[0023] [ka]

[0024] [In the formula, Y 3a and Y 3b each independently represents a monovalent group represented by the following formula (Y3): Y 1a and Y 1b , k1a and k1b, R 2a and R 2b and m2a and m2b are the same as those in formula (1).

[0025] [ka]

[0026] (In the formula, A 3 represents a linear or branched alkylene group, R 3 represents a hydrogen atom or an alkyl group).

[0027] The present invention also includes a resin containing a structural unit represented by the following formula (1P).

[0028] [ka]

[0029] [In the formula, Y 2c and Y 2d each independently represents a divalent group represented by the following formula (Y2c): Y 1a and Y 1b , k1a and k1b, R 2a and R 2b , m2a and m2b are the same as those in formula (1).

[0030] [ka]

[0031] (In the formula, A 1 , A 2 and n2 are the same as in formula (1), A 1 is attached to the 9th position of the fluorene ring).

[0032] The resin may be a polyester resin containing the first diol unit (A1) represented by the formula (1P) as the diol unit (A). The proportion of the first diol unit (A1) represented by the formula (1P) may be about 5 to 100 mol % based on the total diol unit (A).

[0033] The resin may be a polycarbonate resin, in which the diol unit (A) further contains a second diol unit (A2) represented by the following formula (2).

[0034] [ka]

[0035] (In the formula, Z 2a and Z 2b each independently represents an arene ring, R 4 represents a substituent, m4 represents an integer of 0 to 8, R 5a and R 5beach independently represents a substituent; m5a and m5b each independently represent an integer of 0 or 1 or more; A 4a and A 4b each independently represents a linear or branched alkylene group, and n4a and n4b each independently represent an integer of 0 or 1 or more.

[0036] In the formula (2), Z 2a and Z 2b is C 6-10 may be an arene ring, R 5a and R 5b may be a hydrocarbon group, m5a and m5b may be integers of about 0 to 2, A 4a and A 4b is linear or branched C 2-6 It may be an alkylene group, and n4a and n4b may be integers of about 0 to 3.

[0037] In the polycarbonate resin, the ratio of the first diol units (A1) to the second diol units (A2) may be the former / latter (molar ratio)=about 20 / 80 to 80 / 20.

[0038] The resin may be a polyester carbonate resin. In the polyester carbonate resin, the diol unit (A) may further include the second diol unit (A2). The polyester carbonate resin may further include a first dicarboxylic acid unit (B1) represented by the following formula (4) as the dicarboxylic acid unit (B).

[0039] [ka]

[0040] (In the formula, R 6 represents a substituent, m6 represents an integer of 0 to 8, A 6a and A 6beach independently represents a linear or branched alkylene group.

[0041] In the polyester carbonate resin, the ratio of the first diol unit (A1) to the second diol unit (A2) may be the former / the latter (molar ratio) of about 10 / 90 to 50 / 50, The ratio of the dicarboxylic acid unit (B) may be about 0.5 to 0.85 mol per 1 mol of the diol unit (A), The proportion of the first dicarboxylic acid units (B1) may be about 50 to 100 mol % based on the total of the dicarboxylic acid units (B).

[0042] The resin may be a polyester resin, in which the diol unit (A) may further include a third diol unit (A3) represented by the following formula (3).

[0043] [ka]

[0044] (In the formula, A 5 represents a linear or branched alkylene group, and n5 represents an integer of 1 or more.

[0045] The polyester resin may further contain the first dicarboxylic acid unit (B1) as the dicarboxylic acid unit (B). The dicarboxylic acid unit (B) may contain a second dicarboxylic acid unit (B2) represented by the following formula (5).

[0046] [ka]

[0047] (In the formula, Z 3 indicates an arene ring, R 7 represents a substituent, and m7 represents an integer of 0 or 1 or more).

[0048] In the polyester resin, the ratio of the first diol unit (A1) to the third diol unit (A3) may be the former / the latter (molar ratio)=about 70 / 30 to 95 / 5, The ratio of the first dicarboxylic acid unit (B1) may be about 0.3 to 1.5 mol per 1 mol of the first diol unit (A1), The ratio of the first dicarboxylic acid unit (B1) to the second dicarboxylic acid unit (B2) may be the former / latter (molar ratio) of about 50 / 50 to 90 / 10.

[0049] The present invention also includes a molded article containing the resin. The molded article may be an optical member such as an optical film or an optical lens.

[0050] In addition, the present invention may solve the following problems as a secondary object.

[0051] That is, another object of the present invention is to provide a diol compound capable of forming a resin having a high refractive index, high moldability, and low birefringence in a well-balanced manner, a resin containing this diol compound as a polymerization component, and a production method and use thereof.

[0052] Still another object of the present invention is to provide a diol compound capable of forming a resin which satisfies a high refractive index, high moldability, and low birefringence in a well-balanced manner and also exhibits a low Abbe number, a resin which contains this diol compound as a polymerization component, and methods for producing the same and uses thereof.

[0053] In this specification and claims, a "diol unit" means a constituent unit derived from a diol component, i.e., a unit (or a divalent group) obtained by removing hydrogen atoms from two hydroxyl groups of a corresponding diol, and a "diol component" (including compounds exemplified as diol components) may be used synonymously with the corresponding "diol unit".

[0054] The term "dicarboxylic acid unit" refers to a structural unit derived from a dicarboxylic acid component, i.e., a unit (or a divalent group) obtained by removing OH (hydroxyl group) from two carboxyl groups of the corresponding dicarboxylic acid. The term "dicarboxylic acid component" is used to mean not only dicarboxylic acids but also derivatives that can be used as polymerization components, such as ester-forming derivatives, such as dicarboxylic acid esters, dicarboxylic acid halides, and dicarboxylic acid anhydrides. The dicarboxylic acid esters include alkyl esters of dicarboxylic acid components, particularly lower alkyl esters, such as C esters, ethyl esters, and t-butyl esters. 1-4 Examples of the dicarboxylic acid halide include dicarboxylic acid chloride and dicarboxylic acid bromide. The ester-forming derivative may be a monoester (half ester) or a diester. In addition, the term "dicarboxylic acid component" (including compounds exemplified as dicarboxylic acid components) may be used synonymously with the corresponding "dicarboxylic acid unit".

[0055] In this specification and claims, the number of carbon atoms in a substituent is represented by C 1 , C 6 , C 10 For example, an alkyl group with one carbon atom is represented as "C 1 Alkyl" and aryl groups with 6 to 10 carbon atoms are indicated as "C 6-10 It is indicated as "aryl".

[0056] Furthermore, in this specification and claims, unless otherwise specified, the terms "low birefringence" and "low birefringence" mean that the absolute value of birefringence is low (that is, close to 0). Effect of the Invention

[0057] Although the diol compound having a specific chemical structure of the present invention does not have a 9,9-bisarylfluorene skeleton, it can form a resin that exhibits a high refractive index and has excellent moldability (handling ability or productivity). It can also form a resin that has a good balance of not only a high refractive index and high moldability, but also low birefringence. It can also form a resin that has a good balance of a high refractive index, high moldability, low birefringence, and low Abbe number. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0058] [Diol compound represented by formula (1)] The novel diol compound (also referred to as the first diol component) of the present invention is represented by the above formula (1). In the above formula (1), a monovalent group Y 1a and Y 1b Z in the formula (Y1) represents 1 Examples of the arene ring (aromatic hydrocarbon ring) represented by the formula (1) include a monocyclic arene ring such as a benzene ring, a polycyclic arene ring, etc. Examples of the polycyclic arene ring include a condensed polycyclic arene ring (condensed polycyclic aromatic hydrocarbon ring), a ring-assembled arene ring (ring-assembled aromatic hydrocarbon ring), etc.

[0059] The fused polycyclic arene ring includes, for example, fused bicyclic arene rings, fused tricyclic arene rings, and other fused bicyclic to tetracyclic arene rings. The fused bicyclic arene ring includes, for example, fused bicyclic C rings such as naphthalene ring and indene ring. 10-16 Examples of the fused tricyclic arene ring include fused tricyclic C arene rings such as anthracene ring and phenanthrene ring. 14-20 A preferred fused polycyclic arene ring is a fused polycyclic C ring such as a naphthalene ring. 10-14 It is an arene ring.

[0060] Examples of the ring assembly arene ring include biarene rings such as biphenyl ring, phenylnaphthalene ring, and binaphthyl ring; and terarene rings such as terphenyl ring. Preferred ring assembly arene rings are C 12-18 This is a biarene ring.

[0061] In the present specification and claims, a "ring assembly arene ring" refers to two or more ring systems (arene ring systems) directly linked by single bonds or double bonds, and the number of bonds directly linking the rings is one less than the number of ring systems; for example, as described above, a phenylnaphthalene ring, a binaphthyl ring, and the like are classified as ring assembly arene rings even though they have a fused polycyclic arene ring skeleton, and are clearly distinguished from "fused polycyclic arene rings" such as a naphthalene ring (non-ring assembly arene ring).

[0062] Preferred Ring Z 1 As for C 6-14 arene rings, and more preferably C rings such as benzene rings, naphthalene rings, and biphenyl rings. 6-12 C such as an arene ring, more preferably a benzene ring or a naphthalene ring 6-10 arene rings, especially naphthalene rings. 1 When the ring is a condensed polycyclic arene ring such as a naphthalene ring, the refractive index can be effectively improved and the heat resistance can be easily adjusted to an appropriate level, which is preferable.

[0063] Also, the monovalent group Y 1a and Y 1b Ring Z in 1 may be substituted at any of the 1- to 4-positions and the 5- to 8-positions of the fluorene skeleton, and examples of such positions include the 2-position, the 3-position, and / or the 7-position. 1a and Y 1b When the substitution numbers k1a and k1b are 1, preferred substitution positions (or bonding positions) are symmetrical positions on the paper in formula (1), such as 1,8-positions, 2,7-positions, 3,6-positions, and 4,5-positions, and particularly preferred are 2,7-positions.

[0064] In addition, the ring Z of the fluorene skeleton 1The bonding position of the ring Z may be any position. 1 When is a naphthalene ring, it may be at either the 1-position or the 2-position of the naphthalene ring, but is preferably at the 2-position of the naphthalene ring.

[0065] R 1 Examples of the substituent represented by the formula (non-reactive substituent or non-polymerizable substituent) include a halogen atom, a hydrocarbon group (or a group [-R h ]), the group [-OR h ](wherein, R h represents the above-mentioned hydrocarbon group), the group [-SR h ](wherein, R h represents the above-mentioned hydrocarbon group), an acyl group, a nitro group, a cyano group, a mono- or di-substituted amino group, and the like.

[0066] Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0067] R h Examples of the hydrocarbon group represented by the formula (I) include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

[0068] Examples of the alkyl group include linear or branched C alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl groups. 1-10 The alkyl group is preferably a linear or branched C 1-6 Alkyl groups, more preferably linear or branched C 1-4 It is an alkyl group.

[0069] Examples of the cycloalkyl group include C cyclopentyl and cyclohexyl groups. 5-10 Cycloalkyl groups are included.

[0070] Examples of the aryl group include C phenyl, alkylphenyl, biphenylyl, and naphthyl groups. 6-12Examples of the alkylphenyl group include mono- to tri-C alkylphenyl groups such as methylphenyl group (or tolyl group), dimethylphenyl group (or xylyl group), etc. 1-4 Examples include alkyl-phenyl groups.

[0071] Examples of the aralkyl group include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl-C 1-4 Examples of such groups include alkyl groups.

[0072] The group [-OR h Examples of the hydrocarbon group R h Examples of the alkoxy group include linear or branched C alkoxy groups such as methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, and t-butoxy groups. 1-10 Examples of the cycloalkyloxy group include a C alkoxy group such as a cyclohexyloxy group. 5-10 Examples of the aryloxy group include C aryloxy groups such as phenoxy groups. 6-10 Examples of the aralkyloxy group include C aryloxy groups such as benzyloxy groups. 6-10 Aryl-C 1-4 An example of such a group is an alkyloxy group.

[0073] The group [-SR h Examples of the hydrocarbon group R h Examples of the alkylthio group include groups having a C group such as a methylthio group, an ethylthio group, a propylthio group, an n-butylthio group, and a t-butylthio group. 1-10 Examples of the cycloalkylthio group include a C alkylthio group such as a cyclohexylthio group. 5-10Examples of the arylthio group include a C thiophenoxy group. 6-10 Examples of the aralkylthio group include C arylthio groups such as benzylthio groups. 6-10 Aryl-C 1-4 Examples of such groups include alkylthio groups.

[0074] Acyl groups include C such as acetyl groups. 1-6 Examples include alkyl-carbonyl groups.

[0075] Examples of the mono- or di-substituted amino group include a dialkylamino group and a bis(alkylcarbonyl)amino group. Examples of the dialkylamino group include a di-C group such as a dimethylamino group. 1-4 Examples of the bis(alkylcarbonyl)amino group include bis(C 1-4 alkyl-carbonyl)amino groups.

[0076] Typical group R 1 Examples of the group R include a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, a substituted amino group, etc. When m1 is 1 or more, a preferred group R 1 The alkyl group and the alkoxy group are linear or branched C groups such as methyl groups. 1-6 Linear or branched chain C such as alkyl and methoxy groups 1-4 Alkoxy groups are preferred, among which alkyl groups, particularly methyl groups, and the like, 1-4 The alkyl group is preferred. 1 is an aryl group, the group R 1 is Z 1 may form the ring assembly arene ring.

[0077] The number of substitutions m1 is the number of substitutions in the ring Z 1For example, it can be selected from integers of about 0 to 7. Preferred ranges are integers of 0 to 4, 0 to 2, more preferably 0 or 1, and particularly preferably 0. When the number of substitutions m1 is 2 or more, the ring Z 1 Two or more groups R 1 The types of may be the same or different. 1 The substitution position of ring Z is not particularly limited. 1 The selection may be made according to the type of

[0078] Representative monovalent groups Y represented by the above formula (Y1) 1a , Y 1b Examples of the alkyl group include a phenyl group, a naphthyl group such as a 1-naphthyl group or a 2-naphthyl group, and a biphenylyl group, with a phenyl group and a naphthyl group being preferred, a naphthyl group being more preferred, and a 2-naphthyl group being particularly preferred.

[0079] Monovalent group Y 1a , Y 1b The substitution numbers k1a and k1b are, for example, integers of about 0 to 3, preferably 0 to 2, more preferably 1 or 2, and particularly preferably 1. k1a and k1b may be different from each other, but are preferably the same. At least one of k1a and k1b is an integer of 1 or more, preferably both are integers of 1 or more, and more preferably both are 1.

[0080] When k1a and k1b are each 1 or more, the groups Y substituted on different benzene rings among the two benzene rings forming the fluorene skeleton are 1a and Y 1b The types of may be different from each other, but are preferably the same. When k1a and k1b are 2 or more, two or more groups Y 1a , Y 1b The types may be the same or different from each other.

[0081] R 2a , R 2bThe substituent represented by the formula (non-reactive substituent or non-polymerizable substituent) is the group Y 1a , Y 1b Representative examples of the substituent include hydrocarbon groups such as alkyl groups (excluding aryl groups), halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms, and cyano groups. Examples of the alkyl groups include linear or branched C alkyl groups such as methyl groups, ethyl groups, and t-butyl groups. 1-6 When the number of substitutions m2a and m2b is 1 or more, preferred R 2a , R 2b As examples, C such as methyl group 1-4 It is an alkyl group.

[0082] R 2a and R 2b The substitution numbers m2a and m2b are, for example, integers of about 0 to 3, preferably integers 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 and m2b are each 1 or more, R substituted on different benzene rings of the two benzene rings forming the fluorene skeleton is preferably 0. 2a and R 2b The types of m2a and m2b may be different from each other, but are preferably the same. When m2a and m2b are 2 or more, two or more R 2a , R 2b The types of R may be the same or different. 2a and R 2b The substitution position of the group Y 1a , Y 1b It is sufficient that the substitution is made at a position other than the substitution position of the above.

[0083] The total values ​​k1a+m2a and k1b+m2b of the numbers of substitutions in the two benzene rings forming the fluorene skeleton are each, for example, an integer of 0 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and further preferably 1. The total values ​​k1a+m2a and k1b+m2b may be different from each other, but are preferably the same.

[0084] A monovalent group (or a hydroxyl group-containing group) Y bonded to the 9,9-position of the fluorene skeleton 2a and Y 2b In the formula (Y2), A 1 Examples of the linear or branched alkylene group represented by the formula (I) include linear or branched C alkylene groups such as methylene, ethylene, trimethylene, propylene, 1,2-butanediyl, and 2-methylpropane-1,3-diyl. 1-12 Preferred alkylene groups include linear or branched C 1-8 Alkylene groups, specifically, linear or branched C groups such as methylene, ethylene, trimethylene, propylene, and 2-methylpropane-1,3-diyl groups 1-6 An alkylene group is preferable, and a linear or branched C 1-5 is preferably a linear or branched alkylene group. 1-4 Alkylene groups, particularly linear or branched C 2-4 An alkylene group is preferred, and a trimethylene group is particularly preferred.

[0085] A 2 Examples of the linear or branched alkylene group represented by the formula (I) include linear or branched C alkylene groups such as an ethylene group, a propylene group, a trimethylene group, a 1,2-butanediyl group, a 1,3-butanediyl group, and a tetramethylene group. 2-6 Preferred alkylene groups include 2 is linear or branched C 2-4 is preferably a linear or branched alkylene group. 2-3 Among these, an alkylene group is preferable, and an ethylene group or a propylene group is particularly preferable, with an ethylene group being particularly preferable.

[0086] Oxyalkylene group -(A 2The repeat number n2 of (A)- can be selected, for example, from the range of about 0 to 20, and preferred ranges are 0 to 15, 0 to 10, 0 to 8, 0 to 5, 0 to 3, 0 to 2, and 0 to 1, in the following stepwise order, and is particularly 0. The repeat number n2 may be an average value (or an arithmetic average value), that is, the average number of moles added, and the range is the same as the range of integers described above, including the preferred embodiments. When n2 is 2 or more, the (poly)oxyalkylene group -(A 2 O) n2 - 2 or more A's in 2 may be different from each other, but are preferably the same.

[0087] Also, Y 2a and Y 2b The total number of repeat numbers n2 in the formula (1), i.e., the total number of oxyalkylene groups in one molecule of the diol compound represented by the formula (1) (or the average of the total number of moles added) [hereinafter, simply referred to as the total number of n2], can be selected, for example, from a range of about 0 to 30, and preferred ranges are 0 to 20, 0 to 10, 0 to 6, 0 to 4, 0 to 2, and more preferably 0 to 1, particularly 0. The total number of n2 may be an integer or the average of the total number of moles added.

[0088] If the value of n2 or the total number of n2 is too large, the refractive index and heat resistance may decrease.

[0089] The total number of n2 can be measured by a conventional method. For example, the total number of n2 in the formula (1) can be measured by a conventional method. 2a and Y 2b A diol compound in which n2 is 0 [a compound represented by formula (1A) described later] is subjected to an addition reaction with an alkylene oxide (alkylene carbonate or haloalkanol) to obtain a (poly)alkyleneoxy group [-(OA 2 ) n1-], the arithmetic mean or average value can be calculated from the ratio of the amount of diol compound (or hydroxyl value) to the amount of alkylene oxide (alkylene carbonate or haloalkanol) consumed in the reaction, specifically, by the method described in JP 2013-53310 A.

[0090] Representative diol compounds represented by the formula (1) include, for example, compounds in which k1a and k1b are 1 and Z 1 C such as benzene ring, naphthalene ring, biphenyl ring 6-12 arene ring, A 1 is linear or branched C 1-6 is an alkylene group, 2 is linear or branched C 2-4 and a diol compound in which k1a and k1b are each an alkylene group and n2 is 0 or 1 to 10; 1 is a benzene ring or a naphthalene ring, and A 1 is linear or branched C 1-4 is an alkylene group, 2 is a linear or branched chain C such as ethylene group or propylene group 2-3 It is more preferable that k1a and k1b are each 1, and Z 1 is a naphthalene ring, and A 1 is linear or branched C 2-4 is an alkylene group, 2 is an ethylene group, and n2 is 0 or 1; among these, 9,9-bis(3-hydroxypropyl)-dinaphthylfluorenes such as 9,9-bis(3-hydroxypropyl)-di(1-naphthyl)fluorene and 9,9-bis(3-hydroxypropyl)-di(2-naphthyl)fluorene are preferred; and 9,9-bis(3-hydroxypropyl)-2,7-dinaphthylfluorenes such as 9,9-bis(3-hydroxypropyl)-2,7-di(2-naphthyl)fluorene are particularly preferred.

[0091] The diol compound represented by the formula (1) has a high refractive index, and the refractive index nD at a temperature of 25° C. and a wavelength of 589 nm may be, for example, about 1.7 to 1.8, and preferred ranges are 1.73 to 1.78, 1.74 to 1.77, 1.745 to 1.765, and 1.75 to 1.76 in the following stepwise order.

[0092] The melting point of the diol compound represented by the formula (1) may be, for example, about 100 to 250°C, and preferred ranges are 150 to 240°C, 175 to 230°C, and 180 to 225°C, in the following stepwise order.

[0093] The 5% mass loss temperature of the diol compound represented by the formula (1) may be, for example, about 250 to 500°C, and preferred ranges are 350 to 450°C, 370 to 420°C, and 380 to 400°C in the following stepwise order.

[0094] In this specification and claims, the refractive index, melting point and 5% mass loss temperature of the diol compound represented by the formula (1) can be measured by the method described in the examples below.

[0095] [Method for producing diol compound represented by formula (1)] The method for producing the diol compound represented by the formula (1) is not particularly limited. For example, 2a and Y 2b The diol compound in which n2 is 0 [also referred to as a compound represented by formula (1A)] may be prepared according to the following reaction scheme including a reduction step of subjecting a compound represented by the following formula (I) to a reduction reaction.

[0096] [ka]

[0097] [where, X 1a and X 2a And X 1b and X 2beach independently represents a pair of reactive groups capable of forming a carbon-carbon bond (or a direct bond) by a coupling reaction, Y 3a and Y 3b are each independently represented by the following formula (Y3)

[0098] [ka]

[0099] (In the formula, A 3 represents a linear or branched alkylene group, R 3 represents a hydrogen atom or an alkyl group. represents a monovalent group represented by Y 1a and Y 1b , k1a and k1b, R 2a and R 2b , m2a and m2b, and Y 2a and Y 2b (However, Y 2a and Y 2b In the formula (1), n2 represents 0.) is the same as the formula (1) including preferred embodiments.

[0100] (Preparation of Compounds Represented by Formula (I)) The compound represented by formula (I) can be prepared by a coupling reaction (or a cross-coupling reaction) between the compound represented by formula (II) and the compounds represented by formulas (IIIa) and (IIIb).

[0101] Examples of the coupling reaction include conventional coupling reactions, such as Suzuki-Miyaura coupling reaction, Migita-Kosugi-Stille coupling reaction, Negishi coupling reaction, Hiyama coupling reaction, and other coupling reactions using a palladium catalyst (or a palladium(0) catalyst), Kumada-Tamao-Corriu coupling reaction, and other coupling reactions using a nickel catalyst (or a nickel(0) catalyst), etc. Among these coupling reactions, the Suzuki-Miyaura coupling reaction is preferred.

[0102] In the formula (II), X 1a and X 1b each independently represents a reactive group capable of forming a carbon-carbon bond (or a direct bond) by a coupling reaction; in the formulae (IIIa) and (IIIb), X 2a is the above X 1a And, X 2b is the above X 1b and each represent a reactive group capable of forming a carbon-carbon bond by a coupling reaction. Reactive group X 1a and X 1b And X 2a and X 2b can be appropriately selected depending on the type of the coupling reaction. In the case of synthesis by Suzuki-Miyaura coupling reaction, one reactive group, for example, X 1a and X 1b Examples of the fluorinated alkanesulfonyloxy group include a halogen atom or a fluorinated alkanesulfonyloxy group. Examples of the halogen atom include an iodine atom, a bromine atom, and a chlorine atom. Examples of the fluorinated alkanesulfonyloxy group include a fluorinated C such as a trifluoromethanesulfonyloxy group (or a group [-OTf]). 1-4 Alkanesulfonyloxy groups and the like are included. These one reactive groups may be used alone or in combination of two or more. Among these one reactive groups, a halogen atom is preferred, an iodine atom or a bromine atom is more preferred, and a bromine atom is even more preferred. In addition, X 1a and X 1b The types of may be different from each other, but are preferably the same.

[0103] One of the reactive groups X in the Suzuki-Miyaura coupling reaction 1a and X 1b Another reactive group X capable of coupling with 2a and X 2b Examples of the boronic acid group include a dihydroxyboryl group or a group [-B(OH) 2]), and boronate ester groups. Examples of the boronate ester group include dialkoxyboryl groups such as dimethoxyboryl group, diisopropoxyboryl group, and dibutoxyboryl group; and cyclic boronate ester groups such as pinacolatoboryl group (or group [-Bpin]), 1,3,2-dioxaborinane-2-yl group, and 5,5-dimethyl-1,3,2-dioxaborinane-2-yl group. These other reactive groups may be used alone or in combination of two or more. Among the other reactive groups, the group [-B(OH) 2 ] is preferred. 2a and X 2b The types of may be different from each other, but are preferably the same.

[0104] In addition, the group X 1a and X 1b and group X 2a and X 2b X may be any reactive group as long as it is a pair of reactive groups capable of coupling reaction with each other, 1a and X 1b is the other reactive group such as a boronic acid group, and X 2a and X 2b may be one of the reactive groups such as a halogen atom, but X 1a and X 1b is one of the reactive groups such as a halogen atom, and X 2a and X 2b is preferably the other reactive group such as a boronic acid group.

[0105] Also, the monovalent group Y 3a and Y 3b In the formula (Y3), 3 is A in formula (1). 1 A is an alkylene group with one less carbon atom corresponding to the alkylene group A. 3 Examples of the alkyl group include linear or branched C alkyl groups such as methylene, ethylene, trimethylene, propylene, 1,2-butanediyl, and 2-methylpropane-1,3-diyl groups. 1-11Alkylene groups are preferably used, and the following steps are preferably taken: 1-5 Alkylene group, C 1-4 Alkylene group, C 1-3 An alkylene group is preferred, and an ethylene group is particularly preferred.

[0106] R 3 Examples of the alkyl group represented by the formula (I) include linear or branched C alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and t-butyl groups. 1-6 Alkyl groups, etc., are preferred. 1-4 Alkyl groups, more preferably C 1-3 Alkyl groups, especially methyl groups, etc. 1-2 Alkyl groups are preferred. R 3 may be either a hydrogen atom or an alkyl group, but is preferably an alkyl group.

[0107] Examples of the compound represented by the formula (II) include compounds corresponding to the preferred embodiments of the diol compound represented by the formula (1), such as 9,9-bis(alkoxycarbonylalkyl)dihalofluorene.

[0108] Examples of the 9,9-bis(alkoxycarbonylalkyl)dihalofluorene include 9,9-bis(C ) such as 9,9-bis(2-methoxycarbonylethyl)-2,7-dibromofluorene, 9,9-bis(2-ethoxycarbonylethyl)-2,7-dibromofluorene, and 9,9-bis(2-methoxycarbonylpropyl)-2,7-dibromofluorene. 1-4 Alkoxy-carbonyl-C 2-6 9,9-bis(alkoxycarbonylalkyl)dihalofluorenes may be prepared, for example, according to the method described in JP-A-2005-89422, specifically, by reacting a dihalo-9H-fluorene having no substitution at the 9-position, such as 2,7-dibromofluorene, with an acrylic acid ester, such as methyl acrylate, or a haloacetic acid ester, such as methyl bromoacetate, in the presence of a base catalyst, such as trimethylbenzylammonium hydroxide.

[0109] The compound represented by the formula (IIIa) and the compound represented by the formula (IIIb) are compounds corresponding to the preferred embodiment of the diol compound represented by the formula (1), such as phenylboronic acid, 1-naphthylboronic acid, 2-naphthylboronic acid, etc., and 2-naphthylboronic acid is preferred. The compound represented by the formula (IIIa) and the compound represented by the formula (IIIb) are preferably the same compound, and commercially available products can be used.

[0110] The ratio of the compound represented by formula (II) to the total amount of the compound represented by formula (IIIa) and the compound represented by formula (IIIb) may be, for example, the former / latter (molar ratio)=about 1 / 2 to 1 / 10, and preferred ranges are 1 / 2.1 to 1 / 5 and 1 / 2.2 to 1 / 3.5 in the following stepwise manner.

[0111] The coupling reaction may be carried out in the presence of a catalyst. When the synthesis is carried out by the Suzuki-Miyaura coupling reaction, the reaction may be carried out in the presence of a palladium catalyst, and the palladium catalyst may be a conventional coupling catalyst such as a palladium (0) catalyst or a palladium (II) catalyst.

[0112] Palladium(0) catalysts include, for example, tetrakis(triphenylphosphine)palladium(0) [or Pd(PPh 3 ) 4 ], bis(tri-t-butylphosphine)palladium(0) [or Pd(P(t-Bu) 3 ) 2 ] and other palladium(0)-phosphine complexes.

[0113] Palladium(II) catalysts include, for example, [1,2-bis(diphenylphosphino)ethane]palladium(II) dichloride [or PdCl 2 (dppe)], [1,3-bis(diphenylphosphino)propane]palladium(II) dichloride [or PdCl 2(dppp)], [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride [or PdCl 2 (dppf)], bis(triphenylphosphine)palladium(II) dichloride [or PdCl 2 (PPh 3 ) 2 ], bis(tri-o-tolylphosphine)palladium(II) dichloride [or PdCl 2 (P(o-tolyl) 3 ) 2 In addition, when a palladium(II) catalyst is used, the reaction is initiated by reduction to a zero-valent complex by a reducing compound in the reaction system, such as a phosphine, an amine, or an organometallic reagent.

[0114] The palladium catalyst is, for example, tris(dibenzylideneacetone)dipalladium(0) chloroform complex [or Pd 2 (dba) 3 CHCl 3 Alternatively, the catalyst may be prepared in situ by adding a catalyst precursor such as the above-mentioned aryl group, and a ligand such as a phosphine or a carbene.

[0115] These catalysts can be used alone or in combination of two or more. Among these catalysts, Pd(PPh 3 ) 4 The proportion of the catalyst may be, for example, about 0.01 to 0.1 mol, preferably 0.03 to 0.07 mol, and more preferably 0.04 to 0.06 mol, calculated as the metal, relative to 1 mol of the compound represented by the formula (2).

[0116] The Suzuki-Miyaura coupling reaction may be carried out in the presence of a base, such as a metal carbonate or hydrogen carbonate, a metal hydroxide, a metal fluoride, a metal phosphate, a metal organic acid salt, or a metal alkoxide.

[0117] Examples of metal carbonates or hydrogen carbonates include alkali metal carbonates or hydrogen carbonates such as sodium carbonate, potassium carbonate, cesium carbonate, and sodium hydrogen carbonate, and thallium (I) carbonate.

[0118] Examples of metal hydroxides include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and cesium hydroxide, alkaline earth metal hydroxides such as barium hydroxide, and thallium(I) hydroxide.

[0119] Examples of metal fluorides include alkali metal fluorides such as potassium fluoride and cesium fluoride.

[0120] Examples of metal phosphates include alkali metal phosphates such as tripotassium phosphate.

[0121] Examples of metal organic acid salts include alkali metal acetates such as potassium acetate.

[0122] Examples of metal alkoxides include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide.

[0123] These bases can be used alone or in combination of two or more.Preferred bases are metal carbonates such as sodium carbonate and potassium carbonate.The ratio of the base may be, for example, about 0.1 to 50 mol, preferably 1 to 10 mol, and more preferably 3 to 7 mol, relative to 1 mol of the compound represented by the formula (II).

[0124] The coupling reaction may be carried out in the presence or absence of a phase transfer catalyst. Examples of the phase transfer catalyst include tetraalkylammonium halides such as tetrabutylammonium bromide (TBAB) and trioctylmethylammonium chloride. These phase transfer catalysts may be used alone or in combination of two or more.

[0125] The coupling reaction may be carried out in the absence or presence of a solvent inert to the reaction. Examples of the solvent include water, alcohols such as methanol and ethanol, ethers such as cyclic ethers and chain ethers, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, nitriles such as acetonitrile and benzonitrile, amides such as N,N-dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone, sulfoxides such as dimethyl sulfoxide, and hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

[0126] Examples of cyclic ethers include dioxane and tetrahydrofuran. Examples of chain ethers include dialkyl ethers such as diethyl ether and diisopropyl ether, and glycol ethers. Examples of the glycol ethers include (poly)alkylene glycol monoalkyl ethers such as methyl cellosolve and methyl carbitol, and (poly)alkylene glycol dialkyl ethers such as dimethoxyethane.

[0127] Examples of the aliphatic hydrocarbons include hexane and dodecane. Examples of the alicyclic hydrocarbons include cyclohexane. Examples of the aromatic hydrocarbons include toluene and xylene.

[0128] These solvents may be used alone or in combination of two or more. Among these solvents, a mixed solvent of water and an aromatic hydrocarbon such as toluene is preferred.

[0129] The coupling reaction may be carried out under an inert atmosphere, for example, nitrogen gas or a rare gas such as helium or argon. The reaction temperature is, for example, 50 to 200° C., preferably 60 to 100° C., and more preferably 70 to 80° C. The reaction time may be, for example, about 1 to 24 hours, and preferably 3 to 12 hours.

[0130] After completion of the reaction, the reaction mixture may be separated and purified, if necessary, by a conventional separation and purification method, such as washing, extraction, filtration, dehydration, concentration, decantation, drying, crystallization, reprecipitation, column chromatography, adsorption, or a combination of these methods.

[0131] (Preparation of Compound Represented by Formula (1A) (or Reduction Step)) The diol compound represented by the formula (1A) (Y in formula (1) 2a and Y 2b The compound (wherein n2 is 0) can be prepared by reducing the compound represented by formula (I). A conventional reducing agent may be used for the reduction. Examples of the reducing agent include metal hydrides such as metal borohydrides, metal aluminum hydrides, boranes, aluminum hydrides, organosilicon compounds, and organotin compounds.

[0132] Examples of the metal borohydrides include alkali metal borohydrides; zinc borohydride (Zn(BH 4 ) 2 Examples of the alkali metal borohydrides include lithium borohydride (LiBH 4 ), lithium triethylborohydride (LiBH(C 2 H 5 ) 3 ), lithium tri-s-butylborohydride (LiBH(sC 4 H 9 ) 3 ), lithium bis(2,4,6-trimethylphenyl)borohydride (LiBH(Mes) 2 ) and other lithium borohydrides; sodium borohydride (NaBH 4 ), sodium cyanoborohydride (NaBH 3 CN), sodium trimethoxyborohydride (NaBH(OCH 3 ) 3 ), sodium triacetoxyborohydride (NaBH(OCOCH 3 ) 3 ), sodium borohydride sulfide (NaBH2 S 3 ) and other sodium borohydrides; potassium tri-s-butyl borohydride (KBH(sC 4 H 9 ) 3 ) and potassium borohydrides.

[0133] Examples of the metal aluminum hydrides include alkali metal aluminum hydrides. Examples of the alkali metal aluminum hydrides include lithium aluminum hydride (LiAlH 4 ), lithium trimethoxyaluminum hydride (LiAlH(OCH 3 ) 3 ), lithium tri-t-butoxyaluminum hydride (LiAlH(Ot-C 4 H 9 ) 3 ) and other lithium aluminum hydrides; sodium aluminum hydride (NaAlH 4 ), sodium bis(2-methoxyethoxy)aluminum hydride ([(CH 3 OCH 2 CH 2 O) 2 AlH 2 ]Na) and other sodium aluminum hydrides.

[0134] Examples of boranes include diborane; borane complexes such as borane-tetrahydrofuran complex and borane-dimethylsulfide complex; and 9-borabicyclo[3.3.1]nonane (9-BBN).

[0135] Examples of aluminum hydrides include aluminum hydride (AlH 3 ), diisobutylaluminum hydride ((iC 4 H 9 ) 2 AlH).

[0136] Examples of the organosilicon compound include trialkylsilanes such as triethylsilane, diarylsilanes such as diphenylsilane, and aryldialkylsilanes such as phenyldimethylsilane.

[0137] Examples of the organotin compound include trialkylstannanes such as tri-n-butylstannane, dialkylstannanes such as di-n-butylstannane, and diarylstannanes such as diphenylstannane.

[0138] These reducing agents can be used alone or in combination of two or more. Preferred reducing agents are metal borohydrides such as alkali metal borohydrides, and more preferably sodium borohydride (NaBH 4 ) and other sodium borohydrides.

[0139] The amount of the reducing agent used is, for example, 2 to 10 mol, preferably 2.2 to 5 mol, and more preferably 2.5 to 3.5 mol, relative to 1 mol of the compound represented by the formula (I).

[0140] The reducing agent may be used together with other reagents (or activators) depending on the type of the reducing agent and the compound represented by formula (I). For example, sodium borohydride (NaBH 4 When sodium borohydrides such as sodium trifluoride diethyl ether complex are used as the reducing agent, they may be used together with boron trifluoride ether complexes such as boron trifluoride diethyl ether complex. The ratio of the activator is, for example, 0.1 to 10 mol, preferably 0.5 to 5 mol, and more preferably 0.8 to 1.2 mol, relative to 1 mol of the reducing agent.

[0141] The reduction reaction may be carried out in the presence or absence of an inert solvent. Examples of the solvent include water; alcohols such as methanol, ethanol, and isopropanol; ethers, specifically, cyclic ethers such as dioxane and tetrahydrofuran (THF), chain ethers such as dialkyl ethers and glycol ethers; and hydrocarbons, specifically, aliphatic hydrocarbons such as hexane and dodecane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as benzene, toluene, and xylene. Examples of the dialkyl ether include diethyl ether and diisopropyl ether, and examples of the glycol ether include (poly)alkylene glycol monoalkyl ethers such as methyl cellosolve and methyl carbitol, and (poly)alkylene glycol dialkyl ethers such as dimethoxyethane.

[0142] The solvent may be used alone or in combination of two or more. Preferred solvents are ethers, and more preferred are cyclic ethers such as THF.

[0143] The reaction may be carried out under an inert gas atmosphere, for example, nitrogen or a rare gas such as helium or argon. The reaction temperature is, for example, 0 to 50° C., preferably 5 to 35° C. The reaction time is not particularly limited, and is, for example, about 1 to 48 hours, preferably 2 to 12 hours.

[0144] After the reaction is completed, the reducing agent may be quenched by adding water, or it may be gently quenched in advance with acetone to suppress heat generation.

[0145] After completion of the reaction, the reaction mixture may be separated and purified, if necessary, by a conventional separation and purification method, for example, washing, extraction, filtration, dehydration, drying, concentration, decantation, recrystallization, reprecipitation, chromatography, or a combination of these methods.

[0146] In addition, the alkylene group A 2The diol compound represented by the formula (1) may be prepared by reacting the corresponding alkylene oxide (alkylene carbonate or haloalkanol) in a ratio corresponding to the repeating number n2 by a conventional method.

[0147] [Resin made from diol compound represented by formula (1)] The resin (polymer or macromolecule) prepared using the diol compound represented by the formula (1) as a raw material is not particularly limited, and may be a heat- or light-curable resin. However, it is preferably a thermoplastic resin in that it is possible to adjust the moldability (fluidity or handleability) and heat resistance in a well-balanced manner.

[0148] The thermoplastic resin is not particularly limited as long as it contains at least the diol component (A) as a polymerization component, and examples thereof include polyester-based resins and thermoplastic polyurethane-based resins. From the viewpoint of an excellent balance between optical properties such as a high refractive index, low birefringence, and low Abbe number and moldability, polyester-based resins are preferred.

[0149] The polyester resin may be any resin having at least an ester bond [including a carbonate bond (carbonate bond)] as the main chain skeleton, and examples thereof include polyester resin, polyester carbonate resin, polycarbonate resin, etc. Among the polyester resins, polycarbonate resin is preferred in terms of excellent strength (or hardness) and good injection moldability; polyester resin is preferred in terms of excellent stretchability (flexibility or toughness) and good film moldability; polyester carbonate resin is preferred in terms of excellent balance between strength and stretchability, and can achieve a good balance between injection moldability and film moldability; and polyester resin is most preferred in terms of particularly excellent balance between high refractive index, high moldability, low birefringence, and low Abbe number.

[0150] As specific constituent units of the resin, it is sufficient that the resin contains at least a diol unit (A), and may further contain a dicarboxylic acid unit (B), a carbonate unit (C), and the like.

[0151] (Diol unit (A)) First Diol Unit (A1) The diol unit (A) contains at least a constitutional unit represented by the formula (1P) as the first diol unit (A1). Note that the constitutional unit represented by the formula (1P) corresponds to the first diol component represented by the formula (1), so Y in the formula (1P) 1a and Y 1b , k1a and k1b, R 2a and R 2b , m2a and m2b are the same as those in the above formula (1), including preferred embodiments thereof; Y 2c and Y 2d A in 1 , A 2 and n2 are also each independently selected from the group consisting of Y in the formula (1) including preferred embodiments. 2a and Y 2b is the same as.

[0152] Representative examples of the first diol unit (A1) include the diol units corresponding to the examples in the section on the diol compound represented by the formula (1), and the same applies to the preferred embodiments. The first diol unit (A1) may be used alone or in combination of two or more kinds.

[0153] In the resin of the present invention containing the first diol unit (A1), the refractive index can be significantly improved while suppressing an excessive increase in the glass transition temperature Tg (while maintaining or reducing Tg), and both a high refractive index and high moldability (fluidity or handleability) can be achieved. That is, in the fluorene ring of the formula (1P), an aryl group-containing group (group Y 1a and Y 1b ) is substituted at the 1-8 positions of the fluorene ring, not at the 9 position as in the conventional diol compound having a 9,9-bisarylfluorene skeleton, and an alkylene group A is substituted at the 9 position instead of an aryl group. 1In particular, as shown in the examples described later, even if the compound contains the same number of benzene ring skeletons (aromatic ring skeletons) in its chemical structure as the conventional diol compound having a 9,9-bisarylfluorene skeleton, the first diol unit (A1) can effectively improve the refractive index and furthermore can maintain or reduce Tg, which was an unexpected result.

[0154] In addition, the resin of the present invention can improve moldability without significantly impairing heat resistance (without significantly lowering Tg), which is contrary to moldability, and therefore has an excellent balance between heat resistance and moldability. Furthermore, when the resin contains the first diol unit (A1), it is useful in that it can effectively reduce birefringence even if it contains many benzene ring skeletons (aromatic ring skeletons), and can also significantly reduce the Abbe number, and these properties can be satisfied in a well-balanced manner along with the high refractive index and high moldability.

[0155] The proportion of the first diol unit (A1) in the resin may be, for example, about 1 mol % or more relative to the total diol unit (A), and preferred ranges are 5 to 100 mol %, 10 to 95 mol %, and 20 to 90 mol %, stepwise as follows: If the proportion of the first diol unit (A1) is too low, the refractive index and heat resistance may not be sufficiently improved, and conversely, if it is too high, the birefringence may become large on the negative (minus) side, and the absolute value of the birefringence may not be sufficiently reduced.

[0156] The diol unit (A) may be composed of only the first diol unit (A1), or may further contain a different diol unit, for example, a second diol unit (A2) represented by the above formula (2) or a second diol unit (A3) represented by the above formula (3).

[0157] Second Diol Unit (A2) The diol unit (A) may or may not contain the second diol unit (A2) represented by the formula (2). When the second diol unit (A2) is contained, the refractive index and heat resistance can be improved while suppressing the increase in birefringence.

[0158] In the formula (2), Z 2a and Z 2b Examples of the arene ring represented by include, for example, the ring Z described in the section of the diol compound represented by the formula (1). 1 The same arene rings as the examples of the ring Z can be mentioned. Ring Z 2a and Z 2b The types of may be the same as or different from each other, and it is preferable that they are the same. Ring Z 2a and Z 2b Among them, C arenes such as benzene ring, naphthalene ring, biphenyl ring are preferable, and C arenes such as benzene ring, naphthalene ring are more preferable. From the viewpoint of being easily able to increase the refractive index, decrease the Abbe number, and having an excellent balance with low birefringence and heat resistance, the naphthalene ring is particularly preferable. Incidentally, the types of Z 6-12 and Z 6-10 may be different from each other, but it is preferable that they are the same. 2a and Z 2b The types of may be different from each other, but it is preferable that they are the same.

[0159] In addition, the substitution positions of the ring Z 2a and Z 2b bonded to the 9-position of the fluorene ring are not particularly limited. For example, when the ring Z 2a and Z 2b are naphthalene rings, they are the 1-position or 2-position, preferably the 2-position. When the ring Z 2a and Z 2b are biphenyl rings, they are the 2-position, 3-position or 4-position, preferably the 3-position.

[0160] R 4Examples of the substituent represented by the formula (non-reactive substituent or non-polymerizable substituent) include hydrocarbon groups such as alkyl groups and aryl groups; cyano groups; and halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples of the alkyl groups include linear or branched C alkyl groups such as methyl groups, ethyl groups, propyl groups, isopropyl groups, n-butyl groups, and t-butyl groups. 1-6 Examples of the aryl group include C alkyl groups such as phenyl groups. 6-10 When m4 is 1 or more, preferred groups R 4 is an alkyl group, a cyano group, or a halogen atom, more preferably an alkyl group, particularly a linear or branched C 1-4 Alkyl groups are preferred.

[0161] base R 4 The number of substitutions m4 is, for example, an integer of about 0 to 6, preferably an integer of 0 to 4, an integer of 0 to 2, more preferably 0 or 1, particularly preferably 0. When m4 is 2 or more, two or more groups R 4 The types of may be the same or different. 4 The substitution position of is not particularly limited, and examples thereof include 2- to 7-positions such as 2-, 3- and / or 7-position of the fluorene ring, and preferably 2- or 2,7-positions.

[0162] R 5a and R 5b Examples of the substituent represented by the formula (1) (non-reactive substituent or non-polymerizable substituent) include R 1 The same groups as those exemplified as the substituents R 5a and R 5b Among these, representative groups include halogen atoms; hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups; alkoxy groups; acyl groups; nitro groups; cyano groups; and substituted amino groups. When the number of substitutions m5a and m5b is 1 or more, preferred groups R 5a , R 5bExamples of the alkyl group include an alkyl group, a cycloalkyl group, an aryl group, and an alkoxy group, and more preferably a linear or branched C 1-6 C such as alkyl group and cyclohexyl group 5-8 Cycloalkyl groups, phenyl groups, etc. 6-14 Linear or branched C such as aryl and methoxy groups 1-4 Among them, alkyl groups and aryl groups are preferred, and in particular, linear or branched C alkoxy groups such as methyl groups are preferred. 1-4 C such as alkyl group and phenyl group 6-10 An aryl group is preferred. 5a or R 5b is an aryl group, the group R 5a or R 5b is the ring Z 3a or Z 3b may form a ring assembly arene ring together with

[0163] base R 5a , R 5b The number of substitutions m5a and m5b of the ring Z 2a , Z 2b Each of them may be an integer of 0 or more, for example, an integer of about 0 to 8. Preferred ranges are, in the following stepwise order, integers of 0 to 4, integers of 0 to 2, with 0 or 1 being more preferable, and 0 being particularly preferable.

[0164] The numbers of substitutions m5a and m5b may be different from each other, but are preferably the same. 2a , Z 2b Replace with 2 or more R 5a , R 5b The types of may be the same or different. 5a and R 5b may be the same or different. In particular, when m5a and m5b are 1, ring Z 2a , Z 2b is a benzene ring, a naphthalene ring or a biphenyl ring, a group R 5a , R 5bmay be a methyl group. 5a , R 5b The substitution position of ring Z is not particularly limited. 2a , Z 2b and the ether bond (-O-) and the 9-position of the fluorene ring. 2a , Z 2b In this case, it is substituted at the ortho position (the carbon atom adjacent to the bonding position of the ether bond) relative to the ether bond (-O-).

[0165] Alkylene Group A 4a , A 4b Examples of the alkyl group include linear or branched C alkyl groups such as ethylene, propylene (1,2-propanediyl), trimethylene, 1,2-butanediyl, and tetramethylene groups. 2-6 When the repeating numbers n4a and n4b are 1 or more, preferred A 4a , A 4b is linear or branched C 2-4 C alkylene group, more preferably ethylene group, propylene group, etc. 2-3 An alkylene group is preferable, and an ethylene group is particularly preferable. 4a and A 4b The types may be the same or different from each other.

[0166] Oxyalkylene group (-OA 4a -), (-OA 4b The repeat numbers (number of moles added) n4a and n4b of -) may each be selected from the range of integers of 0 or more, for example, about 0 to 15, and preferred ranges are the following stepwise ranges: 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, and 0 to 1. Moreover, the repeat numbers n4a and n4b are preferably 1 or more in terms of improving polymerization reactivity, and more preferred ranges are the following stepwise ranges: 1 to 15, 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, and 1 to 2, and 1 is particularly preferred.

[0167] In the present specification and claims, the "repetition number (number of added moles)" may be an average value (arithmetic mean value, additive mean value) or an average number of added moles. The preferred embodiment of the average number of added moles of n4a and n4b is the same as the preferred range (range of integers) described above. If the repetition numbers n4a and n4b are too large, the refractive index and heat resistance may decrease.

[0168] In addition, the two repeat numbers n4a and n4b may be the same or different. When n4a and n4b are 2 or more, two or more oxyalkylene groups (-OA 4a -), (-OA 4b -) may be the same or different from each other.

[0169] The group [-O-(A 4a O) n4a -], [-O-(A 4b O) n4b -] (also called ether-containing group) 2a , Z 2b The substitution position for the ring Z 2a , Z 2b The substitution position of the ether-containing group may be any suitable position on the ring Z. 2a , Z 2b When the ring Z is a benzene ring, it is preferably substituted at the 2-, 3- or 4-position, particularly the 3- or 4-position, and particularly the 4-position, of the phenyl group bonded to the 9-position of the fluorene ring. 2a , Z 2b When the ring Z is a naphthalene ring, the ether-containing group is preferably substituted at any one 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 (substitution in a 1-naphthyl or 2-naphthyl relationship), and the 1,5-position, 2,6-position, etc., relationship with respect to this substitution position, is preferred, especially the 2,6-position relationship. 2a , Z 2bWhen the ring Z is an assembled arene ring, the substitution position of the ether-containing group is not particularly limited, and may be substituted, for example, on the arene ring bonded to the 9-position of the fluorene ring or on the arene ring adjacent to this arene ring. 2a , Z 2b is a biphenyl ring (or ring Z 2a , Z 2b is a benzene ring, m5a and m5b are 1, R 5a , R 5b is a phenyl group), the 3- or 4-position of the biphenyl ring, preferably the 3-position, may be bonded to the 9-position of the fluorene ring, and when the 3-position of the biphenyl ring is bonded to the 9-position of the fluorene ring, the substitution position of the ether-containing group is, for example, the 2-, 4-, 5-, 6-, 2'-, 3'- or 4'-position of the biphenyl ring, preferably the 6- or 4'-position, and particularly preferably the 6-position.

[0170] Examples of the second diol component corresponding to the second diol unit (A2) include 9,9-bis(hydroxyaryl)fluorenes in which n4a and n4b are 0 in the formula (2); and 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes in which n4a and n4b are 1 or more, for example, about 1 to 10.

[0171] In this specification and claims, unless otherwise specified, the term "(poly)alkoxy" is used to include both an alkoxy group and a polyalkoxy group.

[0172] 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, and 9,9-bis(hydroxynaphthyl)fluorene.

[0173] Examples of 9,9-bis(hydroxyphenyl)fluorene include 9,9-bis(4-hydroxyphenyl)fluorene.

[0174] Examples of the 9,9-bis(alkyl-hydroxyphenyl)fluorene include 9,9-bis[(mono or di)C]fluorene such as 9,9-bis(4-hydroxy-3-methylphenyl)fluorene and 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene. 1-4 alkyl-hydroxyphenyl]fluorene and the like.

[0175] Examples of the 9,9-bis(aryl-hydroxyphenyl)fluorene include 9,9-bis(C 6-10 aryl-hydroxyphenyl)fluorene.

[0176] Examples of 9,9-bis(hydroxynaphthyl)fluorene include 9,9-bis(6-hydroxy-2-naphthyl)fluorene and 9,9-bis(5-hydroxy-1-naphthyl)fluorene.

[0177] Examples of 9,9-bis[hydroxy(poly)alkoxyaryl]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, and 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorene.

[0178] Examples of the 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[hydroxy(mono- to deca)C such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxypropoxy)phenyl]fluorene, and 9,9-bis[4-(2-(2-hydroxyethoxy)ethoxy)phenyl]fluorene. 2-4 alkoxy-phenyl]fluorene and the like.

[0179] Examples of the 9,9-bis[alkyl-hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[(mono or di)C such as 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxypropoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-(2-hydroxyethoxy)ethoxy)-3-methylphenyl]fluorene, and 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene. 1-4 Alkyl-hydroxy(mono or deca)C 2-4 alkoxy-phenyl]fluorene and the like.

[0180] Examples of the 9,9-bis[aryl-hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[C such as 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxypropoxy)-3-phenylphenyl)fluorene, and 9,9-bis[4-(2-(2-hydroxyethoxy)ethoxy)-3-phenylphenyl]fluorene. 6-10 Aryl-hydroxy(mono to deca)C 2-4 alkoxy-phenyl]fluorene and the like.

[0181] Examples of the 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorene include 9,9-bis[hydroxy(mono- to deca)C such as 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, 9,9-bis[6-(2-hydroxypropoxy)-2-naphthyl]fluorene, 9,9-bis[6-(2-(2-hydroxyethoxy)ethoxy)-2-naphthyl]fluorene, and 9,9-bis[5-(2-hydroxyethoxy)-1-naphthyl]fluorene. 2-4 alkoxy-naphthyl]fluorene and the like.

[0182] These second diol units (A2) may be contained alone or in combination of two or more. Of the second diol units (A2), 9,9-bis[hydroxy(mono- to hexa)C 2-4 Alkoxy C 6-10 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes such as 9,9-bis[hydroxy(mono or di)aryl]fluorene; more preferably 9,9-bis[hydroxy(mono or di)aryl]fluorene; 2-4 Alkoxy C 6-10 aryl]fluorene; more preferably 9,9-bis[hydroxyC] such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, and 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene. 2-3 Alkoxy-C 6-12 aryl]fluorene, and in particular, 9,9-bis[hydroxy C aryl]fluorene such as 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, which has an excellent balance of high refractive index, low birefringence, and high heat resistance, is preferred. 2-3 A structural unit derived from an alkoxynaphthyl]fluorene is preferred.

[0183] The third diol unit (A3) The diol unit (A) may or may not contain a third diol unit (A3) represented by the above formula (3) as necessary. When the third diol unit (A3) is contained, the polymerization reactivity is increased and the molecular weight is easily increased. In addition, an excessive increase in the glass transition temperature may be suppressed, and moldability and handling properties may be improved.

[0184] In the formula (3), A 5 Examples of the alkylene group represented by the formula (I) include linear or branched C alkylene groups such as ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, 1,3-butanediyl group, tetramethylene group, 1,5-pentanediyl group, 1,6-hexanediyl group, 1,8-octanediyl group, and 1,10-decanediyl group. 2-12 Preferred alkylene groups A5 The following are the linear or branched chain C 2-10 Alkylene group, C 2-8 Alkylene group, C 2-6 Alkylene group, C 2-4 C alkylene group, more preferably ethylene group, propylene group, etc. 2-3 An alkylene group is preferred, and an ethylene group is particularly preferred.

[0185] The repeat number n5 can be selected, for example, from the range of about 1 to 10, and the preferred ranges are 1 to 6, 1 to 4, and 1 to 2, stepwise, with 1 being particularly preferred. The repeat number n5 may be an average value (arithmetic mean value or additive mean value), and the preferred embodiments are the same as those in the range of integers described above. When n5 is 2 or more, two or more oxyalkylene groups (-A 5 The types of O-) may be different from each other, but are preferably the same.

[0186] Examples of the third diol component corresponding to the third diol unit (A3) include alkanediols (or alkylene glycols), polyalkanediols (or polyalkylene glycols), and the like.

[0187] As the alkylene glycol, for example, there is mentioned the alkylene glycol represented by the formula (3) where n5 is 1, A 5 corresponding to the alkylene group exemplified above, specifically, linear or branched C alkylene glycols 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, and 1,10-decanediol. 2-12 Alkylene glycol and the like are examples of the alkylene group A. 5 The same applies to the corresponding

[0188] As the polyalkylene glycol, in the above formula (3), n5 is 2 or more, for example, about 2 to 10;5 Compounds in which the alkylene group corresponds to the above-mentioned alkylene group, specifically, di- or deca-linear or branched C alkylenes such as diethylene glycol, dipropylene glycol, and triethylene glycol. 2-12 Alkylene glycol, etc., preferably di- or hexaC 2-6 Alkylene glycol, more preferably di- or tetra-C 2-4 Alkylene glycols are included.

[0189] These third diol units (A3) may be contained alone or in combination of two or more. The third diol unit (A3) is preferably an alkylene glycol, more preferably a linear or branched C alkylene glycol such as ethylene glycol or 1,5-pentanediol, because it is difficult to significantly reduce the refractive index. 2-6 C alkylene glycol, more preferably ethylene glycol, propylene glycol, 1,4-butanediol, etc. 2-4 Alkylene glycols, especially ethylene glycol, propylene glycol, and other C 2-3 A structural unit derived from an alkylene glycol, particularly ethylene glycol, is preferred.

[0190] The fourth diol unit (A4) The diol unit (A) may or may not contain a fourth diol unit (A4) different from the first to third diol units (A1) to (A3) as necessary.

[0191] Examples of the fourth diol unit (A4) include alicyclic diols, aromatic diols (excluding the first diol unit (A1) and the second diol unit (A2)), and structural units derived from alkylene oxide (alkylene carbonate or haloalkanol) adducts of these diol components.

[0192] Examples of alicyclic diols include cycloalkane diols such as cyclohexanediol; bis(hydroxyalkyl)cycloalkanes such as cyclohexanedimethanol; and hydrogenated aromatic diols exemplified below, such as hydrogenated bisphenol A.

[0193] Examples of aromatic diols 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.

[0194] Examples of the alkylene oxide (corresponding alkylene carbonate or haloalkanol) adducts of these diol components include, for example, 2-4 Alkylene oxide adducts, preferably ethylene oxide adducts, propylene oxide adducts, and the like 2-3 Examples of the alkylene oxide adduct include an alkylene oxide adduct, and the number of moles of the adduct is not particularly limited. Specifically, examples of the alkylene oxide adduct include an adduct in which about 2 to 10 moles of ethylene oxide are added to 1 mole of a diol such as bisphenol A.

[0195] The diol unit (A) may contain these fourth diol units (A4) alone or in combination of two or more. The proportion of the fourth diol unit (A4) may be selected from the range of, for example, 50 mol% or less (0 to 50 mol%), specifically about 0.1 to 30 mol%, based on the total diol unit (A), and the preferred ranges are 20 mol% or less, 10 mol% or less, and 5 mol% or less in the following stepwise order, and it is preferable that the fourth diol unit (A4) is not substantially contained.

[0196] (Dicarboxylic acid unit (B)) The resin may or may not contain dicarboxylic acid units (B) as required, which can be combined with diol units (A) to form the polyester or polyester carbonate resins.

[0197] First Dicarboxylic Acid Unit (B1) The dicarboxylic acid unit (B) does not necessarily have to contain the first dicarboxylic acid unit (B1) represented by the above formula (4), but may contain it as necessary. If the first dicarboxylic acid unit (B1) is contained, it is easy to reduce the birefringence (or adjust it to the negative (-) side) while maintaining a relatively high refractive index.

[0198] In the formula (4), R 6 The substituent (non-reactive substituent or non-polymerizable substituent) and the number of substitutions m6 represented by the formula (2) in the section on the second diol unit (A2) are 4 and m4 are the same as those exemplified above in terms of the substituents, ranges, and substitution positions, including preferred embodiments thereof.

[0199] A 6a , A 6b As the linear or branched alkylene group represented by the formula (1), for example, 1 and the like. Preferred are C groups such as a methylene group, an ethylene group, a trimethylene group, a propylene group, and a 2-methylpropane-1,3-diyl group. 1-6 Alkylene group, more preferably C 1-4 An alkylene group, more preferably C 2-4 Alkylene groups, especially C groups such as ethylene and propylene. 2-3 An alkylene group is preferred, and an ethylene group is particularly preferred. 6a and A 6b The types of may be different from each other, but are preferably the same.

[0200] Examples of the first dicarboxylic acid component for forming the first dicarboxylic acid unit (B1) include 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)fluorene and 9,9-bis(2-carboxypropyl)fluorene. 2-6 Preferred first dicarboxylic acid units (B1) include 9,9-bis(carboxy C 2-4 and more preferably 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)fluorene and 9,9-bis(2-carboxypropyl)fluorene. 2-3 It is preferable that the first dicarboxylic acid unit (B1) contains a structural unit derived from 9,9-bis(2-carboxyethyl)fluorene, particularly 9,9-bis(2-carboxyethyl)fluorene. These first dicarboxylic acid units (B1) may be used alone or in combination of two or more kinds.

[0201] Second Dicarboxylic Acid Unit (B2) The dicarboxylic acid unit (B) does not necessarily contain the second dicarboxylic acid unit (B2) represented by the above formula (5), but may contain it if necessary. If the second dicarboxylic acid unit (B2) is contained, the birefringence can be adjusted to the plus (+) side (or positive side) while maintaining a relatively high refractive index and glass transition temperature.

[0202] In the formula (5), ring Z 3 As the arene ring represented by the formula (1), the ring Z 1 The preferred ring Z is an arene ring similar to that shown in 3 Examples include C rings such as benzene ring, naphthalene ring, and biphenyl ring. 6-12 arene rings, and more preferably C rings such as benzene rings and naphthalene rings. 6-10 A naphthalene ring is particularly preferred since it is an arene ring and can easily improve the refractive index.

[0203] R 7The substituent represented by the formula (1) (non-reactive substituent or non-polymerizable substituent) is R 1 The substituents, including preferred embodiments, are the same as those exemplified as R 7 is an aryl group, R 7 is Z 3 may form a ring assembly arene ring together with

[0204] R 7 The number of substitutions m7 of the ring Z 3 can be selected according to the type of, for example, an integer of about 0 to 6, preferably an integer of 0 to 4, an integer of 0 to 2, more preferably 0 or 1, particularly preferably 0, in a stepwise manner. 7 The types of may be the same or different. 7 The substitution positions of are not particularly limited, and two carbonyl groups [-C(=O)-] and ring Z 3 It is sufficient that the substitution is made at a position other than the bonding position with the aryl group.

[0205] The positions of the two carbonyl groups [-C(=O)-] are not particularly limited. For example, the ring Z 3 When the ring Z is a benzene ring, the two carbonyl groups [-C(=O)-] may be substituted at the o-position, m-position or p-position, and among these, it is preferable that they are substituted at the m-position or p-position, and particularly preferably at the p-position. 3 When the ring Z is a naphthalene ring, the two carbonyl groups [-C(=O)-] are often substituted at any of the 1-8 positions, for example, in a naphthyl group having one carbonyl group substituted at the 1- or 2-position, the other carbonyl group is substituted at the 5- or 8-position, preferably at the 1,5 or 2,6 positions, particularly preferably at the 2,6 positions. 3 is a biphenyl ring, the two carbonyl groups [-C(=O)-] may be substituted in any positional relationship, but are preferably substituted on different benzene rings, more preferably at the 2,2'-positions, 3,3'-positions or 4,4'-positions, particularly preferably at the 2,2'-positions or 4,4'-positions.

[0206] Representative examples of the second dicarboxylic acid component corresponding to the second dicarboxylic acid unit (B2) include the ring Z 3 Benzenedicarboxylic acids corresponding to the unit where ring Z is a benzene ring; 3 is a polycyclic arene ring; and ester-forming derivatives thereof.

[0207] Examples of benzene dicarboxylic acids include benzene dicarboxylic acid and alkyl benzene dicarboxylic acid. Examples of benzene dicarboxylic acids include phthalic acid, isophthalic acid, and terephthalic acid. Examples of alkyl benzene dicarboxylic acids include C 5-methylisophthalic acid. 1-4 Alkyl-benzene dicarboxylic acids and the like.

[0208] Examples of the polycyclic arene dicarboxylic acids include condensed polycyclic arene dicarboxylic acids and ring-assembled arene dicarboxylic acids.

[0209] Examples of the condensed polycyclic arene dicarboxylic acids include naphthalene dicarboxylic acids such as 1,2-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, and 2,6-naphthalene dicarboxylic acid; anthracene dicarboxylic acid; and condensed polycyclic C such as phenanthrene dicarboxylic acid. 10-24 Preferred condensed polycyclic arene dicarboxylic acids include condensed polycyclic C 10-14 It is an arene-dicarboxylic acid.

[0210] Examples of ring-assembled arene dicarboxylic acids include bi-C dicarboxylic acids such as 2,2'-biphenyl dicarboxylic acid, 3,3'-biphenyl dicarboxylic acid, and 4,4'-biphenyl dicarboxylic acid. 6-10 arene-dicarboxylic acids, etc., preferably biphenyldicarboxylic acid.

[0211] The second dicarboxylic acid unit (B2) derived from these second dicarboxylic acid components may be a single unit or a combination of two or more units. Among these second dicarboxylic acid units (B2), a unit derived from a benzene dicarboxylic acid component such as isophthalic acid or terephthalic acid, or a biphenyl dicarboxylic acid component such as 2,2'-biphenyl dicarboxylic acid may be used. However, from the viewpoint of easiness in improving the refractive index and heat resistance, a condensed polycyclic C 10-14 Fused polycyclic arenedicarboxylic acid moieties such as arene-dicarboxylic acids are preferred, more preferably dicarboxylic acid units derived from naphthalenedicarboxylic acids, especially 2,6-naphthalenedicarboxylic acid.

[0212] Third Dicarboxylic Acid Unit (B3) The dicarboxylic acid unit (B) may or may not contain a third dicarboxylic acid unit (B3) different from the first dicarboxylic acid unit (B1) and the second dicarboxylic acid unit (B2) as necessary.

[0213] Examples of the third dicarboxylic acid unit (B3) include structural units derived from an aliphatic dicarboxylic acid component, an alicyclic dicarboxylic acid component, an aromatic dicarboxylic acid component (excluding the first dicarboxylic acid unit (B1) and the second dicarboxylic acid unit (B2)), etc.

[0214] Examples of the aliphatic dicarboxylic acid component include alkanedicarboxylic acids, specifically, C carboxylic acids such as succinic acid, adipic acid, sebacic acid, and decanedicarboxylic acid. 2-12 Alkane-dicarboxylic acids, etc.; unsaturated aliphatic dicarboxylic acids, specifically, C such as maleic acid, fumaric acid, and itaconic acid 2-10 Alkene-dicarboxylic acids and their ester-forming derivatives are included.

[0215] Examples of the alicyclic dicarboxylic acid component include cycloalkane dicarboxylic acids, specifically, C 1,4-cyclohexane dicarboxylic acid. 5-10Cycloalkane dicarboxylic acids, etc.; bridged cyclic cycloalkane dicarboxylic acids, specifically, di- or tricycloalkane dicarboxylic acids such as decalin dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid, tricyclodecane dicarboxylic acid, etc.; cycloalkene dicarboxylic acids, specifically, C such as cyclohexene dicarboxylic acid, etc. 5-10 Examples of the cycloalkene dicarboxylic acids include bridged cyclic cycloalkene dicarboxylic acids, specifically di- or tricycloalkene dicarboxylic acids such as norbornene dicarboxylic acid, and ester-forming derivatives thereof.

[0216] Examples of the aromatic dicarboxylic acid component include diarylalkane dicarboxylic acids, specifically, di-C such as 4,4'-diphenylmethane dicarboxylic acid. 6-10 Aryl C 1-6 Alkane-dicarboxylic acids, etc.; diaryl ketone dicarboxylic acids, specifically, di(C 6-10 aryl) ketone-dicarboxylic acids, and the like; and ester forming derivatives thereof.

[0217] These third dicarboxylic acid units (B3) may be used alone or in combination of two or more. The proportion of the third dicarboxylic acid units (B3) may be selected from the range of, for example, 50 mol% or less, specifically, about 0 to 30 mol%, based on the total dicarboxylic acid units (B), and the preferred ranges are 20 mol% or less, 10 mol% or less, and 5 mol% or less in the following stepwise order, and it is preferable that the third dicarboxylic acid units (B3) are not substantially contained.

[0218] (Carbonate unit (C)) The resin may or may not contain carbonate units (C) as required, which can be combined with diol units (A) to form the polycarbonate or polyester carbonate resin.

[0219] The carbonate component (or carbonate bond forming component) for forming the carbonate unit (C) may be any compound capable of forming a carbonate bond by reaction with a compound (polymerization component) having a hydroxyl group such as the diol component (A), and representative carbonate components include, for example, phosgenes such as phosgene and triphosgene, and carbonate diesters such as diphenyl carbonate, and the like, with carbonate diesters such as diphenyl carbonate being preferred from the viewpoint of safety, etc. The carbonate components may be used alone or in combination of two or more kinds.

[0220] In this specification and claims, the term "carbonate unit" refers to a structural unit derived from the carbonate component (carbonate bond forming component), i.e., a carbonyl group [-C(=O)-]. In other words, this carbonate unit (carbonyl group) bonds with a structural unit corresponding to the compound (polymerization component) having a hydroxyl group, such as a diol unit (A), to form a carbonate bond together with the terminal oxygen atoms (oxygen atoms derived from hydroxyl groups) of two adjacent structural units.

[0221] (Other structural units (D)) The resin does not have to contain any other structural unit (D) different from the diol unit (A), the dicarboxylic acid unit (B), and the carbonate unit (C), but may contain such a unit, if necessary, within a range that does not impair the effects of the present invention.

[0222] Examples of the other structural unit (D) include structural units derived from hydroxyalkanoic acids and corresponding lactones, and polyfunctional polymerization components having three or more carboxyl groups and / or hydroxyl groups.

[0223] Examples of the hydroxyalkanoic acids and corresponding lactones include hydroxyalkanoic acids such as lactic acid, 3-hydroxybutyric acid, and 6-hydroxyhexanoic acid; and lactones corresponding to hydroxyalkanoic acids such as ε-caprolactone.

[0224] Examples of the polyfunctional polymerization component include polyfunctional polymerization components having a total of three or more carboxyl groups and / or hydroxyl groups, such as trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid, and trivalent or higher polyhydric alcohols such as glycerin and pentaerythritol.

[0225] Such other structural units (D) may be contained alone or in combination of two or more. The ratio of the other structural units (D) to the total amount of the structural units (total amount of the diol unit (A), the dicarboxylic acid unit (B), the carbonate unit (C) and the other structural units (D)) is, for example, 50 mol% or less (0 to 50 mol%), and the preferred range is 30 mol% or less, 10 mol% or less, and 5 mol% or less in the following stepwise manner, and it is usually preferable that the other structural units (D) are not substantially contained. The ratio may be, for example, about 0.01 to 1 mol%.

[0226] (Preferable composition for polyester resin) The resin of the present invention is preferably a polyester-based resin described in the following (1) to (3), since it can simultaneously achieve a high refractive index and high moldability at a high level and further has an excellent balance of low birefringence, heat resistance, and low Abbe number.

[0227] (1) Polycarbonate resin The polycarbonate resin of the present invention is formed from structural units including diol units (A) containing at least the first diol units (A1) and the carbonate units (C). The polycarbonate resin preferably further contains a second diol unit (A2) as the diol unit (A).

[0228] The preferred units in the first diol unit (A1) and the second diol unit (A2) are the same as those in the preferred embodiments described above. Particularly preferred combinations of structural units forming a polycarbonate resin include 9,9-bis(hydroxy C) such as 9,9-bis(3-hydroxypropyl)-2,7-di(2-naphthyl)fluorene as the first diol unit (A1).2-4 and 9,9-bis[hydroxy C, alkyl]-dinaphthylfluorene as the second diol unit (A2). 2-4 and a structural unit derived from an alkoxy-naphthyl]fluorene.

[0229] The ratio of the first diol unit (A1) in the polycarbonate resin may be selected from the range of, for example, about 1 to 100 mol% based on the total diol unit (A), and the preferred ranges are 10 to 90 mol%, 20 to 80 mol%, 30 to 70 mol%, 40 to 60 mol%, and 45 to 55 mol% in the following stepwise order. In addition, from the viewpoint of excellent balance of high moldability, high refractive index, low Abbe number, and low birefringence, the preferred ranges of the ratio are 50 to 80 mol%, 53 to 70 mol%, and 55 to 65 mol% in the following stepwise order. If the ratio of the first diol unit (A1) is too small, the refractive index and heat resistance may not be sufficiently improved, and conversely, if it is too large, the birefringence may become large on the negative (minus) side, and the absolute value of the birefringence may not be sufficiently reduced.

[0230] The total ratio of the first diol unit (A1) and the second diol unit (A2) may be selected from the range of, for example, about 1 to 100 mol% based on the total diol unit (A), and the preferred ranges are 10 mol% or more, 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, stepwise as follows, and substantially 100 mol% is preferred. If the total ratio is too small, the refractive index and moldability may not be sufficiently improved.

[0231] When the second diol unit (A2) is contained, the ratio A1 / A2 of the first diol unit (A1) to the second diol unit (A2) may be selected from the range of, for example, the former / latter (molar ratio)=about 1 / 99 to 99 / 1, and the preferred ranges are as follows: 10 / 90 to 90 / 10, 20 / 80 to 80 / 20, 30 / 70 to 70 / 30, 40 / 60 to 60 / 40, 45 / 55 to 55 / 45. The ratio A1 / A2 is also preferably as follows: 50 / 50 to 90 / 10, 60 / 40 to 85 / 15, 70 / 30 to 80 / 20. Further, from the viewpoint of excellent balance of high moldability, high refractive index, low Abbe number and low birefringence, the preferred range of the ratio A1 / A2 is 50 / 50 to 80 / 20, 53 / 47 to 70 / 30, and 55 / 45 to 65 / 35 in the following stepwise order. If the ratio of the first diol unit (A1) is too small, the refractive index may not be sufficiently improved, the Tg may be too high, resulting in reduced moldability, and the Abbe number may not be reduced. If the ratio of the second diol unit (A2) is too small, the birefringence may not be reduced, and heat resistance may be reduced.

[0232] The ratio of the diol unit (A) to the carbonate unit (C) in the polycarbonate resin is the former / latter (molar ratio)=1 / 0.8 to 1 / 1.2, preferably 1 / 0.9 to 1 / 1.1, and more preferably approximately equimolar.

[0233] The total proportion of the diol unit (A) and the carbonate unit (C) may be selected, for example, from the range of about 50 to 100 mol % relative to all the structural units forming the polycarbonate resin, and is preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably substantially 100 mol %.

[0234] (2) Polyester carbonate resin The polyester carbonate resin of the present invention is formed from constituent units including diol units (A) containing at least the first diol units (A1), the dicarboxylic acid units (B), and the carbonate units (C). A preferred polyester carbonate resin further contains the second diol units (A2) as the diol units (A), and contains the first dicarboxylic acid units (B1) as the dicarboxylic acid units (B).

[0235] The preferred units in the first and second diol units (A1), (A2) and the first dicarboxylic acid unit (B1) are the same as those in the preferred embodiments described above. Particularly preferred combinations of structural units forming a polyester carbonate resin include 9,9-bis(hydroxy C) such as 9,9-bis(3-hydroxypropyl)-2,7-di(2-naphthyl)fluorene as the first diol unit (A1). 2-4 and 9,9-bis[hydroxy C, alkyl]-dinaphthylfluorene as the second diol unit (A2). 2-4 A building block derived from 9,9-bis(alkoxy-naphthyl)fluorene; and a building block derived from 9,9-bis(carboxy C, such as 9,9-bis(2-carboxyethyl)fluorene as the first dicarboxylic acid unit (B1). 2-4 and a structural unit derived from alkyl)fluorene.

[0236] The proportion of the first diol unit (A1) in the polyester carbonate resin may be selected from the range of, for example, about 1 to 100 mol% based on the total diol unit (A), and preferred ranges are 5 to 60 mol%, 10 to 50 mol%, 20 to 45 mol%, and 25 to 40 mol% in the following stepwise order. If the proportion of the first diol unit (A1) is too low, the refractive index and heat resistance may not be sufficiently improved, and conversely, if it is too high, the birefringence may become large on the negative (minus) side, and the absolute value of the birefringence may not be sufficiently reduced.

[0237] The total ratio of the first diol unit (A1) and the second diol unit (A2) may be selected from the range of, for example, about 1 to 100 mol% based on the total diol unit (A), and the preferred ranges are 10 mol% or more, 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, stepwise as follows, and substantially 100 mol% is preferred. If the total ratio is too small, the refractive index and moldability may not be sufficiently improved.

[0238] When the second diol unit (A2) is contained, the ratio A1 / A2 of the first diol unit (A1) to the second diol unit (A2) may be selected from the range of, for example, the former / latter (molar ratio) = about 1 / 99 to 99 / 1, and the preferred ranges are 5 / 95 to 60 / 40, 10 / 90 to 50 / 50, 20 / 80 to 45 / 55, and 25 / 75 to 40 / 60 in the following stepwise manner. If the ratio of the first diol unit (A1) is too small, the refractive index may not be sufficiently improved, the Tg may be too high, resulting in a decrease in moldability, and the Abbe number may not be reduced. If the ratio of the second diol unit (A2) is too small, the birefringence may not be reduced, the heat resistance may decrease, and the molecular weight may not be sufficiently improved.

[0239] When the first dicarboxylic acid unit (B1) is contained, the proportion of the first dicarboxylic acid unit (B1) may be selected from the range of, for example, about 1 to 100 mol% based on the total dicarboxylic acid unit (B), and preferred ranges are 10 to 100 mol%, 30 to 100 mol%, 50 to 100 mol%, 70 to 100 mol%, and 90 to 100 mol%, stepwise as follows, with substantially 100 mol% being preferred. If the proportion of the first dicarboxylic acid unit (B1) is too low, there is a risk that the birefringence cannot be sufficiently reduced.

[0240] The ratio of the diol units (A) to the total amount of the dicarboxylic acid units (B) and carbonate units (C) in the polyester carbonate resin is the former / latter (molar ratio) = 1 / 0.8 to 1 / 1.2, preferably 1 / 0.9 to 1 / 1.1, and more preferably approximately equimolar.

[0241] The ratio of the dicarboxylic acid unit (B) may be selected from the range of, for example, about 0.01 to 0.99 mol per mol of the diol unit (A), and the preferred ranges are 0.1 to 0.9 mol, 0.5 to 0.85 mol, 0.55 to 0.8 mol, and 0.6 to 0.75 mol in the following stepwise order. If the ratio of the dicarboxylic acid unit (B) is too high or too low, it may not be possible to achieve a good balance of properties such as high refractive index, high moldability, low birefringence, low Abbe number, and heat resistance. If the ratio of the dicarboxylic acid unit (B) is too high, the strength (or hardness) may decrease, resulting in a decrease in injection moldability, and if it is too low, the flexibility (or toughness) may decrease, resulting in a decrease in film moldability.

[0242] The total proportion of the diol units (A), dicarboxylic acid units (B) and carbonate units (C) may be selected, for example, from a range of about 50 to 100 mol % relative to all the constituent units forming the polyester carbonate resin, and is preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably substantially 100 mol %.

[0243] (3) Polyester resin The polyester resin of the present invention is formed of a constituent unit containing a diol unit (A) containing at least the first diol unit (A1) and the dicarboxylic acid unit (B). A preferred polyester resin further contains the third diol unit (A3) as the diol unit (A) and the first dicarboxylic acid unit (B1) as the dicarboxylic acid unit (B). The diol unit (A) may further contain the second diol unit (A2) in addition to the first diol unit (A1) and the third diol unit (A3). A more preferred polyester resin further contains the second dicarboxylic acid unit (B2) in addition to the units (A1), (A3) and (B1).

[0244] The preferred units in the first and third diol units (A1) and (A3) and the first and second dicarboxylic acid units (B1) and (B2) are the same as those in the preferred embodiments described above. A more preferred combination of structural units forming a polyester resin is 9,9-bis(hydroxy C) such as 9,9-bis(3-hydroxypropyl)-2,7-di(2-naphthyl)fluorene as the first diol unit (A1). 2-4 (alkyl)-dinaphthylfluorene-derived building blocks; and C such as ethylene glycol as the third diol unit (A3). 2-4 A structural unit derived from an alkylene glycol; and a 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)fluorene as the first dicarboxylic acid unit (B1). 2-4 A particularly preferred combination is a combination of the above combination with a structural unit derived from a naphthalene dicarboxylic acid, such as 2,6-naphthalene dicarboxylic acid, as the second dicarboxylic acid unit (B2).

[0245] When the diol unit (A) contains a diol unit (A2), the diol unit (A2) is, in the above formula (2), Z 2a and Z 2b The structural unit (A2) is preferably a naphthalene ring, and 9,9-bis[hydroxy C] such as 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene is preferably a naphthalene ring. 2-4 In the case where the diol unit (A) contains the diol unit (A2), a more preferred combination of the constituent units forming the polyester resin is a 9,9-bis(hydroxy C) such as 9,9-bis(3-hydroxypropyl)-2,7-di(2-naphthyl)fluorene as the first diol unit (A1). 2-4 (alkyl)-dinaphthylfluorene as the second diol unit (A2); and 9,9-bis[hydroxy C 2-4A building block derived from alkoxy-naphthyl]fluorene; and a C diol unit such as ethylene glycol as the third diol unit (A3). 2-4 A structural unit derived from an alkylene glycol; and a 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)fluorene as the first dicarboxylic acid unit (B1). 2-4 A particularly preferred combination is a combination of the above combination with a structural unit derived from a naphthalene dicarboxylic acid, such as 2,6-naphthalene dicarboxylic acid, as the second dicarboxylic acid unit (B2).

[0246] The proportion of the first diol unit (A1) in the polyester resin may be selected from the range of, for example, about 1 to 100 mol% based on the total diol unit (A), and preferred ranges are 10 to 99 mol%, 30 to 99 mol%, 50 to 99 mol%, 60 to 97 mol%, 70 to 95 mol%, 75 to 92 mol%, and 80 to 90 mol% in the following stepwise order. If the proportion of the first diol unit (A1) is too small, the refractive index and heat resistance may not be sufficiently improved, and conversely, if it is too large, the birefringence may become large on the negative (minus) side, and the absolute value of the birefringence may not be sufficiently reduced.

[0247] When the diol unit (A) contains the diol unit (A1) and the diol unit (A3), the total ratio of the first diol unit (A1) and the third diol unit (A3) may be selected from the range of, for example, about 1 to 100 mol% based on the total diol unit (A), and the preferred ranges are 10 mol% or more, 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more in the following stepwise order, and substantially 100 mol% is preferred. If the total ratio is too small, the refractive index and moldability may not be sufficiently improved.

[0248] When the diol unit (A) contains the diol unit (A1), the diol unit (A2) and the diol unit (A3), the total amount of the first diol unit (A1), the second diol unit (A2) and the third diol unit (A3) may be selected from the range of, for example, about 1 to 100 mol% based on the total diol unit (A), and the preferred ranges are 10 mol% or more, 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more in the following stepwise manner, and substantially 100 mol% is preferred. If the total amount is too small, the refractive index and moldability may not be sufficiently improved.

[0249] When the third diol unit (A3) is contained, the ratio A1 / A3 of the first diol unit (A1) to the third diol unit (A3) may be selected from the range of, for example, the former / latter (molar ratio) = about 1 / 99 to 99.9 / 0.1, and the preferred ranges are 50 / 50 to 99 / 1, 60 / 40 to 97 / 3, 70 / 30 to 95 / 5, 75 / 25 to 92 / 8, and 80 / 20 to 90 / 10 in the following stepwise manner. If the ratio of the first diol unit (A1) is too small, the refractive index may not be sufficiently improved, the Tg may be too high, and the moldability may be reduced, and the Abbe number may not be reduced. If the ratio of the third diol unit (A3) is too small, the molecular weight may not be sufficiently improved, and the moldability may be reduced.

[0250] The second diol unit (A2) [particularly, in the formula (2), Z 2a and Z 2bIn the case where the diol unit (A2) contains a naphthalene ring, the ratio A1 / A2 of the first diol unit (A1) and the second diol unit (A2) may be selected from a range of, for example, the former / latter (molar ratio) of about 1 / 99 to 99.9 / 0.1, and the preferred ranges are 1 / 99 to 70 / 30, 3 / 97 to 50 / 50, 5 / 95 to 40 / 60, and 10 / 90 to 30 / 70 in the following stepwise manner. If the ratio of the first diol unit (A1) is too low, the refractive index may not be sufficiently improved or the Abbe number may not be reduced. If the ratio of the second diol unit (A2) is too low, the birefringence may not be reduced or the molecular weight may not be sufficiently improved, which may result in a decrease in moldability.

[0251] The total ratio of the first dicarboxylic acid unit (B1) and the second dicarboxylic acid unit (B2) may be selected from the range of, for example, about 1 to 100 mol% based on the total dicarboxylic acid unit (B), and the preferred ranges are 10 mol% or more, 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, and substantially 100 mol% is preferred. If the total ratio is too low, it may not be possible to achieve a good balance of properties such as a high refractive index, high moldability, low birefringence, low Abbe number, and heat resistance.

[0252] When the first dicarboxylic acid unit (B1) is contained, the ratio of the first dicarboxylic acid unit (B1) may be selected from the range of, for example, about 1 to 100 mol% based on the total dicarboxylic acid unit (B), and the preferred ranges are 50 to 100 mol%, 60 to 95 mol%, 70 to 90 mol%, and 75 to 85 mol% in the following stepwise order. Furthermore, from the viewpoint of an excellent balance of high moldability, high refractive index, low Abbe number, and low birefringence, the preferred ranges of the ratio are 40 to 100 mol%, 50 to 90 mol%, and 60 to 80 mol% in the following stepwise order. If the ratio of the first dicarboxylic acid unit (B1) is too small, the birefringence may not be sufficiently reduced.

[0253] When the second dicarboxylic acid unit (B2) is contained, the proportion of the second dicarboxylic acid unit (B2) may be selected, for example, from the range of about 1 to 100 mol % based on the total dicarboxylic acid units (B), and preferred ranges are 3 to 90 mol %, 5 to 70 mol %, 10 to 50 mol %, and 20 to 40 mol %, in the following stepwise order.

[0254] In the case where both the first and second dicarboxylic acid units (B1) and (B2) are contained, the ratio B1 / B2 of the first dicarboxylic acid unit (B1) to the second dicarboxylic acid unit (B2) may be selected from a range of, for example, the former / latter (molar ratio)=about 1 / 99 to 99 / 1, and the preferred ranges are 50 / 50 to 99 / 1, 60 / 40 to 95 / 5, 70 / 30 to 90 / 10, and 75 / 25 to 85 / 15 in the following stepwise manner. Furthermore, in terms of excellent balance between high moldability, high refractive index, low Abbe number, and low birefringence, the preferred ranges of the ratio B1 / B2 are 40 / 60 to 95 / 5, 50 / 50 to 90 / 10, and 60 / 40 to 80 / 20 in the following stepwise manner. If the ratio of the first dicarboxylic acid unit (B1) is too small, the birefringence may not be sufficiently reduced. If the proportion of the second dicarboxylic acid unit (B2) is too low, the refractive index, Abbe number and heat resistance may decrease, and the birefringence may not be sufficiently reduced.

[0255] The ratio of the diol unit (A1) to the dicarboxylic acid unit (B1) in the polyester resin may be selected, for example, from a range of about former / latter (molar ratio) of 1 / 0.1 to 1 / 10, and preferred ranges are the following stepwise ranges: 1 / 0.2 to 1 / 8, 1 / 0.25 to 2, 1 / 0.3 to 1 / 1.5, 1 / 0.5 to 1 / 1, and 1 / 0.7 to 1 / 0.9.

[0256] The ratio of the diol unit (A) to the dicarboxylic acid unit (B) in the polyester resin is the former / latter (molar ratio)=1 / 0.8 to 1 / 1.2, preferably 1 / 0.9 to 1 / 1.1, and more preferably approximately equimolar.

[0257] The total proportion of the diol units (A) and the dicarboxylic acid units (B) may be selected, for example, from the range of about 50 to 100 mol % relative to all the constituent units forming the polyester resin, and is preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably substantially 100 mol %.

[0258] [Resin manufacturing method] The method for producing the resin is not particularly limited except for using the diol component (A) containing the first diol component (A1), and a conventional method can be used depending on the type of resin or other polymerization components (copolymerization components), etc. For example, in the case of a polyester resin, it may be produced by reacting a diol component (A) corresponding to each of the diol units described above with a polymerization component containing a dicarboxylic acid component (B) and / or a carbonate component (C) corresponding to each of the dicarboxylic acid units described above.

[0259] Specifically, when the resin contains carbonate units (C), particularly when the resin is a polycarbonate resin, the diol component (A) is reacted (polymerized or condensed) with the carbonate component (C) by, for example, the phosgene method (solvent method) or the transesterification method (melt method), etc. Among these methods, the transesterification method is preferred because it does not require a solvent.

[0260] In the transesterification method, the proportion of the carbonate diester is, for example, 0.8 to 1.5 mol, and preferably 0.9 to 1.2 mol, per 1 mol of the diol component.

[0261] The transesterification reaction may be carried out in the presence of a catalyst. Examples of the catalyst include various catalysts used in transesterification reactions, such as nitrogen-containing compounds and metal compounds.

[0262] Examples of the nitrogen-containing compound include quaternary ammonium hydroxides (e.g., tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide; trialkyl-aralkylammonium hydroxides such as trimethylbenzylammonium hydroxide; tertiary amines (trialkylamines such as trimethylamine and triethylamine; dimethyl-aralkylamines such as dimethylbenzylamine; triarylamines such as triphenylamine); and the like.

[0263] Examples of the metal contained in the metal compound include alkali metals such as sodium, alkaline earth metals such as magnesium, calcium, barium, transition metals such as manganese, zinc, cadmium, lead, cobalt, titanium, etc., metals in Group 13 of the periodic table such as aluminum, metals in Group 14 of the periodic table such as germanium, metals in Group 15 of the periodic table such as antimony, etc. Specific examples of the metal compound include alkoxides, organic acid salts such as acetates and propionates, inorganic acid salts such as borates and carbonates, oxides, hydroxides, etc. of the above metals.

[0264] These catalysts can be used alone or in combination of two or more. Among these catalysts, nitrogen-containing compounds such as quaternary ammonium hydroxides are preferred, and among these, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide are preferred. The amount of catalyst used is, for example, 0.01×10 per mole of the diol component. -4 ~100×10 -4 Molar, preferably 0.1 x 10 -4 ~40×10 -4 It is a mole.

[0265] The reaction may be carried out in the presence of additives, for example, stabilizers such as antioxidants and heat stabilizers, if necessary.

[0266] The reaction can be carried out in an inert gas atmosphere, such as nitrogen gas or a rare gas such as helium or argon. The reaction can also be carried out under reduced pressure, for example, at a pressure of 1×10 2 ~1×10 4 The reaction temperature can be selected depending on the polymerization method, and for example, the reaction temperature in the transesterification method is, for example, 150 to 320° C., preferably 200 to 310° C., and more preferably 250 to 300° C. In particular, when diphenyl carbonate is used as the carbonate diester, it is effective to carry out polycondensation while distilling off phenol at high temperature and reduced pressure.

[0267] On the other hand, when the dicarboxylic acid unit (B) is contained, particularly when the resin is a polyester resin or a polyester carbonate resin, it can be prepared by, for example, a melt polymerization method such as an ester exchange method or a direct polymerization method, a solution polymerization method, an interfacial polymerization method, etc., and the melt polymerization method is preferred. The reaction may be carried out in the presence or absence of a solvent depending on the polymerization method.

[0268] The ratio of the diol component (A) to the dicarboxylic acid component (B) used (or the ratio of the diol component (A) to the dicarboxylic acid component (B) is, for example, 1 / 1.2 to 1 / 0.8, preferably 1 / 1.1 to 1 / 0.9, but it is not necessarily required to be in this range. At least one component selected from the diol component (A) and the dicarboxylic acid component (B) may be used in excess of the expected ratio of introduction and reacted. For example, the third diol component (A3) such as ethylene glycol that can be distilled from the reaction system may be used in excess of the ratio (or the ratio of introduction) introduced into the resin. In addition, when the carbonate component (C) is used, the ratio of the total amount of the dicarboxylic acid component (B) and the carbonate component (C) to the diol component (A) used is, for example, 1 / 1.2 to 1 / 0.8, preferably 1 / 1.1 to 1 / 0.9, for example, the former / latter (molar ratio). In addition, taking into consideration volatilization and decomposition during the reaction, the carbonate component (C) may be used in a slight excess over the planned introduction ratio, and the carbonate component (C) may be used in an excess of, for example, 0.1 to 5 mol %, preferably 2 to 3 mol %, over the total amount of the dicarboxylic acid units (B) and the carbonate units (C) (total amount planned to be introduced into the resin).

[0269] The reaction may be carried out in the presence of a catalyst. As the catalyst, a conventional esterification catalyst, for example, a metal catalyst, etc., can be used. As the metal catalyst, for example, a metal compound containing an alkali metal such as sodium; an alkaline earth metal such as magnesium, calcium, barium, etc.; a transition metal such as titanium, manganese, cobalt, etc.; a metal of Group 12 of the periodic table such as zinc, cadmium, etc.; a metal of Group 13 of the periodic table such as aluminum, etc.; a metal of Group 14 of the periodic table such as germanium, lead, etc.; a metal of Group 15 of the periodic table such as antimony, etc. 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., or hydrates thereof may be used. Representative metal compounds include 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 (titanium(IV) tetrabutoxide), titanium oxalate, and potassium titanium oxalate; manganese compounds such as manganese acetate tetrahydrate; and calcium compounds such as calcium acetate monohydrate.

[0270] These catalysts can be used alone or in combination of two or more. When using multiple 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 catalyst used is, for example, 0.01 x 10 per mole of the dicarboxylic acid component (A). -4 ~100×10 -4 Molar, preferably 0.1 x 10 -4 ~40×10 -4 It is a mole.

[0271] The reaction may be carried out in the presence of a stabilizer such as a heat stabilizer or an antioxidant, if necessary. Usually, a heat stabilizer is often used, and examples of the heat stabilizer include phosphorus compounds such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dibutyl phosphate (dibutyl phosphate or dibutyl phosphate), phosphorous acid, trimethyl phosphite, and triethyl phosphite. Of these, dibutyl phosphate is often used. The amount of the heat stabilizer used is, for example, 0.01×10 per mole of the dicarboxylic acid component (A). -4 ~100×10 -4 Molar, preferably 0.1 x 10 -4 ~40×10 -4 It is a mole.

[0272] The reaction is usually carried out in an atmosphere of an inert gas, such as nitrogen gas, or a rare gas such as helium or argon. The reaction is also carried out under reduced pressure, for example, at a pressure of 1×10 2 ~1×10 4 The reaction temperature can be selected according to the polymerization method, and for example, the reaction temperature in the melt polymerization method is 150 to 320°C, preferably 180 to 310°C, and more preferably 200 to 300°C.

[0273] [Resin characteristics] The resin of the present invention contains the first diol unit (A1), and therefore has a high refractive index and high moldability. In addition to the above properties, the resin also has a high level of properties such as low birefringence, low Abbe number, and high heat resistance in a well-balanced manner.

[0274] The glass transition temperature Tg of the resin may be, for example, about 100 to 250°C, preferably 110 to 200°C, more preferably 120 to 180°C, and particularly preferably 130 to 170°C.

[0275] When the resin is a polycarbonate resin, the Tg is, for example, 120 to 200°C, preferably 140 to 180°C, more preferably 160 to 175°C, and particularly preferably 165 to 170°C.

[0276] When the resin is a polyester carbonate resin, the Tg is, for example, 120 to 190°C, preferably 140 to 175°C, more preferably 150 to 170°C, and particularly preferably 155 to 165°C.

[0277] When the resin is a polyester resin, the Tg is, for example, 100 to 170°C, preferably 125 to 160°C, more preferably 130 to 150°C, and particularly preferably 135 to 145°C.

[0278] If the Tg is too high, molding such as injection molding must be performed at high temperatures, which not only reduces moldability (fluidity or productivity), but also causes deterioration or coloring of the molded product due to an increase in molding temperature, and may require a special mold for cooling in order to suppress distortion in the molded product and prevent a decrease in surface smoothness. On the other hand, if the Tg is too low, the heat resistance may decrease, and the product may be easily deteriorated or discolored (or colored) during molding and / or use, or the molded product may deform in a high-temperature environment, making it impossible to use the resin in applications requiring high heat resistance (or thermal stability), such as optical lenses for vehicles. However, the resin of the present invention has an excellent balance between moldability and heat resistance, as described in the section on the first diol unit (A1), and can be easily adjusted to the above Tg range.

[0279] In addition, when moldability is prioritized, the refractive index is often decreased, but in the present invention, high moldability and high refractive index can be well balanced. Therefore, the refractive index nD of the resin may be, for example, about 1.67 to 1.74 at a temperature of 20° C. and a wavelength of 589 nm, preferably 1.68 to 1.73, more preferably 1.69 to 1.72, and particularly 1.7 to 1.71. In addition, in high refractive index applications, the refractive index nD of the resin is preferably 1.7 to 1.74, more preferably 1.705 to 1.73, and particularly 1.71 to 1.72.

[0280] When the resin is a polycarbonate resin, the nD may be, for example, about 1.69 to 1.72, preferably 1.695 to 1.715, and more preferably 1.7 to 1.71. In addition, the nD of the polycarbonate resin is preferably 1.7 to 1.74, more preferably 1.705 to 1.73, and particularly preferably 1.71 to 1.72, for high refractive index applications.

[0281] When the resin is a polyester carbonate resin, the nD may be, for example, about 1.67 to 1.71, preferably 1.675 to 1.695, and more preferably 1.68 to 1.69.

[0282] When the resin is a polyester resin, the nD may be, for example, about 1.685 to 1.715, preferably 1.69 to 1.71, and more preferably 1.695 to 1.705.

[0283] In the resin of the present invention containing the first diol unit (A1), the Abbe number can be efficiently reduced. Therefore, the Abbe number of the resin at a temperature of 20° C. is, for example, 20 or less, preferably 18 or less, more preferably 10 to 17, and further preferably 12.5 to 16.

[0284] When the resin is a polycarbonate resin, the Abbe number is, for example, 17 or less, preferably 12 to 16, more preferably 12.5 to 15, and particularly preferably 13 to 14.

[0285] When the resin is a polyester carbonate resin, the Abbe number is, for example, 18 or less, preferably 15 to 17, and more preferably 15.5 to 16.5.

[0286] When the resin is a polyester resin, the Abbe number is, for example, 16 or less, preferably 11 to 15, more preferably 12 to 14, and particularly preferably 12.5 to 13.

[0287] The resin of the present invention, which exhibits such a low Abbe number, can be effectively used in applications requiring a lower Abbe number, such as optical components in various cameras, specifically, camera lenses using a combination of concave and convex lenses, etc. In the optical systems of various cameras, a concave lens with a low Abbe number is used to reduce (or cancel) the chromatic aberration (bleed) that occurs in a convex lens, and thus the optical systems are usually constructed by combining multiple concave and convex lenses, but the resin of the present invention can fully meet the low Abbe number required for the concave lens.

[0288] In addition, since the resin of the present invention contains the first diol unit (A1), birefringence can be efficiently reduced. The birefringence of a resin may be evaluated by measuring the birefringence of a stretched film (three-fold stretch birefringence) obtained by uniaxially stretching a film formed from the resin alone at a stretching temperature of glass transition temperature Tg+10°C, a stretching speed of 25 mm / min, and a stretching ratio of three times. The absolute value of the three-fold stretch birefringence of the stretched film is, for example, 100×10 at a measurement temperature of 20°C and a wavelength of 600 nm. -4 The following ranges can be selected, and the preferred ranges are as follows: 70×10 -4 Below, 50 x 10 -4 Below, 25 x 10 -4 Below, 20 x 10 -4 The following is 10 x 10 -4 More preferably, it is 0 to 5×10 -4 It is.

[0289] The weight average molecular weight Mw of the resin can be measured by gel permeation chromatography (GPC) or the like, and can be selected from the range of, for example, about 10,000 to 1,000,000 in terms of standard polystyrene, preferably 20,000 to 100,000, more preferably 30,000 to 80,000, and particularly preferably 35,000 to 50,000. If the weight average molecular weight Mw is too low, moldability (productivity) and heat resistance may decrease. However, in the present invention, even if the weight average molecular weight Mw is low, moldability and the like are excellent, and polyester resins are particularly excellent.

[0290] When the resin is a polycarbonate resin, the Mw is, for example, 10,000 to 100,000, preferably 20,000 to 80,000, further preferably 30,000 to 60,000, and particularly preferably 40,000 to 50,000.

[0291] When the resin is a polyester carbonate resin, the Mw is, for example, 10,000 to 100,000, preferably 20,000 to 80,000, further preferably 30,000 to 60,000, and particularly preferably 40,000 to 50,000.

[0292] When the resin is a polyester resin, the Mw is, for example, 10,000 to 100,000, preferably 30,000 to 80,000, further preferably 50,000 to 75,000, and particularly preferably 60,000 to 70,000.

[0293] In this specification and claims, the glass transition temperature Tg, refractive index nD, Abbe number, 3-fold stretch birefringence, and weight average molecular weight Mw can be measured by the method described in the examples below.

[0294] [Molded body] The molded article of the present invention may contain at least the resin, and has excellent optical properties such as high refractive index, low birefringence, and low Abbe number, as well as a good balance of various properties such as high moldability and high heat resistance, and can be used as an optical member such as an optical film (or optical sheet) or an optical lens. Such a molded article may contain conventional additives. Examples of the additives include fillers or reinforcing agents, colorants such as dyes and pigments, conductive agents, flame retardants, plasticizers, lubricants, release agents, antistatic agents, dispersants, flow control agents, leveling agents, defoamers, surface modifiers, hydrolysis inhibitors, carbon materials, stabilizers, and stress reducing agents. Examples of the stabilizers include antioxidants, ultraviolet absorbers, and heat stabilizers. Examples of the stress reducing agents include silicone oils, silicone rubbers, various plastic powders, and various engineering plastic powders. These additives may be used alone or in combination of two or more.

[0295] The molded article can be produced by, for example, injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, pressure molding, casting molding, or the like.

[0296] The shape of the molded body is not particularly limited, and examples thereof include one-dimensional structures such as linear, fibrous (or fiber-like) and thread-like structures, two-dimensional structures such as film-like, sheet-like and plate-like structures, and three-dimensional structures such as concave or convex lens-like, rod-like and hollow (tubular) structures.

[0297] In particular, the resin of the present invention is useful for forming an optical film because of its excellent optical properties, and therefore the present invention also includes a film (optical film or optical sheet) formed from the resin.

[0298] The average thickness of such a film can be selected from the range of about 1 to 1000 μm depending on the application, and is, for example, 1 to 200 μm, preferably 5 to 150 μm, and more preferably 10 to 120 μm.

[0299] Such a film (optical film) can be produced by forming (or molding) the above-mentioned resin into a film using a conventional film-forming method such as a casting method (solvent casting method), a melt extrusion method, or a calendar method.

[0300] The film may be a stretched film. The film of the present invention can maintain low birefringence even if it is a stretched film. Such a stretched film may be either a uniaxially stretched film or a biaxially stretched film.

[0301] The stretching ratio in each direction in uniaxial or biaxial stretching is, for example, 1.1 to 10 times, preferably 1.2 to 5 times, and more preferably 1.5 to 3 times. In the case of biaxial stretching, it may be equal stretching, for example, stretching about 1.5 to 5 times in both the longitudinal and transverse directions, or uneven stretching, for example, stretching about 1.1 to 4 times in the longitudinal direction and about 2 to 6 times in the transverse direction. In the case of uniaxial stretching, it may be longitudinal stretching, for example, stretching about 2.5 to 8 times in the longitudinal direction, and transverse stretching, for example, stretching about 1.2 to 5 times in the transverse direction.

[0302] The average thickness of the stretched film is, for example, 1 to 150 μm, preferably 3 to 120 μm, and more preferably 5 to 100 μm.

[0303] Such a stretched film can be obtained by stretching the film (or unstretched film) after film formation. The stretching method is not particularly limited, and in the case of uniaxial stretching, either a wet stretching method or a dry stretching method may be used, and in the case of biaxial stretching, either a tenter method (flat method) or a tube method may be used, but the tenter method, which has excellent uniformity in the stretched thickness, is preferred.

[0304] The molded article may be joined or adhered to another substrate, and the type or material of the substrate is not particularly limited, and may be, for example, a substrate having a one-dimensional, two-dimensional or three-dimensional shape formed of a resin material, a ceramic material, a metal material, etc. For example, when the molded article is in the form of a film, it may be combined with a substrate having a two-dimensional shape such as a film to form a laminate or a laminate film.

[0305] The two-dimensional substrate is typically a ceramic substrate such as a glass substrate, a resin film, etc., and is preferably a transparent substrate. The resin forming the resin film is, for example, a polyolefin resin such as a chain olefin resin or a cyclic olefin resin (or a cycloolefin resin); (meth)acrylic resin; a styrene resin; a polyester resin such as a polyalkylene arylate resin, a polyarylate resin, or a polycarbonate resin; a polyamide resin; and may be used by bonding with a resin film formed of a cycloolefin resin, a polyamide resin, etc. EXAMPLES

[0306] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Details of the evaluation methods are shown below.

[0307] [Evaluation method] (HPLC) The HPLC purity [area %] of the sample was calculated by high performance (or high speed) liquid chromatography (HPLC) based on the following measurement equipment and conditions.

[0308] Equipment: Hitachi High-Technologies Corporation "L-2000" Column: Imtakt Co., Ltd. "Cadenza CL-C18 (3 μm) 3.0 × 250 mm" Guard column: Imtakt GCCD0S Detector: L-2420 UV-VIS detector (D 2 lamp, 254 nm) Mobile phase: acetonitrile / distilled water (volume ratio) = 90 / 10 (Kanto Chemical Co., Ltd., LC grade) Flow rate: 0.5mL / min

[0309] (FD-MS) Mass spectrometry (MS) was performed using the following measuring equipment and conditions.

[0310] Equipment used: “JMS-T200GC” manufactured by JEOL Ltd. Ionization method: FD (field desorption) Emitter: Carbon Emitter current: 0~50mA(25mA / min).

[0311] (Melting Point) A differential scanning calorimeter (SII NanoTechnology, Inc., "EXSTAR DSC6200") was used to measure under nitrogen atmosphere at a measurement temperature of 30 to 220°C and a heating rate of 10°C / min. From the obtained DSC chart (DSC curve), the temperature at the top of the endothermic peak due to melting was calculated as the melting point.

[0312] (5% mass reduction temperature) Using a thermogravimetry-differential thermal analyzer (TG-DTA) ("TG / DTA6200" manufactured by SII NanoTechnology, Inc.), the temperature at which the mass of the sample decreased by 5% by mass was measured under conditions of a nitrogen atmosphere and a heating rate of 10°C / min.

[0313] ( 1 H-NMR) The samples were analyzed using a deuterated solvent (CDCl) containing tetramethylsilane as an internal standard. 3 or DMSO-d 6 ) and analyzed using a nuclear magnetic resonance spectrometer (BRUKER "AVANCE III HD"). 1 H-NMR spectrum was measured.

[0314] In the examples where resins (polymers) were prepared, the integral values ​​of the peaks derived from each monomer used in the polymerization were determined for the obtained spectrum, and the proportions of each monomer component (structural unit) introduced into the resin (polymer composition ratio) were calculated.

[0315] (glass transition temperature Tg) The measurement was performed using a differential scanning calorimeter ("EXSTAR6000 DSC6220 ASD-2" manufactured by SII NanoTechnology Inc.) in a nitrogen gas atmosphere at a temperature increase rate of 10° C. / min.

[0316] (molecular weight) The sample was dissolved in chloroform, and the weight average molecular weight Mw in terms of standard polystyrene was determined using gel permeation chromatography ("HLC-8320GPC" manufactured by Tosoh Corporation).

[0317] (Refractive index nD) The refractive indexes of DNFDP-m and DNFPO prepared in Example 1 were measured at a temperature of 25° C. and a wavelength of 589 nm (D line) using a refractometer (DR-M2 (circulating thermostatic bath 60-C3) manufactured by Atago Co., Ltd.). The refractive indexes were calculated by extrapolating the concentration to 100 mass% on a calibration curve (approximation line) prepared by dissolving a sample in dimethyl sulfoxide to prepare solutions with concentrations of 6.05 mass%, 10.94 mass%, and 30.30 mass%, and measuring the refractive index of the obtained solutions.

[0318] The refractive index of the resin sample was measured as follows. The sample was heat pressed at 200 to 240°C to form a film with a thickness of 200 to 300 μm. This film was cut into a rectangular shape with a length of 20 to 30 mm and a width of 10 mm to obtain a test piece. The refractive index nD of the obtained test piece at 589 nm (D line) was measured using a multi-wavelength Abbe refractometer ("DR-M4 (circulating thermostatic bath 60-C3)" manufactured by Atago Co., Ltd.) at a measurement temperature of 20°C and diiodomethane as a contact liquid.

[0319] (Abbe number) Using the test piece for measuring the refractive index nD at 589 nm (D line), the refractive indexes nF and nC were measured in the same manner as for the refractive index nD, except that the measurement wavelengths were changed to 486 nm (F line) and 656 nm (C line). The Abbe number was calculated from the refractive indexes nF, nD, and nC at each wavelength obtained using the following formula.

[0320] (Abbe number)=(nD-1) / (nF-nC).

[0321] (Birefringence (3x stretched birefringence)) The sample was hot pressed at 200-240°C to form a film with a thickness of 200-600μm. This film was cut into a rectangular shape with a width of 10mm and a length of 50mm, and uniaxially stretched in the longitudinal direction at a temperature of glass transition temperature Tg+10°C at 25mm / min so that the stretch ratio was 3 times (so that the length of 50mm became 150mm) to obtain a test piece. The retardation of the obtained test piece was measured by the parallel Nicol rotation method using a retardation film / optical material inspection device (Otsuka Electronics Co., Ltd., "RETS-100") under conditions of a measurement temperature of 20°C and a measurement wavelength of 600nm, and the value was divided by the thickness of the measurement site to calculate the birefringence (or 3-times stretched birefringence).

[0322] [Resin raw material] (Diol component) DNFPO: 2,7-di(2-naphthyl)-9,9-fluorene dipropanol [or 2,7-di(2-naphthyl)-9,9-bis(3-hydroxypropyl)fluorene], synthesized according to Example 1 described below. BNEF: 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, synthesized according to Synthesis Example 1 described in JP2018-59074A BPEF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, manufactured by Osaka Gas Chemicals Co., Ltd. BINOL-2EO: 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, synthesized according to Synthesis Example 2 described in JP-A-2018-59074 EG: Ethylene glycol (Carbonate bond forming component) DPC: Diphenyl carbonate (Dicarboxylic acid component) FDP-m: 9,9-bis(2-methoxycarbonylethyl)fluorene [or dimethyl ester of 9,9-bis(2-carboxyethyl)fluorene], synthesized in the same manner as in Example 1 of JP-A-2005-89422, except that methyl acrylate [37.9 g (0.44 mol)] was used instead of t-butyl acrylate. DMT: Dimethyl terephthalate DMN: 2,6-bis(methoxycarbonyl)naphthalene.

[0323] [Example 1] (Preparation of DBrFDP-m) 2,7-Dibromo-9,9-bis(2-methoxycarbonylethyl)fluorene (DBrFDP-m) was synthesized in the same manner as in Example 1 of JP 2005-89422 A, except that 37.9 g (0.44 mol) of methyl acrylate was used instead of t-butyl acrylate and 54.7 g (0.17 mol) of 2,7-dibromo-9H-fluorene was used instead of fluorene.

[0324] (Preparation of DNFDP-m) In a reactor, 192.3 g (0.39 mol) of DBrFDP-m, 200 g (1.2 mol) of 2-naphthylboronic acid, 4.3 L of dimethoxyethane, and 1 L of 2 M aqueous sodium carbonate solution were charged, and tetrakis(triphenylphosphine)palladium(0) [or Pd(PPh 3 ) 4 ]22.4g (19.4mmol) was added, and the mixture was heated to reflux at an internal temperature of 71-78℃ for 5 hours to react. After cooling to room temperature, 2.0L of toluene and 500mL of ion-exchanged water were added, and the mixture was washed by liquid separation 5 times. The organic layer changed from deep orange to brown. Insoluble matter was filtered and concentrated to obtain 305g of brown crude crystals. The obtained crude crystals were dissolved by heating in a mixture of 1.5kg of ethyl acetate and 300g of isopropyl alcohol (IPA), then cooled to 10℃ or less with ice water and stirred for 1 hour to precipitate crystals. The precipitated crystals were filtered and dried under reduced pressure to obtain 130g of gray-brown crystals. The obtained gray-brown crystals were purified by column chromatography (silica gel carrier, developing solvent chloroform:ethyl acetate (volume ratio) = 4:1), then recrystallized from methanol and dried under reduced pressure to obtain 116 g of 9,9-bis(2-methoxycarbonylethyl)-2,7-di(2-naphthyl)fluorene (DNFDP-m) represented by the following formula (white crystals, yield 54.9%, HPLC purity 99.4% by area). 1 The results of H-NMR and FD-MS are shown below.

[0325] [ka]

[0326] 1 H-NMR (CDCl 3 , 300MHz): δ(ppm)1.7(t,4H),2.6(t,4H),3.4(s,6H),7.5(m,4H),7.7-8.0(m,14H),8.1(s,2H)

[0327] FD-MS: m / z 590(M+).

[0328] The refractive index nD of DNFDP-m was 1.845, the melting point was 191°C, and the 5% mass loss temperature was 390°C.

[0329] (Preparation of DNFPO) In a nitrogen atmosphere, DNFDP-m (1.2 kg, 2.03 mol) and tetrahydrofuran (THF, 9.78 kg) were added to a 20 L separable flask, and the flask was cooled to below 10°C in an ice-water bath. Sodium borohydride (230 g, 6.08 mol) was gradually added to the resulting solution over 13 minutes, and then boron trifluoride ether complex (856 g, 6.09 mol) was added dropwise over 45 minutes. The mixture was then warmed to room temperature and stirred for 4 hours. The mixture was cooled in an ice-water bath, and acetone (1.0 kg, 17.2 mol) was added dropwise over 1 hour, after which the solvent was removed by vacuum concentration. Then, 12 kg of chloroform, 1.0 kg of ion-exchanged water, and 3.0 kg of ice were added, and the aqueous layer was removed. The operation of adding 4.0 kg of ion-exchanged water and removing the aqueous layer was repeated twice (washed twice with ion-exchanged water) to remove only the organic layer. The resulting solution was concentrated under reduced pressure to obtain 1.0 kg of DNFPO represented by the following formula, that is, 2,7-di(2-naphthyl)-9,9-(3-hydroxypropyl)fluorene (white solid, yield 92.1%, HPLC purity 99% by area). 1 The results of H-NMR and FD-MS are shown below.

[0330] [ka]

[0331] 1 H-NMR (DMSO-d 6 , 300MHz): δ(ppm) 0.9(m,4H) ,2.2(m,4H),3.2(t,4H),4.2(t,2H),7.5-8.4(m,20H).

[0332] FD-MS: m / z 535 (M+).

[0333] The refractive index nD of DNFPO was 1.756, the melting points were 186°C and 220°C, and the 5% mass loss temperature was 392°C.

[0334] [Polycarbonate resin] [Example 2] 0.50 mol of DNFPO and 0.50 mol of BPEF as diol components, 1.05 mol of DPC as carbonate component (carbonate bond forming component), and 2 × 10 tetramethylammonium hydroxide as an ester exchange catalyst. -4 mol was added, and gradually heated to melt while stirring under a nitrogen gas atmosphere. The temperature was raised to 250°C, and then the pressure was reduced stepwise to 10,000 Pa. Phenol was removed while gradually raising the temperature and reducing the pressure until it reached 270°C and 130 Pa or less. After reaching a predetermined stirring torque, the contents were removed from the reactor to obtain a polycarbonate resin. 50 mol% of the diol units constituting the obtained polycarbonate resin were derived from DNFPO and 50 mol% were derived from BPEF.

[0335] [Example 3] A polycarbonate resin was obtained in the same manner as in Example 2, except that 0.30 mol of DNFPO and 0.70 mol of BPEF were used as the diol components, and 1.05 mol of DPC was used as the carbonate component. 30 mol% of the diol units constituting the obtained polycarbonate resin were derived from DNFPO, and 70 mol% were derived from BPEF.

[0336] [Comparative Example 1] A polycarbonate resin was obtained in the same manner as in Example 2, except that 1.00 mol of BPEF was used as the diol component and 1.05 mol of DPC was used as the carbonate component. 100 mol % of the diol units constituting the obtained polycarbonate resin were derived from BPEF.

[0337] [Example 4] A polycarbonate resin was obtained in the same manner as in Example 2, except that 0.50 mol of DNFPO and 0.50 mol of BNEF were used as the diol components, and 1.05 mol of DPC was used as the carbonate component. 50 mol% of the diol units constituting the obtained polycarbonate resin were derived from DNFPO and 50 mol% were derived from BNEF.

[0338] [Example 5] A polycarbonate resin was obtained in the same manner as in Example 2, except that 0.60 mol of DNFPO and 0.40 mol of BNEF were used as the diol components, and 1.05 mol of DPC was used as the carbonate component. 60 mol% of the diol units constituting the obtained polycarbonate resin were derived from DNFPO, and 40 mol% were derived from BNEF.

[0339] [Comparative Example 2] A polycarbonate resin was obtained in the same manner as in Example 2, except that 1.00 mol of BNEF was used as the diol component and 1.05 mol of DPC was used as the carbonate component. 100 mol % of the diol units constituting the obtained polycarbonate resin were derived from BNEF.

[0340] Table 1 shows the charge ratios in the examples and comparative examples for preparing polycarbonate resins, and Table 2 shows the evaluation results.

[0341] [Table 1]

[0342] [Table 2]

[0343] As is clear from Table 2, the polycarbonate resins obtained in the Examples were able to significantly improve the refractive index without excessively increasing Tg compared to the corresponding Comparative Examples, and were able to achieve both high moldability and refractive index. Note that even an increase in the refractive index of about 0.01 is considered to be advantageous, and this can be said to be a remarkable effect. In addition, in the Examples, the Abbe number was significantly reduced compared to the Comparative Examples, and the absolute value of the 3-fold stretch birefringence was reduced or kept low. Among them, Examples 4 to 5, and especially Example 5, were able to achieve a good balance of high moldability, high refractive index, low Abbe number, and low birefringence at a higher level.

[0344] [Polyester carbonate resin] [Example 6] As diol components, 0.30 mol of DNFPO and 0.30 mol of BNEF, 0.21 mol of DPC as carbonate components, 0.40 mol of FDP-m as dicarboxylic acid components, and titanium (IV) tetrabutoxide (2.7 mg (8 μmol)) as a catalyst for transesterification and polycondensation reactions were charged, and the mixture was heated and stirred at 210 ° C for 1 hour under a nitrogen gas atmosphere, and then gradually heated to 240 ° C and stirred to carry out transesterification. After removing the alcohol components and phenol components generated by the transesterification reaction, the temperature was gradually raised to 290 ° C and 130 Pa, the pressure was reduced, and the polycondensation reaction was carried out until a predetermined stirring torque was reached. After the reaction was completed, the contents were removed from the reactor to obtain a polyester carbonate resin. Of the diol units constituting the obtained polyester carbonate resin, 50 mol % were derived from DNFPO and 50 mol % were derived from BNEF, and of the carbonate units and dicarboxylic acid units constituting the resin, 33 mol % were derived from DPC and 67 mol % were derived from FDP-m.

[0345] [Example 7] A polyester carbonate resin was obtained in the same manner as in Example 6, except that 0.20 mol of DNFPO and 0.40 mol of BNEF were used as the diol components, 0.21 mol of DPC as the carbonate component, and 0.40 mol of FDP-m as the dicarboxylic acid component. Of the diol units constituting the obtained polyester carbonate resin, 33 mol% were derived from DNFPO and 67 mol% were derived from BNEF, and of the carbonate units and dicarboxylic acid units constituting the resin, 33 mol% were derived from DPC and 67 mol% were derived from FDP-m.

[0346] [Comparative Example 3] A polyester carbonate resin was obtained in the same manner as in Example 6, except that 0.60 mol of BNEF was used as the diol component, 0.21 mol of DPC was used as the carbonate component, and 0.40 mol of FDP-m was used as the dicarboxylic acid component. 100 mol% of the diol units constituting the obtained polyester carbonate resin were derived from BNEF, 33 mol% of the carbonate units and dicarboxylic acid units constituting the resin were derived from DPC, and 67 mol% were derived from FDP-m.

[0347] Table 3 shows the charge ratios in the examples and comparative examples for preparing polyester carbonate resins, and Table 4 shows the evaluation results.

[0348] [Table 3]

[0349] [Table 4]

[0350] As is clear from Table 4, the polyester carbonate resins obtained in the Examples were able to significantly improve the refractive index without excessively increasing the Tg, and were able to achieve both high moldability and high refractive index, compared to the corresponding Comparative Examples. In addition, in the Examples, the Abbe number was significantly reduced, and the absolute value of the birefringence after 3-fold stretching was also reduced, compared to the Comparative Examples. In particular, in Example 7, high moldability, high refractive index, low Abbe number, and low birefringence were achieved in a well-balanced manner at a higher level.

[0351] [Polyester resin] [Example 8] As diol components, 0.75 mol of DNFPO and 2.25 mol of EG, 1 mol of FDP-m as a dicarboxylic acid component, titanium (IV) tetrabutoxide (1.4 mg (4 μmol)) as a catalyst for transesterification and polycondensation, and dibutyl phosphate (8.4 mg (40 μmol)) as a heat stabilizer were charged, and the mixture was gradually heated to 245 ° C. under a nitrogen gas atmosphere and stirred to carry out a transesterification reaction. After removing the alcohol component produced by the transesterification reaction, the temperature was gradually raised to 280 ° C. and 130 Pa, the pressure was reduced, and the polycondensation reaction was carried out until a predetermined stirring torque was reached while removing EG. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin. 75 mol % of the diol units constituting the obtained polyester resin were derived from DNFPO, 25 mol % were derived from EG, and 100 mol % of the dicarboxylic acid units constituting the resin were derived from FDP-m.

[0352] [Comparative Example 4] A polyester resin was obtained in the same manner as in Example 8, except that 0.75 mol of BNEF and 2.25 mol of EG were used as the diol components, and 1 mol of FDP-m was used as the dicarboxylic acid component. 75 mol% of the diol units constituting the obtained polyester resin were derived from BNEF, 25 mol% were derived from EG, and 100 mol% of the dicarboxylic acid units constituting the resin were derived from FDP-m.

[0353] [Comparative Example 5] A polyester resin was obtained in the same manner as in Example 8, except that 0.80 mol of BNEF and 2.20 mol of EG were used as the diol components, and 1 mol of DMN was used as the dicarboxylic acid component. 80 mol% of the diol units constituting the obtained polyester resin were derived from BNEF and 20 mol% were derived from EG, and 100 mol% of the dicarboxylic acid units constituting the resin were derived from DMN.

[0354] [Example 9] A polyester resin was obtained in the same manner as in Example 8, except that 0.85 mol of DNFPO and 2.15 mol of EG were used as the diol components, and 0.70 mol of FDP-m and 0.30 mol of DMN were used as the dicarboxylic acid components. 85 mol% of the diol units constituting the obtained polyester resin were derived from DNFPO and 15 mol% were derived from EG, and 70 mol% of the dicarboxylic acid units constituting the resin were derived from FDP-m and 30 mol% were derived from DMN.

[0355] [Comparative Example 6] A polyester resin was obtained in the same manner as in Example 8, except that 0.85 mol of BPEF and 2.15 mol of EG were used as the diol components, and 0.70 mol of FDP-m and 0.30 mol of DMN were used as the dicarboxylic acid components. 85 mol% of the diol units constituting the obtained polyester resin were derived from BPEF and 15 mol% were derived from EG, and 70 mol% of the dicarboxylic acid units constituting the resin were derived from FDP-m and 30 mol% were derived from DMN.

[0356] [Example 10] A polyester resin was obtained in the same manner as in Example 8, except that 0.7 mol of DNFPO and 2.3 mol of EG were used as the diol components, and 1 mol of DMT was used as the dicarboxylic acid component. 70 mol % of the diol units constituting the obtained polyester resin were derived from DNFPO and 30 mol % were derived from EG, and 100 mol % of the dicarboxylic acid units constituting the resin were derived from DMT.

[0357] [Comparative Example 7] A polyester resin was obtained in the same manner as in Example 8, except that 0.7 mol of BPEF and 2.3 mol of EG were used as the diol components, and 1 mol of DMT was used as the dicarboxylic acid component. 70 mol % of the diol units constituting the obtained polyester resin were derived from BPEF and 30 mol % were derived from EG, and 100 mol % of the dicarboxylic acid units constituting the resin were derived from DMT.

[0358] [Example 11] A polyester resin was obtained in the same manner as in Example 8, except that 0.4 mol of DNFPO, 0.4 mol of BNEF, and 2.2 mol of EG were used as the diol components, and 0.50 mol of FDP-m and 0.50 mol of DMN were used as the dicarboxylic acid components. 40 mol% of the diol units constituting the obtained polyester resin were derived from DNFPO, 40 mol% were derived from BNEF, and 20 mol% were derived from EG, and 50 mol% of the dicarboxylic acid units constituting the resin were derived from FDP-m and 50 mol% were derived from DMN.

[0359] [Comparative Example 8] A polyester resin was obtained in the same manner as in Example 8, except that 0.4 mol of BNEF, 0.4 mol of BINOL-2EO, and 2.2 mol of EG were used as the diol components, and 0.50 mol of FDP-m and 0.50 mol of DMN were used as the dicarboxylic acid components. 40 mol% of the diol units constituting the obtained polyester resin were derived from BNEF, 40 mol% were derived from BINOL-2EO, and 20 mol% were derived from EG, and 50 mol% of the dicarboxylic acid units constituting the resin were derived from FDP-m and 50 mol% were derived from DMN.

[0360] [Example 12] A polyester resin was obtained in the same manner as in Example 8, except that 0.15 mol of DNFPO, 0.6 mol of BNEF, and 2.25 mol of EG were used as the diol components, and 1 mol of FDP-m was used as the dicarboxylic acid component. 15 mol% of the diol units constituting the obtained polyester resin were derived from DNFPO, 60 mol% were derived from BNEF, and 25 mol% were derived from EG, and 100 mol% of the dicarboxylic acid units constituting the resin were derived from FDP-m.

[0361] Table 5 shows the charge ratios of the polyester resins prepared in the Examples and Comparative Examples, and Table 6 shows the evaluation results.

[0362] [Table 5]

[0363] [Table 6]

[0364] As is clear from Table 6, the polyester resins obtained in the Examples were able to significantly improve the refractive index without excessively increasing the Tg, and were able to achieve both high moldability and refractive index, compared to the corresponding Comparative Examples. In addition, in the Examples, the Abbe number was significantly reduced, and the absolute value of the 3-fold stretched birefringence was reduced or kept low, compared to the Comparative Examples. In particular, in Example 9, high moldability, high refractive index, low Abbe number, and low birefringence were achieved in a well-balanced manner at a higher level.

[0365] In comparison between Example 11 and Comparative Example 8, a high refractive index was achieved by using DNFPO instead of BINOL-2EO. In Example 12, by using BNEF as the second diol unit (A2), a high refractive index and low birefringence were achieved, although the refractive index was slightly lower than in Example 9.

[0366] Moreover, the polyester resins of the examples were easier to handle than polycarbonate resins and polyester carbonate resins, probably due to their better mechanical properties such as flexibility (toughness), and when molded into lenses, films, etc., they had particularly high moldability (or productivity) compared to polycarbonate resins and polyester carbonate resins. [Industrial Applicability]

[0367] The diol compound of the present invention can be used as a resin raw material (or monomer) for forming a resin exhibiting excellent optical properties such as a high refractive index and high moldability. Therefore, the resin obtained by using the diol compound of the present invention as a raw material can be used for various applications by taking advantage of the above properties, such as coating agents or coating films, specifically, paints, inks, protective films for electronic devices and liquid crystal members, adhesives, pressure sensitive adhesives, resin fillers, electric and electronic materials or electric and electronic parts (electric and electronic devices), specifically, antistatic agents, carrier transport agents, light emitting bodies, organic photoreceptors, thermal recording materials, photochromic materials, hologram recording materials, charging trays, conductive sheets, optical disks, 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 parts (equipment), specifically, automotive materials or parts, aerospace-related materials or parts, sliding members, etc.

[0368] The resin of the present invention can be particularly effectively used as an optical member. Representative examples of the optical member include optical films (optical sheets) such as films for liquid crystal and organic electroluminescence (EL) films, optical lenses such as lenses for glasses and lenses for cameras, prisms, holograms, optical fibers, etc.

[0369] Examples of optical films include polarizing films, polarizing elements and polarizing plate protective films constituting polarizing films, diffusion plates (films), prism sheets, light guide plates, brightness enhancing films, near-infrared absorbing films, reflective films, anti-reflection (AR) films, reflection reducing (LR) films, anti-glare (AG) films, transparent conductive (ITO) films, anisotropic conductive films (ACF), electromagnetic 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 electroluminescent displays (OLEDs), plasma displays (PDPs), field emission displays (FEDs), and electronic paper, and specific devices or apparatuses include televisions; personal computers (PCs) such as desktop PCs, notebook PCs, and tablet PCs; smartphones, mobile phones; car navigation systems; and devices or apparatuses equipped with flat panel displays (FPDs) such as touch panels.

[0370] Examples of optical lenses include glasses lenses, contact lenses, camera lenses, VTR zoom lenses, pickup lenses, Fresnel lenses, solar concentrating lenses, objective lenses, rod lens arrays, etc., and among them, the optical lenses are suitable for use in lenses that require a low Abbe number, such as camera lenses. Representative examples of devices or apparatuses that incorporate such optical lenses include small devices or mobile devices with camera functions, such as smartphones, mobile phones, and digital cameras; vehicle-mounted cameras, such as drive recorders and backup cameras (rear cameras), etc.

Claims

1. The following formula (1) 【Chemistry 1】 [In the formula, Y １ａ and Y １ｂ each independently represents the following formula (Y1): 【Chemistry 2】 (In the formula, Z １ indicates an arene ring, R １ represents a substituent, and m1 represents an integer of 0 or 1 or more. k1a and k1b each independently represent an integer of 0 to 4, and at least one of k1a and k1b is 1 or more; R ２ａ and R ２ｂ each independently represents a substituent; m2a and m2b each independently represent an integer of 0 to 4; k1a + m2a and k1b + m2b are each independently 4 or less; Y ２ａ and Y ２ｂ each independently represents the following formula (Y2): 【Chemistry 3】 (In the formula, A １ and A ２ each independently represents a linear or branched alkylene group, and n2 represents 0 or an integer of 1 or more. It represents a monovalent group represented by the following formula: A method for producing a diol compound represented by the following formula: The following formula (I) 【Chemistry 4】 [In the formula, Y 3a and Y 3b each independently represent the following formula (Y3): 【Chemistry 5】 (In the formula, A 3 represents a linear or branched alkylene group, R 3 represents a hydrogen atom or an alkyl group. represents a monovalent group represented by Y 1a and Y 1b , k1a and k1b, R 2a and R 2b , and m2a and m2b are the same as those in formula (1). A method for producing a diol compound, comprising a reduction step of reducing a compound represented by the following formula:

2. In the formula (1), Z １ C ６－１２ arene rings, k1a and k2b are integers from 1 to 2, A １ is linear or branched C １－６ is an alkylene group, A ２ is linear or branched C ２－４ 2. The process according to claim 1, wherein n2 is an alkylene group, and n3 is 0 or an integer of 1 to 10.

3. In the formula (1), Z １ is a benzene ring or a naphthalene ring, k1a and k2b are 1, A １ is linear or branched C １－４ is an alkylene group, The method according to claim 1 or 2, wherein n2 is 0.

4. The diol unit (A) is represented by the following formula (1P): 【Chemistry 6】 [In the formula, Y ２ｃ and Y ２ｄ each independently represents the following formula (Y2c) 【Chemistry 7】 (In the formula, A １ represents a trimethylene group, n2 represents 0, A 2 is the same as in formula (1) of claim 1, A １ is bonded to the 9th position of the fluorene ring. represents a divalent group represented by Y １ａ and Y １ｂ , k1a and k1b, R ２ａ and R ２ｂ , m2a and m2b are the same as those in formula (1) of claim 1. and a first diol unit (A1) represented by the following formula (2): 【Chemistry 8】 (In the formula, Z 2a and Z 2b each independently represent an arene ring; R 4 represents a substituent; m4 represents an integer of 0 to 8; R 5a and R 5b each independently represent a substituent; m5a and m5b each independently represent an integer of 0 or 1 or more; A 4a and A 4b each independently represent a linear or branched alkylene group, and n4a and n4b each independently represent an integer of 0 or 1 or more. and a second diol unit (A2) represented by the following formula:

5. In the formula (2), Z 2a and Z 2b are C 6-10 arene rings; R 5a and R 5b are a hydrocarbon group, m5a and m5b are integers of 0 to 2, The polycarbonate resin according to claim 4, wherein A 4a and A 4b are linear or branched C 2-6 alkylene groups, and n4a and n4b are integers of 0 to 3.

6. 6. The polycarbonate resin according to claim 4, wherein the proportion of the first diol unit (A1) represented by the formula (1P) is 5 to 100 mol % based on the total diol units (A).

7. The polycarbonate resin according to any one of claims 4 to 6, wherein a ratio of the first diol unit (A1) to the second diol unit (A2) is the former / the latter (molar ratio) = 20 / 80 to 80 / 20.

8. As the diol unit (A), 【Chemistry 9】 [In the formula, Y 2c and Y 2d each independently represent the following formula (Y2c): 【Chemistry 10】 (In the formula, A 1 , A 2 and n2 are the same as those in the formula (1) of claim 1, and A 1 is bonded to the 9-position of the fluorene ring.) represents a divalent group represented by Y 1a and Y 1b , k1a and k1b , R 2a and R 2b , and m2a and m2b are the same as those in formula (1) of claim 1 . The polyester carbonate resin contains a first diol unit (A1) represented by the following formula:

9. A polyester carbonate resin according to claim 8, wherein the proportion of the first diol unit (A1) represented by the formula (1P) is 5 to 100 mol % based on the total diol units (A).

10. The polyester carbonate resin according to claim 8 or 9, wherein the diol unit (A) further comprises the second diol unit (A2) according to claim 4 or 5.

11. As the dicarboxylic acid unit (B), 【Chemistry 11】 (In the formula, R ６ represents a substituent, m6 represents an integer of 0 to 8, A ６ａ and A ６ｂ each independently represents a linear or branched alkylene group.

12. The diol unit (A) further comprises the second diol unit (A2) according to claim 4 or 5, and a ratio of the first diol unit (A1) to the second diol unit (A2) (the former / the latter) (molar ratio) is 10 / 90 to 50 / 50; the ratio of the dicarboxylic acid unit (B) is 0.5 to 0.85 mol per 1 mol of the diol unit (A), 12. The polyester carbonate resin according to claim 11, wherein the proportion of the first dicarboxylic acid units (B1) is 50 to 100 mol % based on the total of the dicarboxylic acid units (B).

13. The diol unit (A) is represented by the following formula (1P): 【Chemistry 12】 [In the formula, Y 2c and Y 2d each independently represent the following formula (Y2c): 【Chemistry 13】 (In the formula, A 1 , A 2 and n2 are the same as those in the formula (1) of claim 1, and A 1 is bonded to the 9-position of the fluorene ring.) represents a divalent group represented by Y 1a and Y 1b , k1a and k1b , R 2a and R 2b , and m2a and m2b are the same as those in formula (1) of claim 1 . and as the dicarboxylic acid unit (B), the first dicarboxylic acid unit (B1) according to claim 11.

14. The diol unit (A) is represented by the following formula (3): 【Chemistry 14】 (In the formula, A ５ represents a linear or branched alkylene group, and n5 represents an integer of 1 or more. The polyester resin according to claim 13, further comprising a third diol unit (A3) represented by:

15. The dicarboxylic acid unit (B) is represented by the following formula (5): 【Chemistry 15】 (In the formula, Z ３ indicates an arene ring, R ７ represents a substituent, and m7 represents an integer of 0 or 1 or more. The polyester resin according to claim 13 or 14, further comprising a second dicarboxylic acid unit (B2) represented by the following formula:

16. The diol unit (A) further comprises a third diol unit (A3) according to claim 14, a molar ratio of the first diol unit (A1) to the third diol unit (A3) is the former / the latter=70 / 30 to 95 / 5, the ratio of the first dicarboxylic acid unit (B1) is 0.3 to 1.5 moles per mole of the first diol unit (A1); The dicarboxylic acid unit (B) further comprises a second dicarboxylic acid unit (B2) according to claim 15, The polyester resin according to any one of claims 13 to 15, wherein a ratio of the first dicarboxylic acid unit (B1) to the second dicarboxylic acid unit (B2) is the former / the latter (molar ratio) = 50 / 50 to 90 / 10.

17. A molded article comprising the polycarbonate resin according to any one of claims 4 to 7, the polyester carbonate resin according to any one of claims 8 to 12, or the polyester resin according to any one of claims 13 to 16.

18. The molded article according to claim 17, which is an optical member.

19. The molded article according to claim 17 or 18, which is an optical film or an optical lens.

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