JP2022040080A - Fluorene derivative and resin, and production method and application thereof - Google Patents

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

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 method and application for producing the same.

A diol compound having a fluorene skeleton is often used as an optical plastic (or an optical resin material) by taking advantage of its optical properties such as high refractive index. Among them, the diol compound having a 9,9-bisarylfluorene skeleton is known to exhibit particularly excellent optical properties due to the cardo structure. For example, Patent Documents 1 to 4 describe 9, A polyester resin or a polycarbonate resin containing a diol compound having a 9-bisarylfluorene skeleton as a polymerization component is disclosed.

In Patent Document 5, a polyester resin containing a diol compound having a predetermined fluorene skeleton as a polymerization component, which is not a 9,9-bisarylfluorene skeleton, exhibits negative birefringence. This polyester resin is used. It is disclosed that a multilayer optical film is formed.

Japanese Unexamined Patent Publication No. 2017-179323 Japanese Unexamined Patent Publication No. 2018-104691 Japanese Unexamined Patent Publication No. 2016-69643 Japanese Unexamined Patent Publication No. 2018-172658 U.S. Patent Application Publication No. 2012/0170118

In the examples of Patent Documents 1 and 2, as the diol compound having a 9,9-bisarylfluorene skeleton, 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene (BNEF), 9, Polycarbonate resins containing 9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BPEF), 9,9-bis (6-hydroxy-2-naphthyl) fluorene (BNF) and the like as polymerization components have been prepared. ..

Further, in the examples of Patent Documents 3 to 4, as the diol compound having a 9,9-bisarylfluorene skeleton, the above-mentioned BNEF, BPEF, 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] ] A polyester resin containing fluorene (BOPPEF) as a polymerization component has been prepared.

Although the resins obtained in the examples of Patent Documents 1 to 4 show a high refractive index, the demand for a high refractive index for the optical resin material is still high, and there are cases where it cannot be sufficiently met depending on the application.

Attempting to form a resin with a monomer having many benzene ring skeletons (or aromatic ring skeletons) in order to obtain a higher refractive index causes the glass transition temperature Tg to rise excessively due to the rigidity of the benzene ring skeleton. Therefore, the fluidity (melt fluidity) is lowered, injection molding becomes difficult, and the moldability (handleability or productivity) is lowered. That is, the relationship between the high refractive index and the high formability is in a trade-off relationship, and it is not easy to cope with the further high refractive index.
Further, since the relationship between the high refractive index and the low birefringence is also in a trade-off relationship, there is a possibility that the birefringence tends to increase in the resin in which a large amount of benzene ring skeleton is introduced.

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

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 so high.

Therefore, an object of the present invention is a novel diol compound capable of forming a resin having a high refractive index and excellent moldability (handleability or productivity), a resin containing this diol compound as a polymerization component, and these. To provide manufacturing methods and uses.

As a result of diligent studies to achieve the above-mentioned problems, the present inventors have found that a diol compound having a specific chemical structure in which an aryl group is bonded to the 1st to 8th positions of the fluorene skeleton and an alkylene group is bonded to the 9th and 9th positions. , 9,9- Although it does not have a bisarylfluorene skeleton, it has been found that a resin exhibiting a remarkably high refractive index can be formed without impairing moldability, and the present invention has been completed.

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

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

(In the formula, Z ¹ indicates an arene ring,
^R1 represents a substituent and m1 represents 0 or an integer greater than or equal to 1. )

(In the equation, A ¹ and A ² independently represent a linear or branched alkylene group, and n2 represents 0 or an integer greater than or equal to 1).

In the above formula (1), Z ¹ may be a C _6-12 arene ring, and k1a and k2b may be integers of about 1 to 2.
A ¹ may be a linear or branched C _1-6 alkylene group.
A ² may be a linear or branched C _2-4 alkylene group, and n2 may be an integer of about 0 or 1 to 10.

Further, in the above formula (1), Z ¹ may be a benzene ring or a naphthalene ring, and k1a and k2b may be 1.
A ¹ may be a linear or branched C _1-4 alkylene group.
n2 may be 0.

The present invention includes a method for producing the diol compound, which comprises a reduction step of reducing the compound represented by the following formula (I).

[In the formula, Y ^3a and Y ^3b each independently represent 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 the above formula (1), respectively. ]

( ^In the formula, A3 represents a linear or branched alkylene group.
R ³ indicates a hydrogen atom or an alkyl group).

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

[In the formula, Y ^2c and Y ^2d each independently indicate 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 the above formula (1), respectively. ]

(In the formula, A ¹ , A ² and n 2 are the same as the above formula (1), respectively, and A ¹ is bonded to the 9-position of the fluorene ring).

The resin may be a polyester resin containing the first diol unit (A1) represented by the formula (1P) as the diol unit (A). The ratio of the first diol unit (A1) represented by the formula (1P) may be about 5 to 100 mol% with respect to the entire diol unit (A).

The resin may be a polycarbonate resin. In the polycarbonate resin, the diol unit (A) may further contain a second diol unit (A2) represented by the following formula (2).

(In the equation, Z ^2a and Z ^2b each independently represent an arene ring,
^R4 indicates a substituent, m4 indicates an integer of 0 to 8, and the m4 indicates an integer of 0 to 8.
R ^5a and R ^5b each independently indicate a substituent, and m5a and m5b independently indicate an integer of 0 or 1 or more, respectively.
A ^4a and A ^4b independently represent linear or branched alkylene groups, respectively, and n4a and n4b independently represent an integer greater than or equal to 0 or 1, respectively).

In the above formula (2), Z ^2a and Z ^2b may be a C _6-10 arene ring, R ^5a and R ^5b may be a hydrocarbon group, and m5a and m5b are integers of about 0 to 2. May be
A ^4a and A ^4b may be linear or branched C _2-6 alkylene groups, and n4a and n4b may be integers of about 0 to 3.

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

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

(In the formula, R ⁶ indicates a substituent, m 6 indicates an integer of 0 to 8, and
A ^6a and A ^6b each independently indicate a linear or branched chain alkylene group).

In the polyester carbonate resin, the ratio of the first diol unit (A1) to the second diol unit (A2) may be about 10/90 to 50/50 of the former / latter (molar ratio). Often,
The ratio of the dicarboxylic acid unit (B) may be about 0.5 to 0.85 mol with respect to 1 mol of the diol unit (A).
The ratio of the first dicarboxylic acid unit (B1) may be about 50 to 100 mol% with respect to the entire dicarboxylic acid unit (B).

Further, the resin may be a polyester resin. In the polyester resin, the diol unit (A) may further contain a third diol unit (A3) represented by the following formula (3).

( ^In the formula, A5 represents a linear or branched alkylene group, and n5 represents an integer of 1 or more).

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).

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

In the polyester resin, the ratio of the first diol unit (A1) to the third diol unit (A3) may be about 70/30 to 95/5 of the former / the latter (molar ratio). ,
The ratio of the first dicarboxylic acid unit (B1) may be about 0.3 to 1.5 mol with respect to 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 about 50/50 to 90/10 of the former / the latter (molar ratio).

The present invention also includes a molded product containing the resin. The molded body may be an optical member such as an optical film or an optical lens.

In the present invention, the following problems may be solved as a secondary object.

That is, another object of the present invention is a diol compound capable of forming a resin satisfying 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 method for producing these. And to provide uses.

Still another object of the present invention is a diol compound capable of forming a resin exhibiting a low Abbe number while satisfying a high refractive index, high formability and low birefringence in a well-balanced manner, and a resin containing this diol compound as a polymerization component. , And to provide these manufacturing methods and uses.

In the present specification and the scope of patent claims, the "diol unit" is a structural unit derived from a diol component, that is, a unit (or a divalent group) obtained by removing a hydrogen atom from two hydroxyl groups of the corresponding diol. The term "diol component" (including compounds exemplified as the diol component) may be used synonymously with the corresponding "diol unit".

Further, the "dicarboxylic acid unit" means a structural unit derived from a dicarboxylic acid component, that is, 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 that, in addition to the dicarboxylic acid, a derivative that can be used as a polymerization component, for example, an ester-forming derivative such as a dicarboxylic acid ester, a dicarboxylic acid halide, or a dicarboxylic acid anhydride is included. Examples of the dicarboxylic acid ester include dicarboxylic acid component alkyl esters, and among them, lower alkyl esters such as C _1-4 alkyl esters such as methyl esters, ethyl esters, and t-butyl esters. 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. Further, the "dicarboxylic acid component" (including a compound exemplified as a dicarboxylic acid component) may be used synonymously with the corresponding "dicarboxylic acid unit".

In the present specification and claims, the number of carbon atoms of the substituent may be indicated by C ₁ , C ₆ , C ₁₀ , and the like. For example, an alkyl group having 1 carbon atom is represented by "C ₁ alkyl", and an aryl group having 6 to 10 carbon atoms is represented by "C _6-10 aryl".

Further, in the present specification and claims, the description such as "low birefringence" or "low birefringence" means that the absolute value of birefringence is low (that is, close to 0) unless otherwise specified. do.

The diol compound having a specific chemical structure of the present invention exhibits a high refractive index and is excellent in moldability (handleability or productivity) even though it does not have a 9,9-bisarylfluorene skeleton. Resin can be formed. Further, it is possible to form a resin in which not only high refractive index and high moldability but also low birefringence are satisfied in a well-balanced manner. Further, it is possible to form a resin in which a low Abbe number is satisfied in a well-balanced manner as well as a high refractive index, high formability and low birefringence.

[Glycol compound represented by the formula (1)]
The novel diol compound (or also referred to as the first diol component) of the present invention is represented by the above formula (1). In the formula (1), the arene ring (aromatic hydrocarbon ring) represented by Z ¹ in the formula (Y1) representing the monovalent groups Y ^1a and Y ^1b is, for example, a simple benzene ring or the like. Examples include a cyclic arene ring and a polycyclic arene ring. Examples of the polycyclic arene ring include a fused polycyclic arene ring (condensed polycyclic aromatic hydrocarbon ring), a ring-assembled arene ring (ring-aggregated aromatic hydrocarbon ring), and the like.

Examples of the fused polycyclic arene ring include fused bicyclic and tetracyclic arene rings such as fused bicyclic arene ring and condensed tricyclic arene ring. Examples of the fused bicyclic arene ring include a fused bicyclic _C10-16 arene ring such as a naphthalene ring and an indene ring. Examples of the fused tricyclic arene ring include fused tricyclic C _14-20 arene rings such as an anthracene ring and phenanthrene ring. A preferred fused polycyclic arene ring is a fused polycyclic C _10-14 arene ring, such as a naphthalene ring.

Examples of the ring-set arene ring include a beerene ring such as a biphenyl ring, a phenylnaphthalene ring, and a binaphthyl ring; and a terarene ring such as a terphenyl ring. A preferred ring-set arene ring is a C12-18 _beerlane ring, such as a biphenyl ring.

In addition, in the present specification and the scope of patent claims, a "ring-aggregated arene ring" is a ring in which two or more ring systems (alene ring systems) are directly connected by a single bond (single bond) or a double bond, and the rings are directly connected. It means that the number of bonds to be formed is only one less than the number of ring systems. It is classified as a ring and is clearly distinguished from a "condensed polycyclic allene ring" such as a naphthalene ring (an acyclic allale ring).

Preferred ring Z ¹ includes C _6-14 arene ring, more preferably C _6-12 arene ring such as benzene ring, naphthalene ring and biphenyl ring, and further preferably C _6- such as benzene ring and naphthalene ring. It is a ₁₀ arene ring, especially a naphthalene ring. It is preferable that Z ¹ is a condensed polycyclic arene ring such as a naphthalene ring because the refractive index can be effectively improved and the heat resistance can be easily adjusted to an appropriate level.

Further, the ring Z ¹ in the monovalent groups Y ^1a and Y ^1b may be substituted at any of the positions 1 to 4 and 5 to 8 of the fluorene skeleton, respectively, but for example, the positions 2 and 3 and / Or 7th place and so on. When the substitution numbers k1a and k1b of Y ^1a and Y ^1b are 1, the preferred substitution positions (or binding positions) are 1,8-position, 2,7-position, 3,6-position, and 4,5-. Positions and the like In the above formula (1), the positions are symmetrical on the paper surface, and the 2,7-position is particularly preferable.

The bonding position on the ring Z ¹ with respect to the fluorene skeleton may be any position, and when the ring Z ¹ is a naphthalene ring, it may be either the 1-position or the 2-position of the naphthalene ring, but naphthalene. It is preferably the second position of the ring.

Examples of the substituent (non-reactive substituent or non-polymerizable substituent) represented by R ¹ include a halogen atom, a hydrocarbon group (or group [-R ^h ]), and a group [-OR ^h ] (formula). Among them, R ^h indicates the above-mentioned hydrocarbon group), a group [-SR ^h ] (in the formula, R ^h indicates the above-mentioned hydrocarbon group), an acyl group, a nitro group, a cyano group, a mono or a di-substituted amino group, etc. Can be mentioned.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

Examples of the hydrocarbon group represented by R ^h include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and the like.

Examples of the alkyl group include a linear or branched C _1-10 alkyl such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. Examples thereof include a linear or branched C _1-6 alkyl group, and more preferably a linear or branched C _1-4 alkyl group.

Examples of the cycloalkyl group include a C _5-10 cycloalkyl group such as a cyclopentyl group and a cyclohexyl group.

Examples of the aryl group include a _C6-12 aryl group such as a phenyl group, an alkylphenyl group, a biphenylyl group and a naphthyl group. Examples of the alkylphenyl group include a mono- or tri-C _1-4 alkyl-phenyl group such as a methylphenyl group (or trill group) and a dimethylphenyl group (or xsilyl group).

Examples of the aralkyl group include a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group and a phenethyl group.

Examples of the group [−OR ^h ] include an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group and the like, and specifically, a group corresponding to the example of the hydrocarbon group ^Rh is used. Can be mentioned. Examples of the alkoxy group include a linear or branched C _1-10 alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group and a t-butoxy group. Examples of the cycloalkyloxy group include a C _5-10 cycloalkyloxy group such as a cyclohexyloxy group. Examples of the aryloxy group include a _C6-10 aryloxy group such as a phenoxy group. Examples of the aralkyloxy group include a C _6-10 aryl-C _1-4 alkyloxy group such as a benzyloxy group.

Examples of the group [-SR ^h ] include an alkylthio group, a cycloalkylthio group, an arylthio group, an ^aralkylthio group and the like, and specific examples thereof include a group corresponding to the example of the hydrocarbon group Rh. .. Examples of the alkylthio group include C _1-10 alkylthio groups such as a methylthio group, an ethylthio group, a propylthio group, an n-butylthio group and a t-butylthio group. Examples of the cycloalkylthio group include a C _5-10 cycloalkylthio group such as a cyclohexylthio group. Examples of the arylthio group include a _C6-10 arylthio group such as a thiophenoxy group. Examples of the aralkylthio group include a C _6-10 aryl-C _1-4 alkylthio group such as a benzylthio group.

Examples of the acyl group include a C _1-6 alkyl-carbonyl group such as an acetyl group.

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 diC _1-4 alkylamino group such as a dimethylamino group. Examples of the bis (alkylcarbonyl) amino group include a bis (C _1-4 alkyl-carbonyl) amino group such as a diacetylamino group.

Typical groups R ¹ include a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, a substituted amino group and the like. When m1 is 1 or more, the preferred group ^R1 is an alkyl group or an alkoxy group, and specifically, a linear or branched C _1-6 alkyl group such as a methyl group, a methoxy group or the like. Examples thereof include a linear or branched C _1-4 alkoxy group, and among them, an alkyl group, particularly a C _1-4 alkyl group such as a methyl group is preferable. When the group R ¹ is an aryl group, the group R ¹ may form the ring-set arene ring together with the ring Z ¹ .

The substitution number m1 may be selected according to the type of the ring Z ¹ , for example, it can be selected from an integer of about 0 to 7, and the preferred range is an integer of 0 to 4 and 0 to 2 in a stepwise manner. Yes, more preferably 0 or 1, especially 0. When the number of substitutions m1 is 2 or more, the types of the two or more groups ^R1 substituted with the ring Z ¹ may be the same or different from each other. Further, the substitution position of the group ^R1 is not particularly limited, and may be selected according to the ^type of the ring Z1.

Examples of the typical monovalent group Y ^1a and Y ^1b represented by the above formula (Y1) include a phenyl group, a naphthyl group such as a 1-naphthyl group and a 2-naphthyl group, a biphenylyl group and the like, and a phenyl group. , Naphtyl group is preferable, naphthyl group is more preferable, and 2-naphthyl group is particularly preferable.

The substitution numbers k1a and k1b of the monovalent groups Y ^1a and Y ^1b 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. Of k1a and k1b, at least one is an integer of 1 or more, preferably both are integers of 1 or more, and more preferably both are 1.

When ^k1a and ^k1b are 1 or more, the types of the groups Y1a and Y1b substituting for different benzene rings among the two benzene rings forming the fluorene skeleton may be different from each other and are the same. It is preferable to have it. When k1a and k1b are 2 or more, the types of the two or more groups Y ^1a and Y ^1b that substitute for the same benzene ring among the two benzene rings may be the same or different from each other.

The substituent (non-reactive substituent or non-polymerizable substituent) represented by R ^2a and R ^2b may be any substituent other than the above groups Y ^1a and Y ^1b , and a typical group is alkyl. Examples thereof include a hydrocarbon group such as a group (excluding an aryl group), a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, and a cyano group. Examples of the alkyl group include a linear or branched C _1-6 alkyl group such as a methyl group, an ethyl group and a t-butyl group. When the number of substitutions m2a and m2b is 1 or more, the preferred R ^2a and R ^2b are C _1-4 alkyl groups such as a methyl group.

The substitution numbers m2a and m2b of R ^2a and R ^2b are, for example, an integer of about 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly 0. Although m2a and m2b may be different from each other, they are preferably the same. When m2a and m2b are 1 or more, the types of R ^2a and R ^2b that are substituted with different benzene rings among the two benzene rings forming the fluorene skeleton may be different from each other and are the same. Is preferable. When m2a and m2b are 2 or more, the types of two or more R ^2a and R ^2b that are substituted with the same benzene ring among the two benzene rings may be the same or different from each other. The substitution positions of R ^2a and R ^2b are not particularly limited, and may be substituted at positions other than the substitution positions of the groups Y ^1a and Y ^1b .

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

In the above formula (Y2) showing Y ^2a and Y ^2b of ^monovalent groups (or hydroxyl group-containing groups) bonded to the 9,9-position of the fluorene skeleton, the linear or branched alkylene represented by A1. Examples of the group include a linear or branched C _1-12 alkylene such as a methylene group, an ethylene group, a trimethylene group, a propylene group, a 1,2-butanediyl group and a 2-methylpropane-1,3-diyl group. The group is mentioned. Preferred alkylene groups include linear or branched C _1-8 alkylene groups, specifically methylene groups, ethylene groups, trimethylene groups, propylene groups, 2-methylpropane-1,3-diyl groups and the like. Examples thereof include a linear or branched C _1-6 alkylene group, more preferably a linear or branched C _1-5 alkylene group, and further preferably a linear or branched C _1-4 . It is an alkylene group, and among them, a linear or branched C _2-4 alkylene group is preferable, and a trimethylene group is particularly preferable.

Examples of the linear or branched alkylene group represented by A ² include a straight chain such as an ethylene group, a propylene group, a trimethylene group, a 1,2-butandyl group, a 1,3-butandyl group and a tetramethylene group. Examples thereof include a C _2-6 alkylene group having a form or a branched chain. The preferred alkylene group A ² is a linear or branched C _2-3 alkylene group, more preferably a linear or branched C _2-3 alkylene group, and among them, an ethylene group or a propylene group. Is preferable, and an ethylene group is particularly preferable.

The number of repetitions n2 of the oxyalkylene group − (A ² O) − can be selected from, for example, about 0 to 20, and the preferred range is 0 to 15, 0 to 10, 0 to 8, 0 in the following steps. It is ~ 5, 0 ~ 3, 0 ~ 2, 0 ~ 1, especially 0. The number of repetitions n2 may be an average value (or an arithmetic mean value or an arithmetic mean value), that is, an average number of added moles, and the range thereof is the same as the range of the integers including the preferred embodiment. When n2 is 2 or more, the types of 2 or more A ^2s in the (poly) oxyalkylene group- (A ² O) _n2- may be different from each other, but are preferably the same.

Further, the total number of repetitions n2 in Y ^2a and Y ^2b , that is, the total number of oxyalkylene groups in one molecule of the diol compound represented by the above formula (1) (or the average value of the total number of added moles) [hereinafter. , Simply referred to as the total number of n2] can be selected from, for example, a range of about 0 to 30, and the preferred range is 0 to 20, 0 to 10, 0 to 6, 0 to 4, 0 to 0 in the following steps. It is 2, more preferably 0 to 1, and particularly 0. Further, the total number of n2 may be an integer or an average value of the total number of added moles.

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

The total number of n2 can be measured by a conventional method. For example, the diol compound in which n2 in Y ^2a and Y ^2b of the above formula (1) is 0 [represented by the formula (1A) described later). Compound] is subjected to an addition reaction with an alkylene oxide (alkylene carbonate or haloalkanol) to form a (poly) alkyleneoxy group [-(OA ² ) _n1- ], and the amount (or hydroxyl value) of the diol compound is formed. And a method of calculating as a value of arithmetic mean or arithmetic mean from the ratio of the amount of alkylene oxide (alkylene carbonate or haloalkanol) consumed in the reaction, specifically, Japanese Patent Application Laid-Open No. 2013-53310. It can be measured by a method or the like.

As a typical diol compound represented by the above formula (1), for example, k1a and k1b are 1, Z ¹ is a C _6-12 allene ring such as a benzene ring, a naphthalene ring, and a biphenyl ring, and A. ¹ is a linear or branched C _1-6 alkylene group, A ² is a linear or branched C _2-4 alkylene group, and n2 is 0 or 1 to 10 diol compounds. Preferably, k1a and k1b are 1, Z ¹ is a benzene ring or a naphthalene ring, A ¹ is a linear or branched C _1-4 alkylene group, and A ² is an ethylene group. A linear or branched _C2-3 alkylene group such as a propylene group, a diol compound in which n2 is 0 or 1-6; more preferably, k1a and k1b are 1 and Z ¹ is naphthalene. It is a ring, A ¹ is a linear or branched C _2-4 alkylene group, A ² is an ethylene group, and n 2 is a diol compound of 0 or 1; among them, 9,9-. 9,9-Bis (3-hydroxypropyl) -di such as bis (3-hydroxypropyl) -di (1-naphthyl) fluorene, 9,9-bis (3-hydroxypropyl) -di (2-naphthyl) fluorene, etc. Naftylfluorene is preferred; in particular 9,9-bis (3-hydroxypropyl) -2,7-dinaphthyl such as 9,9-bis (3-hydroxypropyl) -2,7-di (2-naphthyl) fluorene. Fluorene is preferred.

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, which is a preferable range. The temperature is 1.73 to 1.78, 1.74 to 1.77, 1.745 to 1.765, and 1.75 to 1.76 in stages.

The melting point of the diol compound represented by the formula (1) may be, for example, about 100 to 250 ° C., and the preferred range is 150 to 240 ° C., 175 to 230 ° C., 180 to 225 in a stepwise manner. ℃.

The 5% mass reduction temperature of the diol compound represented by the formula (1) may be, for example, about 250 to 500 ° C., and the preferred range is, in the following steps, 350 to 450 ° C. and 370 to 420 ° C. It is 380 to 400 ° C.

In the present specification and claims, the refractive index, melting point and 5% mass reduction temperature of the diol compound represented by the above formula (1) can be measured by the methods described in Examples described later.

[Method for producing a diol compound represented by the formula (1)]
The method for producing the diol compound represented by the formula (1) is not particularly limited. For example, in the formula (1), the diol compound in which n2 in Y ^2a and Y ^2b is 0 [represented by the formula (1A). Also called a compound to be produced. ] May be prepared according to the following reaction process formula including a reduction step of subjecting the compound represented by the following formula (I) to a reduction reaction.

[In the formula, X ^1a and X ^2a and X ^1b and X ^2b each independently represent a pair of reactive groups capable of forming a carbon-carbon bond (or direct bond) by a coupling reaction, respectively.
Y ^3a and Y ^3b are independently expressed by the following equation (Y3).

( ^In the formula, A3 represents a linear or branched alkylene group.
R ³ represents a hydrogen atom or an alkyl group. )
Indicates 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 (where n2 in Y ^2a and Y ^2b indicates 0) include the above formula (where n2 in Y 2a and Y 2b indicates 0). Same as 1)].

(Preparation of compound represented by formula (I))
The compound represented by the formula (I) is a coupling reaction (or cross-coupling reaction) between the compound represented by the formula (II) and the compounds represented by the formulas (IIIa) and (IIIb). Can be prepared by.

Coupling reactions include conventional coupling reactions such as Suzuki-Miyaura coupling reaction, Umeda-Kosugi-Stille coupling reaction, Negishi coupling reaction, Hiyama coupling reaction and other palladium catalysts (or palladium (or palladium). 0) Coupling reaction by catalyst), coupling reaction by nickel catalyst (or nickel (0) catalyst) such as Kumada-Tamao-Corriu coupling reaction, and the like. Of these coupling reactions, the Suzuki-Miyaura coupling reaction is preferable.

In the formula (II), X ^1a and X ^1b show reactive groups capable of independently forming a carbon-carbon bond (or a direct bond) by a coupling reaction; in the formulas (IIIa) and (IIIb). , X ^2a indicate a reactive group capable of forming a carbon-carbon bond by a coupling reaction with the X ^1a and X 2 ^b with the X 1 ^b , respectively. The reactive groups X ^1a and X ^1b and X ^2a and X ^2b can be appropriately selected depending on the type of the coupling reaction. When synthesized by the Suzuki-Miyaura coupling reaction, examples of one of the reactive groups, for example, ^{X1a and X1b ,} include a halogen atom or an alkanesulfonyloxy group fluoride. Examples of the halogen atom include an iodine atom, a bromine atom, a chlorine atom and the like. Examples of the fluorinated alkane sulfonyl oxy group include a fluorinated C _1-4 alkane sulfonyl oxy group such as a trifluoromethanesulfonyl oxy group (or group [-OTf]). One of these reactive groups may be used alone or in combination of two or more. Of these one reactive group, a halogen atom is preferable, an iodine atom and a bromine atom are more preferable, and a bromine atom is further preferable. Further, the types of X ^1a and X ^1b may be different from each other, but are preferably the same.

Examples of the other reactive groups X ^2a and X ^2b that can be coupled to the one reactive group X ^1a and X ^1b in the Suzuki-Miyaura coupling reaction include a boronic acid group (dihydroxyboryl group or group [-B]. (OH) ₂ ]), boronic acid ester group and the like can be mentioned. Examples of the boronic acid ester group include a dialkoxyboryl group such as a dimethoxyboryl group, a diisopropoxyboryl group and a dibutoxyboryl group; a pinacholate boron group (or group [-Bpin]), 1,3,2-dioxabolinan-2. -Il group, cyclic boronic acid ester group such as 5,5-dimethyl-1,3,2-dioxabolinan-2-yl group and the like can be mentioned. These other reactive groups may be used alone or in combination of two or more. Of the other reactive groups, the group [-B (OH) ₂ ] is preferable. Further, the types of X ^2a and X ^2b may be different from each other, but are preferably the same.

The groups X ^1a and X ^1b and the groups X ^2a and X ^2b may be any reactive group as long as they are a pair of reactive groups capable of coupling with each other, respectively, and the groups X ^1a and X ^1b may be used. Is the other reactive group such as a boronic acid group, and X ^2a and X ^2b may be the one reactive group such as a halogen atom, but X ^1a and X ^1b are the one such as a halogen atom. It is preferable that X ^2a and X ^2b are the other reactive groups such as a boronic acid group.

Further, in the formula (Y3) showing the monovalent groups Y ^3a and Y ^3b , the linear or branched alkylene group A ³ has one less carbon number than A ¹ in the formula (1). It is the basis. Typical alkylene groups A3 include linear or branched chains such as methylene group ^, ethylene group, trimethylene group, propylene group, 1,2-butanediyl group and 2-methylpropane-1,3-diyl group. Examples thereof include a C _1-11 alkylene group, preferably a C _1-5 alkylene group, a C _1-4 alkylene group, and a C _1-3 alkylene group in a stepwise manner, and an ethylene group is particularly preferable.

Examples of the alkyl group represented by R ³ include a linear or branched C _1-6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and a t-butyl group. , And preferably a C _1-4 alkyl group, more preferably a C _1-3 alkyl group, and particularly a C _1-2 alkyl group such as a methyl group. R ³ may be either a hydrogen atom or an alkyl group, but is preferably an alkyl group.

Examples of the compound represented by the formula (II) include compounds corresponding to a preferred embodiment of the diol compound represented by the formula (1), for example, 9,9-bis (alkoxycarbonylalkyl) dihalofluorene and the like. Be done.

Examples of the 9,9-bis (alkoxycarbonylalkyl) dihalofluorene include 9,9-bis (2-methoxycarbonylethyl) -2,7-dibromofluorene and 9,9-bis (2-ethoxycarbonylethyl). 9,9-Bis (C _1-4 alkoxy-carbonyl-C _2-6 alkyl) such as -2,7-dibromofluorene, 9,9-bis (2-methoxycarbonylpropyl) -2,7-dibromofluorene- Dihalofluorene and the like can be mentioned. The 9,9-bis (alkoxycarbonylalkyl) dihalofluorene may be prepared, for example, according to the method described in JP-A-2005-89422, and specifically, such as 2,7-dibromofluorene. A method of reacting dihalo-9H-fluorenes in which the 9-position is unsubstituted 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. It may be prepared by such as.

As the compound represented by the formula (IIIa) and the compound represented by the formula (IIIb), a compound corresponding to a preferred embodiment of the diol compound represented by the formula (1), for example, phenylboronic acid, 1- Examples thereof include naphthylboronic acid and 2-naphthylboronic acid, and 2-naphthylboronic acid is preferable. The compound represented by the formula (IIIa) and the compound represented by the formula (IIIb) are preferably the same compound, and commercially available products and the like can be used.

The ratio of the compound represented by the formula (II) to the total amount of the compound represented by the formula (IIIa) and the compound represented by the formula (IIIb) is, for example, the former / the latter (molar ratio) =. It may be about 1/2 to 1/10, and the preferred range is 1 / 2.1 to 1/5 and 1 / 2.2 to 1 / 3.5 in stages.

The coupling reaction may be carried out in the presence of a catalyst. When synthesizing by the Suzuki-Miyaura coupling reaction, the reaction may be carried out in the presence of a palladium catalyst, and examples of the palladium catalyst include conventional coupling catalysts such as palladium (0) catalyst and palladium (II) catalyst. Be done.

Examples of the palladium (0) catalyst include tetrakis (triphenylphosphine) palladium (0) [or Pd (PPh ₃ ) ₄ ], bis (tri-t-butylphosphine) palladium (0) [or Pd (P (t)). -Bu) Palladium (0) -phosphine complex such as ₃ ) ₂ ] and the like can be mentioned.

Examples of the palladium (II) catalyst include [1,2-bis (diphenylphosphino) ethane] palladium (II) dichloride [or PdCl ₂ (dppe)] and [1,3-bis (diphenylphosphino) propane]. Palladium (II) dichloride [or PdCl ₂ (dpppp)], [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride [or PdCl ₂ (dpppf)], bis (triphenylphosphine) palladium ( II) Palladium (II)-such as dichloride [or PdCl ₂ (PPh ₃ ) ₂ ], bis (tri-o-tolylphosphine) palladium (II) dichloride [or PdCl ₂ (P (o-polyl) ₃ ) ₂ ]. Examples include phosphine complex. When a palladium (II) catalyst is used, it is reduced to a zero-valent complex by a reducing compound in the reaction system such as phosphine, amine, or organometallic reagent, and the reaction starts.

The palladium catalyst is coordinated with a catalyst precursor such as tris (dibenzylideneacetone) dipalladium (0) chloroform complex [or Pd ₂ (dba) ₃ · CHCl ₃ ], and phosphins, carbene and the like. It may be prepared in the reaction system by adding the child.

These catalysts can also be used alone or in combination of two or more. Of these catalysts, a palladium (0) -phosphine complex such as Pd (PPh ₃ ) ₄ is preferred. The ratio of the catalyst may be, for example, about 0.01 to 0.1 mol, preferably 0.03 to 0.07, in terms of metal with respect to 1 mol of the compound represented by the above formula (2). It is mol, more preferably 0.04 to 0.06 mol.

The Suzuki-Miyaura coupling reaction may be carried out in the presence of a base. Examples of the base include metal carbonates or bicarbonates, metal hydroxides, metal fluorides, metal phosphates, metal organic acid salts, metal alkoxides and the like.

Examples of the metal carbonate or hydrogen carbonate include alkali metal carbonates or hydrogen carbonates such as sodium carbonate, potassium carbonate, cesium carbonate, and sodium hydrogen carbonate, and tarium (I) carbonate.

Examples of the metal hydroxide include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and cesium hydroxide, alkaline earth metal hydroxides such as barium hydroxide, and tallium hydroxide (I). Be done.

Examples of the metal fluoride include alkali metal fluorides such as potassium fluoride and cesium fluoride.

Examples of the metal phosphate include alkali metal phosphates such as tripotassium phosphate.

Examples of the metal organic acid salt include alkali metal acetates such as potassium acetate.

Examples of the metal alkoxide include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide.

These bases can also be used alone or in combination of two or more. As the preferred base, metal carbonates such as sodium carbonate and potassium carbonate are preferable. 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 with respect to 1 mol of the compound represented by the above formula (II). Is.

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

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, N-methyl-2-pyrrolidone; Sulfoxides such as dimethylsulfoxide; aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, etc. Hydrocarbons and the like can be mentioned.

Examples of the cyclic ether include dioxane and tetrahydrofuran. Examples of the chain ether include dialkyl ethers such as diethyl ether and diisopropyl ether, glycol ethers and the like. 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.

Examples of aliphatic hydrocarbons include hexane and dodecane. Examples of alicyclic hydrocarbons include cyclohexane. Examples of aromatic hydrocarbons include toluene, xylene and the like.

These solvents may be used alone or in combination of two or more. Of these solvents, a mixed solvent of water and aromatic hydrocarbons such as toluene is preferable.

The coupling reaction may be carried out under an inert atmosphere such as nitrogen gas; 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, preferably 3 to 12 hours.

After completion of the reaction, the reaction mixture was optionally combined with conventional separation and purification methods such as washing, extraction, filtration, dehydration, concentration, decantation, drying, crystallization, reprecipitation, column chromatography, adsorption. It may be separated and purified by a method or the like.

(Preparation (or reduction step) of the compound represented by the formula (1A))
The diol compound represented by the formula (1A) (the compound in which n2 in Y ^2a and Y ^2b in the formula (1) is 0) can be prepared by reducing the compound represented by the formula (I). For the reduction, a conventional reducing agent or the like may be used. Examples of the reducing agent include metal hydrides such as boron hydride metals, aluminum hydride metals, boranes, aluminum hydrides, organosilicon compounds, and organotin compounds.

Examples of the boron hydride metals include boron hydride alkali metals; zinc hydrides such as zinc hydride (Zn (BH ₄ ) ₂ )). Examples of the sodium borohydride alkali metals include lithium borohydride (LiBH ₄ ), lithium triethyl borohydride (LiBH (C ₂ H ₅ ) ₃ ), and lithium tris-butyl borohydride (LiBH (s—C)). ₄ H ₉ ) ₃ ), bis (2,4,6-trimethylphenyl) borohydride lithium borohydride (LiBH (Mes) ₂ ) and other lithium borohydrides; sodium borohydride (NaBH ₄ ), boron cyanoborohydride Sodium (NaBH ₃ CN), sodium trimethoxyborohydride (NaBH (OCH ₃ ) ₃ ), sodium triacetoxyborohydride (NaBH (OCOCH ₃ ) ₃ ), sulfide of sodium borohydride (NaBH ₂ S ₃ ), etc. Sodium borohydrides; Examples thereof include sodium borohydrides such as tri-s-butyl potassium borohydride (KBH (s _- C 4H ₉ ) ₃ ).

Examples of the aluminum hydride metals include aluminum hydride alkali metals and the like. Lithium aluminum hydride (LiAlH ₄ ), lithium hydride trimethoxyaluminum lithium (LiAlH (OCH ₃ ) ₃ ), and lithium hydride trit-butoxyaluminum lithium (LiAlH (Ot-C ₄ H ₉ )) are examples of lithium aluminum hydride alkali metals. ) ₃ ) Lithium aluminum hydride; sodium aluminum hydride (NaAlH ₄ ), bis (2-methoxyethoxy) aluminum sodium hydride ([(CH ₃ OCH ₂ CH ₂ O) ₂ AlH ₂ ] Na), etc. Examples include lithium aluminum hydride.

Examples of boranes include diborane; borane-tetrahydrofuran complex, borane-dimethyl sulfide complex and other borane complexes; 9-borabicyclo [3.3.1] nonane (9-BBN) and the like.

Examples of aluminum hydrides include aluminum hydride (AlH ₃ ), diisobutylaluminum hydride ((i _- C 4H ₉ ) ₂ AlH) and the like.

Examples of the organosilicon compound include trialkylsilanes such as triethylsilane, diallylsilanes such as diphenylsilane, and aryldialkylsilanes such as phenyldimethylsilane.

Examples of the organotin compound include trialkylstannan such as tri-n-butylstannan, dialkylstannan such as din-butylstannan, and diarylstannan such as diphenylstannan.

These reducing agents may be used alone or in combination of two or more. Preferred reducing agents are sodium borohydride metals such as boron borohydride alkali metals, and more preferably sodium borohydride such as sodium borohydride (NaBH ₄ ).

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

The reducing agent may be used together with other reagents (or activators) depending on the type and the compound represented by the formula (I), for example, sodium borohydride (NaBH ₄ ) and the like. When sodium borohydride is used as a reducing agent, it may be used together with boron trifluoride / ether complex 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 with respect to 1 mol of the reducing agent.

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), and chain ethers such as dialkyl ether and glycol ether. Examples include 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 ether such as methyl cellosolve and methyl carbitol, and (poly) alkylene glycol dialkyl ether such as dimethoxyethane. And so on.

The solvent can be used alone or in combination of two or more. The preferable solvent is ethers, and cyclic ethers such as THF are more preferable.

The reaction may be carried out in an atmosphere of an inert gas such as nitrogen; 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.

After completion of the reaction, the reducing agent may be quenched. The quenching may be carried out by adding water, or may be gently quenched with acetone in advance in order to suppress heat generation.

After completion of the reaction, if necessary, the reaction mixture is subjected to conventional separation and purification methods such as washing, extraction, filtration, dehydration, drying, concentration, decantation, recrystallization, reprecipitation, chromatography, and a combination thereof. It may be separated and purified by such means.

The alkylene oxide (alkylene carbonate or haloalkanol) corresponding to the alkylene group ^A2 is conventionally added to the diol compound represented by the formula (1A) thus obtained at a ratio corresponding to the number n2. The diol compound represented by the above formula (1) may be prepared by reacting according to the above method.

[Resin made from a diol compound represented by the formula (1)]
The resin (polymer or polymer) prepared from the diol compound represented by the formula (1) is not particularly limited and may be a thermosetting resin or a photocurable resin, but may be moldable (fluidity or handling). Properties) and heat resistance can be adjusted in a well-balanced manner, and thus a thermoplastic resin is preferable.

The thermoplastic resin is not particularly limited as long as it is a resin containing at least a diol component (A) as a polymerization component, and examples thereof include polyester-based resins and thermoplastic polyurethane-based resins, which have high refractive index and low compound refraction. A polyester resin is preferable from the viewpoint of excellent balance between optical properties such as a low number of abbreviations and moldability.

The polyester resin may be any resin having at least an ester bond [including a carbonic acid ester bond (carbonic acid bond)] as the main chain skeleton, and examples thereof include polyester resin, polyester carbonate resin, and polycarbonate resin. Among polyester resins, polycarbonate resin is preferable in terms of excellent strength (or hardness) and good injection moldability; polyester resin is preferable in terms of excellent stretchability (flexibility or toughness) and good film moldability. Preferred; polyester carbonate resin is preferable in that it has an excellent balance between strength and stretchability and can achieve both injection moldability and film moldability in a well-balanced manner; a balance between high refractive index, high moldability, low compound refraction and low Abbe number. Is particularly excellent, polyester resin is most preferable.

The specific constituent unit of the resin may contain at least a diol unit (A), and may further contain a dicarboxylic acid unit (B), a carbonate unit (C), and the like.

(Glycol unit (A))
First diol unit (A1)
The diol unit (A) contains at least a structural unit represented by the above formula (1P) as the first diol unit (A1). Since the structural unit represented by the formula (1P) corresponds to the first diol component represented by the formula (1), Y ^1a and Y ^1b , k1a and k1b, R in the formula (1P). ^2a and R ^2b , m2a and m2b are the same as the above formula (1) including the preferred embodiments, and A ¹ , A ² and n2 in Y ^2c and Y ^2d are also the same as the above formula including the preferred embodiments. It is the same as Y ^2a and Y ^2b of (1).

Moreover, as a typical first diol unit (A1), the diol unit corresponding to the example in the section of the diol compound represented by the formula (1) can be mentioned, and it is the same including the preferable embodiment. The first diol unit (A1) may be contained alone or in combination of two or more.

The resin of the present invention containing the first diol unit (A1) can greatly improve the refractive index while suppressing an excessive increase in the glass transition temperature Tg (while retaining or reducing Tg), and has a high refractive index and a high index. Both formability (fluidity or handleability) can be achieved. That is, in the fluorene ring of the above formula (1P), an aryl group-containing group (groups Y ^1a and Y ^1b ) that easily has a high refractive index is used as a conventional (diol compound having a 9,9-bisarylfluorene skeleton). By combining the point of substituting at the ^1st to 8th positions instead of the 9th position and the point of substituting the alkylene group A1 at the 9th position instead of the aryl group, the above-mentioned characteristics can be compatible at a higher level than before. Is. In particular, as shown in Examples described later, even if the chemical structure contains the same number of benzene ring skeletons (aromatic ring skeletons) as the conventional diol compound having a 9,9-bisarylfluorene skeleton, the first It was an unexpected result that the diol unit (A1) could effectively improve the refractive index and also could retain or reduce Tg.

Further, since the resin of the present invention can improve the moldability without significantly impairing the heat resistance which is contrary to the moldability (without significantly reducing Tg), the balance between the heat resistance and the moldability is also excellent. Furthermore, when the first diol unit (A1) is contained, birefringence can be effectively reduced even if a large number of benzene ring skeletons (aromatic ring skeletons) are contained, and the Abbe number can also be significantly reduced. It is useful and can satisfy these characteristics in a well-balanced manner together with the high refractive index and high formability.

The ratio of the first diol unit (A1) in the resin may be, for example, about 1 mol% or more with respect to the entire diol unit (A), and the preferred range is 5 to 100 in stages below. Mol%, 10-95 mol%, 20-90 mol%. 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 becomes large on the negative (minus) side, resulting in birefringence. The absolute value may not be reduced sufficiently.

The diol unit (A) may be composed of only the first diol unit (A1), but a different diol unit, for example, the second diol unit (A2) represented by the formula (2), said. It may further contain a second diol unit (A3) represented by the formula (3).

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

In the formula (2), as the arene ring represented by Z ^2a and Z ^2b , for example, the same arene ring as the example of the ring Z ¹ described in the section of the diol compound represented by the formula (1) is used. Can be mentioned. The types of rings Z ^2a and Z ^2b may be the same or different from each other, and are preferably the same. Of the rings Z ^2a and Z ^2b , a C _6-12 arene ring such as a benzene ring, a naphthalene ring, and a biphenyl ring is preferable, and a C _6-10 arene ring such as a benzene ring and a naphthalene ring is more preferable, and a higher refractive index is obtained. A naphthalene ring is particularly preferable because it is easy to reduce the number of abbene and has an excellent balance with low compound refraction and heat resistance. The types of Z ^2a and Z ^2b may be different from each other, but are preferably the same.

The substitution positions of the rings Z ^2a and Z ^2b bonded to the 9-position of the fluorene ring are not particularly limited. For example, when the rings Z ^2a and Z ^2b are naphthalene rings, the 1-position or 2-position, preferably the 2-position is preferable. When the rings Z ^2a and Z ^2b are biphenyl rings, they are at the 2-position, 3-position or 4-position, preferably 3-position.

Examples of the substituent (non-reactive substituent or non-polymerizable substituent) represented by ^R4 include a hydrocarbon group such as an alkyl group and an aryl group; a cyano group; a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. Halogen atom and the like can be mentioned. Examples of the alkyl group include a linear or branched C _1-6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and a t-butyl group. Examples of the aryl group include a _C6-10 aryl group such as a phenyl group. When m4 is 1 or more, the preferred group R ⁴ is an alkyl group, a cyano group, a halogen atom, more preferably an alkyl group, and particularly a linear or branched C _1-4 alkyl group such as a methyl group. Is preferable.

The substitution number m4 of the group R ⁴ is, for example, an integer of about 0 to 6, preferably an integer of 0 to 4 and an integer of 0 to 2 in a stepwise manner, more preferably 0 or 1, particularly 0. Is. When m4 is 2 or more, the types of 2 or more groups ^R4 may be the same or different from each other. Further, the substitution position of the group ^R4 is not particularly limited, and examples thereof include 2- to 7-positions such as the 2-position, 3-position and / or 7-position of the fluorene ring, and preferably 2-position or 2,7-position. Is.

Examples of the substituent (non-reactive substituent or non-polymerizable substituent) represented by R ^5a and R ^5b include the diol compound represented by the above formula (1) (or the first diol unit (A1)). ), The same group as the substituent exemplified as ^R1 can be mentioned. Among these groups R ^5a and R ^5b , typical groups are halogen atoms; hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups; alkoxy groups; acyl groups; nitro groups; cyano groups. ; Substituted amino group and the like can be mentioned. When the number of substitutions m5a and ^m5b is 1 or more, preferred groups ^R5a and R5b include an alkyl group, a cycloalkyl group, an aryl group and an alkoxy group, and more preferably a linear or branched group such as a methyl group. C _5-8 cycloalkyl groups such as chain C _1-6 alkyl groups and cyclohexyl groups, C _6-14 aryl groups such as phenyl groups, and linear or branched C _1-4 alkoxy groups such as methoxy groups. Can be mentioned. Of these, an alkyl group and an aryl group are preferable, and a linear or branched C _1-4 alkyl group such as a methyl group and a C _6-10 aryl group such as a phenyl group are particularly preferable. When the group R ^5a or R ^5b is an aryl group, the group R ^5a or R ^5b may form a ring-aggregated arene ring together with the rings Z ^3a or Z ^3b .

The substitution numbers m5a and m5b of the groups R ^5a and R ^5b can be appropriately selected according to the types of the rings Z ^2a and Z ^2b , and may be an integer of 0 or more, for example, an integer of about 0 to 8, as a preferable range. Is an integer of 0 to 4 and an integer of 0 to 2, and 0 or 1 is more preferable, and 0 is particularly preferable.

The substitution numbers m5a and m5b may be different from each other, but are preferably the same. When the number of substitutions m5a and m5b is 2 or more, the types of 2 or more R ^5a and R ^5b to be substituted with the same ring Z ^2a and Z ^2b may be the same or different from each other. Further, the types of the groups R ^5a and R ^5b may be the same or different from each other. In particular, when m5a and m5b are 1, the rings Z ^2a and Z ^2b may be a benzene ring, a naphthalene ring or a biphenyl ring, and the groups R ^5a and R ^5b may be a methyl group. Further, the substitution positions of the groups R ^5a and R ^5b are not particularly limited, and may be any positions other than the bonding positions of the rings Z ^2a and Z ^2b and the 9-position of the ether bond (—O—) and the fluorene ring. Preferably, in rings Z ^2a and Z ^2b , the ether bond (—O—) is replaced with an ortho position (a carbon atom adjacent to the bond position of the ether bond).

Examples of the alkylene group A ^4a and A ^4b include a linear or branched C such as an ethylene group, a propylene group (1,2-propanediyl group), a trimethylene group, a 1,2-butanediyl group, and a tetramethylene group. Examples thereof include _2-6 alkylene groups, and when the number of repetitions n4a and n4b is 1 or more, preferably A ^4a and A ^4b are linear or branched C _2-4 alkylene groups, more preferably ethylene groups and propylene groups. Such as C _2-3 alkylene group, and ethylene group is particularly preferable. The types of A ^4a and A ^4b may be the same or different from each other.

The number of repetitions (number of added moles) n4a and n4b of the oxyalkylene group (-OA ^4a- ) and (-OA ^4b- ) may be selected from 0 or more, for example, an integer range of about 0 to 15, which is preferable. The range is 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, 0-1 in the following steps. The number of repetitions n4a and n4b is preferably 1 or more in terms of improving the polymerization reactivity, and more preferably 1 to 15, 1 to 10, 1 to 8, 1 to 6 in stages. It is 1 to 4, 1 to 3, 1 to 2, and 1 is particularly preferable.

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

Further, the two repetition numbers n4a and n4b may be the same as or different from each other. When n4a and n4b are 2 or more, the types of 2 or more oxyalkylene groups (-OA ^4a- ) and (-OA ^4b- ) may be the same or different from each other.

The substitution positions of the groups [-O- (A ^4a O) _n4a- ] and [-O- (A ^4b O) _n4b- ] (also referred to as ether-containing groups) with respect to the rings Z ^2a and Z ^2b are not particularly limited. It suffices to replace the rings Z ^2a and Z ^2b with appropriate positions, respectively. When the rings Z ^2a and Z ^2b are benzene rings, the substitution positions of the ether-containing group are the 2-position, 3-position or 4-position, particularly the 3-position or 4-position of the phenyl group bonded to the 9-position of the fluorene ring. It is particularly preferable to replace it with the 4-position. When the rings Z ^2a and Z ^2b are naphthalene rings, the ether-containing group is preferably substituted at any position of the 5 to 8 positions of the naphthyl group bonded to the 9-position of the fluorene ring, for example, the fluorene ring. The 1-position or 2-position of the naphthalene ring is substituted for the 9-position of (1-naphthyl or 2-naphthyl relationship), and the 1,5-position, 2,6-position, etc. are substituted for this substitution position. It is preferable to replace with the relation of 2,6-position. When the rings Z ^2a and Z ^2b are ring-set arene rings, the substitution position of the ether-containing group is not particularly limited, and for example, the arene ring bonded to the 9-position of the fluorene ring or the arene adjacent to the arene ring. It may be replaced with a ring. For example, when rings Z ^2a and Z ^2b are biphenyl rings (or rings Z ^2a and Z ^2b are benzene rings, m5a and m5b are 1, R ^5a and R ^5b are phenyl groups), 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-position of the biphenyl ring. 4th, 5th, 6th, 2', 3'or 4', preferably 6th or 4', particularly 6th.

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 above formula (2); n4a and n4b. Examples thereof include 9,9-bis [hydroxy (poly) alkoxyaryl] fluorenes having a value of 1 or more, for example, about 1 to 10.

In the present specification and claims, unless otherwise specified, "(poly) alkoxy" is used to mean including both an alkoxy group and a polyalkoxy group.

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

Examples of the 9,9-bis (hydroxyphenyl) fluorene include 9,9-bis (4-hydroxyphenyl) fluorene.

Examples of the 9,9-bis (alkyl-hydroxyphenyl) fluorene include 9,9-bis (4-hydroxy-3-methylphenyl) fluorene and 9,9-bis (4-hydroxy-3,5-dimethylphenyl). ) Fluorene and the like 9,9-bis [(mono or di) C _1-4 alkyl-hydroxyphenyl] fluorene and the like can be mentioned.

Examples of the 9,9-bis (aryl-hydroxyphenyl) fluorene include 9,9-bis (C _6-10 aryl-hydroxyphenyl) such as 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene. Fluorene and the like can be mentioned.

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

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

Examples of the 9,9-bis [hydroxy (poly) alkoxyphenyl] fluorene include 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and 9,9-bis [4- (2-hydroxypropoxy). ) Phenyl] fluorene, 9,9-bis [4- (2- (2-hydroxyethoxy) ethoxy) phenyl] fluorene and other 9,9-bis [hydroxy (mono or deca) C _2-4 alkoxy-phenyl] fluorene And so on.

Examples of the 9,9-bis [alkyl-hydroxy (poly) alkoxyphenyl] fluorene include 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene and 9,9-bis [4. -(2-Hydroxypropoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2- (2-hydroxyethoxy) ethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-Hydroxyethoxy) -3,5-dimethylphenyl] fluorene and the like 9,9-bis [(mono or di) C _1-4 alkyl-hydroxy (mono or deca) C _2-4 alkoxy-phenyl] fluorene and the like Can be mentioned.

Examples of the 9,9-bis [aryl-hydroxy (poly) alkoxyphenyl] fluorene include 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene and 9,9-bis (4). -(2-Hydroxypropoxy) -3-phenylphenyl) fluorene, 9,9-bis [4- (2- (2-hydroxyethoxy) ethoxy) -3-phenylphenyl] fluorene, etc. 9,9-bis [C _6-10 aryl-hydroxy (mono or deca) C _2-4 alkoxy-phenyl] fluorene and the like can be mentioned.

Examples of the 9,9-bis [hydroxy (poly) alkoxynaphthyl] fluorene include 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene and 9,9-bis [6- (2). -Hydroxypropoxy) -2-naphthyl] fluorene, 9,9-bis [6- (2- (2-hydroxyethoxy) ethoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2-hydroxyethoxy) ethoxy) ) -1-Naphtyl] Fluorene and the like 9,9-bis [hydroxy (mono or deca) C _2-4 alkoxy-naphthyl] fluorene and the like can be mentioned.

These second diol units (A2) may be contained alone or in combination of two or more. Of the second diol unit (A2), preferably 9,9-bis [hydroxy (poly) alkoxy) such as 9,9-bis [hydroxy (mono or hexa) C _2-4 alkoxy C _6-10 aryl] fluorene. Aryl] fluorenes; more preferably 9,9-bis [hydroxy (mono or di) C _2-4 alkoxy C _6-10 aryl] fluorene; more preferably 9,9-bis [4- (2-hydroxyethoxy) 9, 9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene, etc. 9-bis [Hydroxy C _2-3 alkoxy-C _6-12 aryl] Fluorene, especially 9,9-bis [6- (2) because of its excellent balance of high refractive index, low double refraction, and high heat resistance. Constituent units derived from 9,9-bis [hydroxy C _2-3 alkoxynaphthyl] fluorene such as -hydroxyethoxy) -2-naphthyl] fluorene are preferred.

Third diol unit (A3)
The diol unit (A) may or may not contain the third diol unit (A3) represented by the formula (3), if necessary. When the third diol unit (A3) is contained, the polymerization reactivity is enhanced and the molecular weight is easily increased. In addition, it may be possible to suppress an excessive increase in the glass transition temperature and improve moldability and handleability.

In the above formula ( ³ ), examples of the alkylene group represented by A5 include an ethylene group, a propylene group, a trimethylene group, a 1,2-butanjiyl group, a 1,3-butanjiyl group, a tetramethylene group, and 1,5. Examples thereof include a linear or branched C _2-12 alkylene group such as a pentandiyl group, a 1,6-hexanediyl group, a 1,8-octanediyl group and a 1,10-decandyl group. Preferred alkylene groups ^A5 are linear or branched C _2-10 alkylene groups, C _2-8 alkylene groups, C _2-6 alkylene groups, and C _2-4 alkylene groups in a stepwise manner. A _C2-3 alkylene group such as an ethylene group or a propylene group is more preferable, and an ethylene group is particularly preferable.

The repetition number n5 can be selected from, for example, a range of about 1 to 10, and the preferred range is 1 to 6, 1 to 4, 1 to 2 in stages, and 1 is particularly preferable. The repetition number n5 may be an average value (arithmetic mean value or arithmetic mean value), and the preferred embodiment is the same as the range of the integers. When n5 is 2 or more, the types of 2 or more oxyalkylene groups ( ^—A5O— ) may be different from each other, but are preferably the same.

Examples of the third diol component corresponding to the third diol unit (A3) include alkanediol (or alkylene glycol) and polyalkanediol (or polyalkylene glycol).

As the alkylene glycol, for example, in the above formula ( ³ ), n5 is 1 and A5 is a compound corresponding to the above-exemplified alkylene group, specifically, ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butane. Diol, 1,3-butanediol, tetramethylene glycol (or 1,4-butanediol), 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,10 Examples thereof include linear or branched C _2-12 alkylene glycol such as decanediol, and preferred embodiments are the ^same corresponding to the alkylene group A5.

As the polyalkylene glycol, n5 is 2 or more in the formula (3), for example, about ² to 10, and A5 is a compound corresponding to the above-exemplified alkylene group, specifically, diethylene glycol, dipropylene glycol, or triethylene glycol. Examples thereof include di or deca linear or branched C _2-12 alkylene glycols, preferably di to hexa C _2-6 alkylene glycols, and more preferably di to tetra C _2-4 alkylene glycols. ..

These third diol units (A3) may be contained alone or in combination of two or more. The preferred third diol unit (A3) is alkylene glycol because it is difficult to significantly reduce the refractive index, and more preferably linear or branched _C2 such as ethylene glycol or 1,5-pentanediol. _-6 alkylene glycols, more preferably C _{2-3 alkylene glycols such as ethylene glycol, propylene glycol and 1,4-butanediol, especially C 2-3 alkylene} glycols such as ethylene glycol and propylene glycol, especially ethylene glycol. Derived structural units are preferred.

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), if necessary. May be good.

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 diol components thereof. Examples thereof include structural units derived from the alkylene oxide (alkylene carbonate or haloalkanol) adduct of the above.

Examples of the alicyclic diol include cycloalkane diols such as cyclohexanediol; bis (hydroxyalkyl) cycloalkanes such as cyclohexanedimethanol; hydrogenated products of aromatic diols exemplified after hydrogenated products of bisphenol A and the like. Can be mentioned.

Examples of the aromatic diol include dihydroxyarene 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; p, Examples thereof include biphenols such as p'-biphenol.

Examples of the alkylene oxide (corresponding alkylene carbonate or haloalkanol) adduct of these diol components include _C2-4 alkylene oxide adducts, preferably _C2-3 alkylene oxide adducts such as ethylene oxide adducts and propylene oxide adducts. Examples thereof include an adduct, and the number of adducts is not particularly limited. Specific examples thereof include an adduct in which about 2 to 10 mol of ethylene oxide is added to 1 mol of diol such as bisphenol A.

The diol unit (A) may contain these fourth diol units (A4) alone or in combination of two or more. The ratio of the fourth diol unit (A4) is, for example, 50 mol% or less (0 to 50 mol%), specifically, from the range of about 0.1 to 30 mol% with respect to the entire diol unit (A). It may be selected, and the preferable range is 20 mol% or less, 10 mol% or less, 5 mol% or less in a stepwise manner, and it is preferable that the fourth diol unit (A4) is not substantially contained. ..

(Dicarboxylic acid unit (B))
The resin may or may not contain the dicarboxylic acid unit (B), if necessary. By combining such a dicarboxylic acid unit (B) with a diol unit (A), the polyester resin or polyester carbonate resin can be formed.

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 if necessary. When the first dicarboxylic acid unit (B1) is contained, birefringence can be easily reduced (or adjusted to the minus (−) side) while maintaining a relatively high refractive index.

In the above formula (4), the substituent (non-reactive substituent or non ^- polymerizable substituent) represented by R6 and the number of substitutions m6 thereof are the above-mentioned formula in the section of the second diol unit (A2). The same applies to the substituents and ranges exemplified as ^R4 and m4 in (2), the substitution positions, and the like, including preferred embodiments.

Examples of the linear or branched alkylene group represented by A ^6a and A ^6b include the same group as the alkylene group exemplified as A ¹ in the section of the diol compound represented by the above formula (1). , Preferably C _1-6 alkylene groups such as methylene group, ethylene group, trimethylene group, propylene group, 2-methylpropane-1,3-diyl group, and more preferably C _1-4 alkylene group. A C _2-3 alkylene group is more preferable, and a C _2-3 alkylene group such as an ethylene group and a propylene group is preferable, and an ethylene group is particularly preferable. The types of A ^6a and A ^6b may be different from each other, but are preferably the same.

Examples of the first dicarboxylic acid component for forming the first dicarboxylic acid unit (B1) include 9,9-bis (2-carboxyethyl) fluorene and 9,9-bis (2-carboxypropyl) fluorene. Such as 9,9-bis (carboxyC _2-6 alkyl) fluorene, and ester-forming derivatives thereof can be mentioned. The preferred first dicarboxylic acid unit (B1) is 9,9-bis (carboxyC _2-4 alkyl) fluorene, and more preferably 9,9-bis (2-carboxyethyl) fluorene, 9,9-. It preferably contains a structural unit derived from 9,9-bis (carboxyC _2-3 alkyl) fluorene such as bis (2-carboxypropyl) 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.

Second dicarboxylic acid unit (B2)
The dicarboxylic acid unit (B) does not necessarily have to contain the second dicarboxylic acid unit (B2) represented by the above formula (5), but may contain it if necessary. The inclusion of a second dicarboxylic acid unit (B2) allows birefringence to be adjusted to the plus (+) side (or positive side) while maintaining a relatively high index of refraction and glass transition temperature.

In the formula (5), the arene ring represented by the ring Z ³ includes the same arene ring as the ring Z ¹ described in the section of the diol compound represented by the formula (1). Preferred ring Z ³ is a C _6-12 arene ring such as a benzene ring, a naphthalene ring, or a biphenyl ring, and more preferably a C _6-10 arene ring such as a benzene ring or a naphthalene ring, which improves the refractive index. A naphthalene ring is particularly preferable because it is easy to use.

As the substituent (non-reactive substituent or non-polymerizable substituent) represented by R ⁷ , the substituent exemplified as R ¹ described in the section of the diol compound represented by the above formula (1) is preferable. It is the same including the aspect. When R ⁷ is an aryl group, R ⁷ may form a ring-set arene ring together with ring Z ³ .

The substitution number m7 of R ⁷ can be selected according to the type of ring Z ³ , for example, an integer of about 0 to 6, preferably an integer of 0 to 4, an integer of 0 to 2, and more preferably 0 in a stepwise manner. Or 1, especially 0. When m7 is 2 or more, the types of 2 or more groups ^R7 may be the same or different from each other. Further, the substitution position of the group R ⁷ is not particularly limited, and it may be substituted at a position other than the bond position between the two carbonyl groups [−C (= O) −] and the ring Z ³ .

The substitution position of the two carbonyl groups [-C (= O)-] is not particularly limited. For example, when the ring ^Z3 is a benzene ring, the two carbonyl groups [-C (= O)-] are o. It may be replaced by the positional relationship of the − position, the m-position or the p-position, and it is particularly preferable to replace it by the positional relationship of the m-position or the p-position, particularly the p-position. Further, when the ring Z ³ is a naphthalene ring, the two carbonyl groups [-C (= O)-] are substituted at any position from the 1 to 8 positions, for example, one carbonyl group is replaced with the 1 or 2 position. In many cases, the other carbonyl group is substituted at the 5- to 8-position with respect to the naphthyl group, and it is preferable to substitute the naphthyl group at the 1,5-position or the 2,6-position, particularly at the 2,6-position. When the ring Z ³ is a biphenyl ring, the two carbonyl groups [-C (= O)-] may be substituted in any positional relationship, but it is preferable to replace them with different benzene rings, respectively. It is preferable to replace with the 2,2'-position, 3,3'-position or 4,4'-position, particularly the 2,2'-position or 4,4'-position.

As a typical second dicarboxylic acid component corresponding to the second dicarboxylic acid unit (B2), for example, in the above formula (5), the benzene dicarboxylic acids corresponding to the unit in which the ring ^Z3 is a benzene ring; the ring. Examples include polycyclic allenedicarboxylic acids corresponding to the unit in which Z ³ is a polycyclic allene ring; and ester-forming derivatives thereof.

Examples of the benzenedicarboxylic acid include benzenedicarboxylic acid and alkylbenzenedicarboxylic acid. Examples of the benzenedicarboxylic acid include phthalic acid, isophthalic acid, and terephthalic acid. Examples of the alkylbenzene dicarboxylic acid include C _1-4 alkyl-benzene dicarboxylic acid such as 5-methylisophthalic acid.

Examples of the polycyclic arenedicarboxylic acids include condensed polycyclic arenedicarboxylic acids and ring-assembled arenedicarboxylic acids.

Examples of the fused polycyclic arenedicarboxylic acid include 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid and 2,3-naphthalenedicarboxylic acid. Examples thereof include acid, naphthalenedicarboxylic acid such as 2,6-naphthalenedicarboxylic acid; anthracendicarboxylic acid; condensed polycyclic C _10-24 arene-dicarboxylic acid such as phenanthrange carboxylic acid. A preferred fused polycyclic arene dicarboxylic acid is a condensed polycyclic C _10-14 arene-dicarboxylic acid.

Examples of the ring-aggregated arenedicarboxylic acid include biC _6-10 arene-dicarboxylic acids such as 2,2'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid and 4,4'-biphenyldicarboxylic acid. It is preferably a biphenyldicarboxylic acid.

The second dicarboxylic acid unit (B2) derived from these second dicarboxylic acid components may be used alone or in combination of two or more. Of these second dicarboxylic acid units (B2), units derived from a benzenedicarboxylic acid component such as isophthalic acid and terephthalic acid and a biphenyldicarboxylic acid component such as 2,2'-biphenyldicarboxylic acid may be used. A condensed polycyclic allene dicarboxylic acid component such as a condensed polycyclic C _10-14 allene-dicarboxylic acid is preferable, and a naphthalenedicarboxylic acid, particularly 2,6- A dicarboxylic acid unit derived from a naphthalenedicarboxylic acid is preferable.

Third dicarboxylic acid unit (B3)
The dicarboxylic acid unit (B) may contain, if necessary, a first dicarboxylic acid unit (B1) and a third dicarboxylic acid unit (B3) different from the second dicarboxylic acid unit (B2). Well, it does not have to be included.

Examples of the third dicarboxylic acid unit (B3) include an aliphatic dicarboxylic acid component, an alicyclic dicarboxylic acid component, and an aromatic dicarboxylic acid component [however, the first dicarboxylic acid unit (B1) and the second dicarboxylic acid. Excluding the unit (B2)] and the like.

Examples of the aliphatic dicarboxylic acid component include alcandicarboxylic acids, specifically C _2-12 alkane-dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and decandicarboxylic acid; unsaturated aliphatic dicarboxylic acids, and the like. Specific examples thereof include C _2-10 alkene-dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, and ester-forming derivatives thereof.

Examples of the alicyclic dicarboxylic acid component include cycloalcandicarboxylic acid, specifically C _{5-10 cycloalcan} -dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid; crosslinked cyclic cycloalcandicarboxylic acid, specific. Di or tricycloalkandicarboxylic acids such as _{decalindicarboxylic} acid, norbornandicarboxylic acid, adamantandicarboxylic acid, tricyclodecanedicarboxylic acid; ₁₀ Cycloalkene-dicarboxylic acids and the like; crosslinked cyclic cycloalkhendicarboxylic acids, specifically di or tricycloalkhendicarboxylic acids such as norbornendicarboxylic acids; and ester-forming derivatives thereof and the like.

Examples of the aromatic dicarboxylic acid component include diarylalkanedicarboxylic acid, specifically, _{diC6-10arylC 1-6alcan} -dicarboxylic acid such as 4,4'-diphenylmethanedicarboxylic acid; and diarylketone dicarboxylic acid. Specific examples thereof include di (C _6-10aryl ) ketone-dicarboxylic acids such as 4.4'-diphenylketone dicarboxylic acids; and ester-forming derivatives thereof.

These third dicarboxylic acid units (B3) may be used alone or in combination of two or more. The ratio of the third dicarboxylic acid unit (B3) may be selected from, for example, 50 mol% or less, specifically, about 0 to 30 mol% with respect to the entire dicarboxylic acid unit (B), which is preferable. The range is preferably 20 mol% or less, 10 mol% or less, 5 mol% or less in a stepwise manner, and does not substantially contain the third dicarboxylic acid unit (B3).

(Carbonate unit (C))
The resin may or may not contain the carbonate unit (C), if necessary. By combining such a carbonate unit (C) with a diol unit (A), the polycarbonate resin or polyester carbonate resin can be formed.

The carbonic acid component (or carbonic acid bond forming component) for forming the carbonic acid unit (C) is a compound capable of forming a carbonic acid bond by reacting with a compound having a hydroxyl group (polymerization component) such as the diol component (A). As a typical carbonate component, for example, phosgenes such as phosgene and triphosgene, carbonic acid diesters such as diphenyl carbonate, and the like are mentioned, and carbonic acid diesters such as diphenyl carbonate are preferable from the viewpoint of safety and the like. The carbonate component may be used alone or in combination of two or more.

In the present specification and claims, the "carbonate unit" means a structural unit derived from the carbonate component (carbonate bond forming component), that is, a carbonyl group [-C (= O)-]. .. In other words, this carbonate unit (carbonyl group) is bonded to a structural unit corresponding to the compound having a hydroxyl group (polymerization component), for example, a diol unit (A), and is a terminal in two adjacent structural units. It forms a carbonate bond with an oxygen atom (an oxygen atom derived from a hydroxyl group).

(Other building blocks (D))
The resin does not have to contain another structural unit (D) different from the diol unit (A), the dicarboxylic acid unit (B) and the carbonate unit (C), but the present invention may be used as necessary. It may be included in a range that does not impair the effect of.

Examples of the other structural unit (D) include a structural unit derived from a hydroxyalkanoic acid, a corresponding lactone, a polyfunctional polymerization component having three or more carboxyl groups and / or a hydroxyl group, and the like.

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

The polyfunctional polymerization component includes, for example, trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid, and trihydric or higher polyhydric alcohols such as glycerin and pentaerythritol, in total of 3 or more. Examples thereof include a polyfunctional polymerization component having a carboxyl group and / or a hydroxyl group.

Such other structural units (D) may be contained alone or in combination of two or more. The ratio of the other structural unit (D) is, for example, 50 to the entire structural unit (total amount of the diol unit (A), the dicarboxylic acid unit (B), the carbonate unit (C) and the other structural unit (D)). Mol% or less (0 to 50 mol%), preferably in a stepwise manner, 30 mol% or less, 10 mol% or less, 5 mol% or less, and usually, the other structural unit (D) is substantially used. It is preferable not to include it in. The ratio may be, for example, about 0.01 to 1 mol%.

(Preferable composition in polyester resin)
The resin of the present invention can achieve both high refractive index and high moldability at a high level, and is also excellent in balance with low birefringence, heat resistance, and low Abbe number. The polyester resin described above is preferable.

(1) Polycarbonate Resin The polycarbonate resin of the present invention is formed of a diol unit (A) containing at least the first diol unit (A1) and a constituent unit containing the carbonate unit (C). Further, the polycarbonate resin preferably further contains a second diol unit (A2) as the diol unit (A).

The preferred units in the first diol unit (A1) and the second diol unit (A2) are the same as in the preferred embodiments described in the above items. A particularly preferred combination of structural units forming the polycarbonate resin is 9 such as 9,9-bis (3-hydroxypropyl) -2,7-di (2-naphthyl) fluorene as the first diol unit (A1). , 9-Bis (Hydroxy C _2-4 Alkyl) -Constituent units derived from dinaphthylfluorene; 9,9-Bis [6- (2-Hydroxyethoxy) -2- as the second diol unit (A2) Examples thereof include a combination with a constituent unit derived from 9,9-bis [hydroxy C _2-4 alkoxy-naphthyl] fluorene such as naphthyl] fluorene.

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% with respect to the entire diol unit (A), and the preferred range is as follows. In addition, it is 10 to 90 mol%, 20 to 80 mol%, 30 to 70 mol%, 40 to 60 mol%, and 45 to 55 mol%. Further, from the viewpoint of excellent balance of high formability, high refractive index, low Abbe number and low birefringence, the preferable range of the ratio is as follows, in stages, 50 to 80 mol%, 53 to 70 mol%, 55. It is ~ 65 mol%. 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 becomes large on the negative (minus) side, resulting in birefringence. The absolute value may not be reduced sufficiently.

The ratio of the total amount 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% with respect to the entire diol unit (A), which is preferable. The range is 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 preferable. If the ratio of the total amount is too small, the refractive index and moldability may not be sufficiently improved.

When the second diol unit (A2) is included, the ratio A1 / A2 of the first diol unit (A1) and the second diol unit (A2) is, for example, the former / the latter (molar ratio) = 1/99. It may be selected from the range of about 99/1, and the preferable range is 10/90 to 90/10, 20/80 to 80/20, 30/70 to 70/30, 40 / in the following steps. It is 60 to 60/40 and 45/55 to 55/45. Further, the ratio A1 / A2 is preferably 50/50 to 90/10, 60/40 to 85/15, 70/30 to 80/20 in a stepwise manner. Further, from the viewpoint of excellent balance of high formability, high refractive index, low Abbe number and low birefringence, the preferable range of the ratio A1 / A2 is as follows, in stages, from 50/50 to 80/20, 53 /. It is 47 to 70/30 and 55/45 to 65/35. 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, the moldability may be lowered, and the Abbe number may not be reduced. If the ratio of the second diol unit (A2) is too small, there is a possibility that low birefringence cannot be achieved or the heat resistance is lowered.

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

Further, the ratio of the total amount of the diol unit (A) and the carbonate unit (C) may be selected from the range of, for example, about 50 to 100 mol% with respect to the entire constituent units forming the polycarbonate resin, and is preferable. It is 70 mol% or more, more preferably 90 mol% or more, and substantially 100 mol% is particularly preferable.

(2) Polyester Carbonate Resin The polyester carbonate resin of the present invention contains the diol unit (A) containing at least the first diol unit (A1), the dicarboxylic acid unit (B), and the carbonate unit (C). It is formed by the constituent units including it. The preferred polyester carbonate resin further contains the second diol unit (A2) as the diol unit (A); and the first dicarboxylic acid unit (B1) as the dicarboxylic acid unit (B).

The preferred units in the first and second diol units (A1), (A2), and the first dicarboxylic acid unit (B1) are the same as in the preferred embodiments described in the above items. Particularly preferred combinations of the building blocks that form the polyester carbonate resin include 9,9-bis (3-hydroxypropyl) -2,7-di (2-naphthyl) fluorene as the first diol unit (A1). 9,9-Bis (Hydroxy C _2-4 Alkyl) -Constituent units derived from dinaphthylfluorene; 9,9-Bis [6- (2-Hydroxyethoxy) -2 as the second diol unit (A2) -Constituent units derived from 9,9-bis [hydroxy C _2-4 alkoxy-naphthyl] fluorene such as [naphthyl] fluorene; 9,9-bis (2-carboxyethyl) as the first dicarboxylic acid unit (B1). ) A combination with a constituent unit derived from 9,9-bis (carboxyC _2-4 alkyl) fluorene such as fluorene can be mentioned.

The ratio 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% with respect to the entire diol unit (A), and the preferred range is as follows. In particular, it is 5 to 60 mol%, 10 to 50 mol%, 20 to 45 mol%, and 25 to 40 mol%. 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 becomes large on the negative (minus) side, resulting in birefringence. The absolute value may not be reduced sufficiently.

The ratio of the total amount 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% with respect to the entire diol unit (A), which is preferable. The range is 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 preferable. If the ratio of the total amount is too small, the refractive index and moldability may not be sufficiently improved.

When the second diol unit (A2) is included, the ratio A1 / A2 of the first diol unit (A1) and the second diol unit (A2) is, for example, the former / the latter (molar ratio) = 1/99. It may be selected from the range of about 99/1, and the preferable range is 5/95 to 60/40, 10/90 to 50/50, 20/80 to 45/55, 25 / in the following steps. It is 75 to 40/60. 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, the moldability may be lowered, and the Abbe number may not be reduced. If the ratio of the second diol unit (A2) is too small, it may not be possible to reduce the birefringence, the heat resistance may be lowered, or the molecular weight may not be sufficiently improved.

When the first dicarboxylic acid unit (B1) is included, the ratio of the first dicarboxylic acid unit (B1) is selected from the range of, for example, about 1 to 100 mol% with respect to the entire dicarboxylic acid unit (B). Also, the preferred range is, in stages, 10 to 100 mol%, 30 to 100 mol%, 50 to 100 mol%, 70 to 100 mol%, 90 to 100 mol%, and substantially 100 mol. % Is preferable. If the proportion of the first dicarboxylic acid unit (B1) is too small, it may not be possible to achieve sufficiently low birefringence.

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

Further, the ratio of the dicarboxylic acid unit (B) may be selected from the range of, for example, about 0.01 to 0.99 mol with respect to 1 mol of the diol unit (A), and the preferable range is as follows in stages. In addition, it is 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. If the proportion of the dicarboxylic acid unit (B) is too large or too small, the characteristics such as high refractive index, high moldability, low birefringence, low Abbe number, and heat resistance may not be satisfied in a well-balanced manner. Further, if the proportion of the dicarboxylic acid unit (B) is too large, the strength (or hardness) may decrease and the injection moldability may decrease, and if it is too small, the flexibility (or toughness) decreases and the film formability deteriorates. It may decrease.

The ratio of the total amount of the diol unit (A), the dicarboxylic acid unit (B) and the carbonate unit (C) ranges from, for example, about 50 to 100 mol% with respect to the entire constituent units forming the polyester carbonate resin. It may be selected, preferably 70 mol% or more, more preferably 90 mol% or more, and substantially 100 mol% is particularly preferable.

(3) Polyester Resin The polyester resin of the present invention is formed of a diol unit (A) containing at least the first diol unit (A1) and a constituent unit containing the dicarboxylic acid unit (B). The 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 preferable polyester resin further contains the second dicarboxylic acid unit (B2) in addition to the units (A1), (A3) and (B1).

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 in the preferred embodiments described in the above items, respectively. be. A more preferable combination of the constituent units forming the polyester resin is 9 such as 9,9-bis (3-hydroxypropyl) -2,7-di (2-naphthyl) fluorene as the first diol unit (A1). , 9-Bis (hydroxy C _2-4 alkyl) -constituent units derived from dinaphthylfluorene; and structural units derived from C _2-4 alkylene glycols such as ethylene glycol as the third diol unit (A3); It is a combination with a constituent unit derived from 9,9-bis (carboxyC _2-4 alkyl) fluorene such as 9,9-bis (2-carboxyethyl) fluorene as the first dicarboxylic acid unit (B1). As a particularly preferable combination, a combination containing a structural unit derived from a naphthalenedicarboxylic acid such as 2,6-naphthalenedicarboxylic acid as a second dicarboxylic acid unit (B2) can be mentioned as a further preferable combination.

When the diol unit (A) contains the diol unit (A2), the diol unit (A2) is preferably the structural unit (A2) in which Z ^2a and Z ^2b are naphthalene rings in the above formula (2). Building blocks derived from 9,9-bis [hydroxy C _2-4 alkoxy-naphthyl] fluorene, such as 9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene, are particularly preferred. When the diol unit (A) contains the diol unit (A2), a more preferable combination of the constituent units forming the polyester resin is 9,9-bis (3-hydroxypropyl) as the first diol unit (A1). 9,9-Bis (hydroxy C _2-4 alkyl) -dinaphthylfluorene-derived constituent units such as -2,7-di (2-naphthyl) fluorene; 9, as a second diol unit (A2), 9-Bis [Hydroxy C _2-4 alkoxy-naphthyl] Fluorene-derived structural units; and C _2-4 alkylene glycol-derived structural units such as ethylene glycol as the third diol unit (A3); It is a combination with a constituent unit derived from 9,9-bis (carboxyC _2-4 alkyl) fluorene such as 9,9-bis (2-carboxyethyl) fluorene as the dicarboxylic acid unit (B1). As a particularly preferable combination, a combination containing a structural unit derived from a naphthalenedicarboxylic acid such as 2,6-naphthalenedicarboxylic acid as a second dicarboxylic acid unit (B2) can be mentioned as a further preferable combination.

The ratio of the first diol unit (A1) in the polyester resin may be selected from the range of, for example, about 1 to 100 mol% with respect to the entire diol unit (A), and the preferred range is as follows. In addition, it is 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%. 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 becomes large on the negative (minus) side, resulting in birefringence. The absolute value may not be reduced sufficiently.

When the diol unit (A) contains a diol unit (A1) and a diol unit (A3), the ratio of the total amount of the first diol unit (A1) and the third diol unit (A3) is the entire diol unit (A). On the other hand, for example, it may be selected from the range of about 1 to 100 mol%, and the preferable range is as follows, in stages, 10 mol% or more, 30 mol% or more, 50 mol% or more, 70 mol% or more, It is 90 mol% or more, preferably 100 mol%. If the ratio of the total amount is too small, the refractive index and moldability may not be sufficiently improved.

When the diol unit (A) includes a diol unit (A1), a diol unit (A2) and a diol unit (A3), the first diol unit (A1), the second diol unit (A2) and the third diol unit The ratio of the total amount of (A3) may be selected from the range of, for example, about 1 to 100 mol% with respect to the entire diol unit (A). It is 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, and substantially 100 mol% is preferable. If the ratio of the total amount is too small, the refractive index and moldability may not be sufficiently improved.

When the third diol unit (A3) is included, the ratio A1 / A3 of the first diol unit (A1) and the third diol unit (A3) is, for example, the former / the latter (molar ratio) = 1/99. It may be selected from the range of about 99.9 / 0.1, and the preferable range is 50/50 to 99/1, 60/40 to 97/3, 70/30 to 95 / in the following steps. 5, 75/25 to 92/8, 80/20 to 90/10. 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, the moldability may be lowered, and the Abbe number may not be reduced. If the proportion of the third diol unit (A3) is too small, the molecular weight cannot be sufficiently improved and the moldability may be deteriorated.

When the second diol unit (A2) [in particular, the structural unit (A2) in which Z ^2a and Z ^2b are naphthalene rings in the above formula (2)] is contained, the first diol unit (A1) and the second diol unit (A1) are included. The ratio A1 / A2 to the diol unit (A2) may be selected from the range of, for example, the former / the latter (molar ratio) = 1/99 to 99.9 / 0.1, and the preferred range is as follows. In stages, it is 1/99 to 70/30, 3/97 to 50/50, 5/95 to 40/60, and 10/90 to 30/70. If the ratio of the first diol unit (A1) is too small, 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 small, the birefringence cannot be lowered, the molecular weight cannot be sufficiently improved, and the moldability may be deteriorated.

The ratio of the total amount 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% with respect to the entire dicarboxylic acid unit (B). The preferred range is preferably 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 preferable. If the ratio of the total amount is too small, the characteristics such as high refractive index, high formability, low birefringence, low Abbe number, and heat resistance may not be satisfied in a well-balanced manner.

When the first dicarboxylic acid unit (B1) is included, the ratio of the first dicarboxylic acid unit (B1) is selected from the range of, for example, about 1 to 100 mol% with respect to the entire dicarboxylic acid unit (B). Also, the preferred range is 50 to 100 mol%, 60 to 95 mol%, 70 to 90 mol%, 75 to 85 mol% in a stepwise manner. Further, from the viewpoint of excellent balance of high formability, high refractive index, low Abbe number and low birefringence, the preferable range of the ratio is as follows, 40 to 100 mol%, 50 to 90 mol%, 60 in stages. ~ 80 mol%. If the proportion of the first dicarboxylic acid unit (B1) is too small, it may not be possible to achieve sufficiently low birefringence.

When the second dicarboxylic acid unit (B2) is included, the ratio of the second dicarboxylic acid unit (B2) is selected from the range of, for example, about 1 to 100 mol% with respect to the entire dicarboxylic acid unit (B). Also, the preferred range is 3 to 90 mol%, 5 to 70 mol%, 10 to 50 mol%, and 20 to 40 mol% in a stepwise manner.

When both the first and second dicarboxylic acid units (B1) and (B2) are included, the ratio B1 / B2 of the first dicarboxylic acid unit (B1) and the second dicarboxylic acid unit (B2) is, for example, , The former / the latter (molar ratio) = may be selected from the range of about 1/99 to 99/1, and the preferred range is 50/50 to 99/1 and 60/40 to 95 / in the following steps. 5, 70/30 to 90/10, 75/25 to 85/15. Further, from the viewpoint of excellent balance of high formability, high refractive index, low Abbe number and low birefringence, the preferable range of the ratio B1 / B2 is set in the following steps from 40/60 to 95/5, 50 /. It is 50 to 90/10 and 60/40 to 80/20. If the proportion of the first dicarboxylic acid unit (B1) is too small, it may not be possible to achieve sufficiently low birefringence. If the proportion of the second dicarboxylic acid unit (B2) is too small, the refractive index, Abbe number, and heat resistance may decrease, and it may not be possible to achieve sufficiently low birefringence.

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

The ratio of the diol unit (A) and the dicarboxylic acid unit (B) in the polyester resin is the former / the latter (molar ratio) = 1 / 0.8 to 1 / 1.2, preferably 1 / 0. It is 9 to 1 / 1.1, more preferably almost equimolar.

Further, the ratio of the total amount of the diol unit (A) and the dicarboxylic acid unit (B) may be selected from the range of, for example, about 50 to 100 mol% with respect to the entire constituent units forming the polyester resin, and is preferable. It is 70 mol% or more, more preferably 90 mol% or more, and substantially 100 mol% is particularly preferable.

[Resin manufacturing method]
The method for producing the resin is not particularly limited except that the diol component (A) containing the first diol component (A1) is used, depending on the type of resin or other polymerization component (copolymerization component). Conventional methods are available. For example, in the case of a polyester resin, a polymerization containing the diol component (A) corresponding to each of the above-mentioned diol units and the dicarboxylic acid component (B) and / or the carbonate component (C) corresponding to each of the above-mentioned dicarboxylic acid units. It may be produced by reacting the components.

Specifically, when the carbonate unit (C) is contained, particularly when the resin is a polycarbonate resin, for example, by the phosgene method (solvent method) or the transesterification method (melting method), the diol component (A) and the carbonate component ( C) is reacted (polymerized or condensed). Of these methods, the transesterification method is preferable because it does not require a solvent.

In the transesterification method, the ratio of the carbonic acid diester is, for example, 0.8 to 1.5 mol, preferably 0.9 to 1.2 mol, with respect to 1 mol of the diol component.

The transesterification reaction may be carried out in the presence of a catalyst. Examples of the catalyst include various catalysts used in the transesterification reaction, for example, nitrogen-containing compounds and metal compounds.

Examples of the nitrogen-containing compound include quaternary ammonium hydroxides (eg, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide; and trialkyls such as trimethylbenzylammonium hydroxide. -Aralkylammonium hydroxide and the like); Tertiary amines (trialkylamines such as trimethylamine and triethylamine; dimethyl-aralkylamines such as dimethylbenzylamine; triarylamines such as triphenylamine) and the like.

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

These catalysts can be used alone or in combination of two or more. Among these catalysts, nitrogen-containing compounds such as quaternary ammonium hydroxide are preferable, and among them, tetraalkylammonium hydroxide such as tetramethylammonium hydroxide is preferable. The amount of the catalyst used is, for example, 0.01 × 10 ^-4 to 100 × 10 ^-4 mol, preferably 0.1 × 10 ^-4 to 40 × 10 ^-4 mol, per 1 mol of the diol component.

Further, the reaction may be carried out in the presence of an additive, for example, a stabilizer such as an antioxidant or a heat stabilizer, if necessary.

The reaction can be carried out in an atmosphere of an inert gas such as nitrogen gas; a rare gas such as helium or argon. The reaction can also be carried out under reduced pressure, for example, at about 1 × 10 ² to 1 × 10 ⁴ Pa. The reaction temperature can be selected according to the polymerization method. 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 carbonic acid diester, it is effective to carry out polycondensation while distilling off phenol under high temperature and reduced pressure.

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 is prepared by, for example, a melt polymerization method such as a transesterification method or a direct polymerization method, a solution polymerization method, or a surface polymerization method. The melt polymerization method is preferable. The reaction may be carried out in the presence or absence of a solvent, depending on the polymerization method.

The usage ratio (or charging ratio) of the diol component (A) and the dicarboxylic acid component (B) is the former / the latter (molar ratio) = for example, 1 / 1.2 to 1 / 0.8, preferably 1/1. It is 1 to 1 / 0.9, but it is not always in this range, and at least one component selected from the diol component (A) and the dicarboxylic acid component (B) is added to the planned introduction ratio. It may be reacted by using it excessively. For example, the third diol component (A3) such as ethylene glycol that can be distilled off from the reaction system may be used in excess of the ratio (or introduction ratio) introduced into the resin. 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) is, for example, the former / the latter (molar ratio) = 1 /. It is 1.2 to 1 / 0.8, preferably 1 / 1.1 to 1 / 0.9. The carbonate component (C) may be used in a slightly excessive amount with respect to the planned introduction ratio in consideration of volatilization and decomposition in the reaction, and the total amount of the dicarboxylic acid unit (B) and the carbonate unit (C) (resin). The carbonate component (C) may be used in an excess of, for example, 0.1 to 5 mol%, preferably 2 to 3 mol% with respect to the total amount to be introduced into the mixture.

The reaction may be carried out in the presence of a catalyst. As the catalyst, a conventional esterification catalyst, for example, a metal catalyst or the like can be used. Examples of the metal catalyst include alkali metals such as sodium; alkaline earth metals such as magnesium, calcium and barium; transition metals such as titanium, manganese and cobalt; periodic table group 12 metals such as zinc and cadmium; aluminum and the like. A metal compound containing a metal of Group 13 of the periodic table; a metal of Group 14 of the periodic table such as germanium and lead; a metal of Group 15 of the periodic table such as antimony is used. The metal compound may be, for example, an alkoxide; an organic acid salt such as an acetate or a propionate; an inorganic acid salt such as a borate or a carbonate; an oxide or the like, and is a hydrate thereof. May be good. Typical metal compounds include, for example, germanium compounds such as germanium dioxide, germanium hydroxide, germanium oxalate, germanium tetraethoxydo, germanium-n-butoxide; antimonates such as antimony trioxide, antimonate acetate, and antimonate ethylene glycolate. Compounds; Titanium compounds such as tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate (titanium (IV) tetrabutoxide), titanium oxalate, potassium titanium oxalate; manganese acetate, tetrahydrate, etc. Manganese compounds; calcium compounds such as calcium acetate and monohydrate can be mentioned.

These catalysts can be used alone or in combination of two or more. When a plurality of catalysts are used, 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 and the like are preferable. The amount of the catalyst used is, for example, 0.01 × 10 ^-4 to 100 × 10 ^-4 mol, preferably 0.1 × 10 ^-4 to 40 × 10 ^-4 per 1 mol of the dicarboxylic acid component (A). It is a mole.

Further, the reaction may be carried out in the presence of a stabilizer such as a heat stabilizer or an antioxidant, if necessary. Usually, heat stabilizers are often used, for example, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dibutyl phosphate (dibutyl phosphate or dibutyl phosphate), phosphite, trimethyl phosphite, phosphorus compounds such as triethyl phosphite, etc. Can be mentioned. Of these, dibutyl phosphate is often used. The amount of the heat stabilizer used is, for example, 0.01 × 10 ^-4 to 100 × 10 ^-4 mol, preferably 0.1 × 10 ^-4 to 40 × 10 per 1 mol of the dicarboxylic acid component (A). ^-4 mol.

The reaction is usually carried out in an atmosphere of an inert gas such as a nitrogen gas; a rare gas such as helium or argon. The reaction can also be carried out under reduced pressure, for example, at about 1 × 10 ² to 1 × 10 ⁴ Pa. Usually, the transesterification reaction is often carried out in an atmosphere of an inert gas such as nitrogen gas, and the polycondensation reaction is often carried out under reduced pressure. The reaction temperature can be selected depending on the polymerization method. 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.

[Characteristics of resin]
Since the resin of the present invention contains the first diol unit (A1), it has a high refractive index and high moldability. Further, in addition to the above-mentioned characteristics, characteristics such as low birefringence, low Abbe number, and high heat resistance can be satisfied at a high level in a well-balanced manner.

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 130 to 170 ° C.

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 165 to 170 ° C.

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 155 to 165 ° C.

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

If the Tg is too high, it is necessary to perform molding processing such as injection molding at a high temperature, which not only lowers the moldability (fluidity or productivity), but also causes the molding temperature to rise, resulting in a molded product. Deterioration and coloring may occur, and a special cooling mold may be required to suppress strain in the molded product and prevent deterioration of surface smoothness. On the other hand, if the Tg is too low, the heat resistance is lowered, and there is a possibility that deterioration or discoloration (or coloring) is likely to occur during molding and / or use, and the obtained molded product may be deformed in a high temperature environment. It may not be usable in applications that require high heat resistance (or thermal stability) such as in-vehicle optical lenses. However, the resin of the present invention has an excellent balance between moldability and heat resistance as described in the section of the first diol unit (A1), and can be easily adjusted within the range of Tg.

Further, if the formability is prioritized, the refractive index often decreases, but in the present invention, both high formability and high refractive index can be achieved in a well-balanced manner. 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, and more preferably 1.69 to 1. It is .72, especially 1.7 to 1.71. Further, the 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 for high refractive index applications.

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. The nD of the polycarbonate resin is preferably 1.7 to 1.74, more preferably 1.705 to 1.73, and particularly 1.71 to 1.72 for high refractive index applications.

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. ..

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.

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 even more preferably 12.5 to 16.

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 13 to 14.

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.

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 12.5 to 13.

The resin of the present invention exhibiting such a low Abbe number is also effective for applications requiring a lower Abbe number, for example, an optical member in various cameras, specifically, a camera lens used in combination with a concave lens and a convex lens. Can be used for. In the optical system of various cameras, in order to reduce (or cancel) chromatic aberration (bleeding) caused by a convex lens by using a concave lens having a low Abbe number, it is usually composed of a combination of a plurality of concave lenses and a convex lens. The resin can sufficiently cope with the low Abbe number required for the concave lens.

Further, since the resin of the present invention contains the first diol unit (A1), birefringence can be efficiently reduced. Birefringence of a resin is a birefringence of a stretched film obtained by uniaxially stretching a film formed of a resin alone at a stretching temperature: glass transition temperature Tg + 10 ° C., stretching speed: 25 mm / min, stretching ratio: 3 times. ) May be evaluated. The absolute value of the triple-stretched birefringence of the stretched film can be selected from a range of, for example, 100 × 10 ^-4 or less at a measurement temperature of 20 ° C. ^and a wavelength of 600 nm. It is ⁴ or less, 50 × 10 ^-4 or less, 25 × 10 ^-4 or less, 20 × 10 ^-4 or less, 10 × 10 ^-4 or less, and more preferably 0 to 5 × 10 ^-4 .

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. It is preferably 35,000 to 50,000. If the weight average molecular weight Mw is too low, the moldability (productivity) and heat resistance may decrease. However, in the present invention, even if the weight average molecular weight Mw is low, the moldability is excellent, and the polyester resin is particularly excellent.

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

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

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

In the present specification and claims, the glass transition temperature Tg, the refractive index nD, the Abbe number, the triple-stretched double refraction, and the weight average molecular weight Mw can be measured by the methods described in Examples described later.

[Molded product]
The molded body 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, and a balance of various properties such as high moldability and high heat resistance. Therefore, it can be used as an optical member such as an optical film (or an optical sheet) or an optical lens. Such moldings may contain conventional additives. Additives include, for example, fillers or reinforcing agents, colorants such as dyes, conductive agents, flame retardants, plasticizers, lubricants, mold release agents, antistatic agents, dispersants, flow regulators, leveling agents, and defoamers. It may contain a foaming agent, a surface modifier, a hydrolysis inhibitor, a carbon material, a stabilizer, a low stress agent and the like. Examples of the stabilizer include an antioxidant, an ultraviolet absorber, a heat stabilizer and the like. Examples of the low stress agent include silicone oil, silicone rubber, various plastic powders, and various engineering plastic powders. These additives may be used alone or in combination of two or more.

The molded body can be manufactured by using, for example, an injection molding method, an injection compression molding method, an extrusion molding method, a transfer molding method, a blow molding method, a pressure molding method, a casting molding method, or the like.

The shape of the molded body is not particularly limited, and is, for example, a one-dimensional structure such as linear, fibrous (or fibrous), or thread-like, a two-dimensional structure such as film-like, sheet-like, or plate-like, or concave. Alternatively, a three-dimensional structure such as a convex lens shape, a rod shape, or a hollow shape (tubular) can be mentioned.

In particular, the resin of the present invention is excellent in various optical properties and is therefore useful for forming an optical film. Therefore, the present invention also includes a film (optical film or optical sheet) formed of the resin.

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.

Such a film (optical film) is produced by forming (or molding) the resin by using a conventional film forming method, for example, a casting method (solvent casting method), a melt extrusion method, a calendar method, or the like. can.

The film may be a stretched film. The film of the present invention can maintain low birefringence even if it is a stretched film. In addition, such a stretched film may be either a uniaxially stretched film or a biaxially stretched film.

The draw ratio is, for example, 1.1 to 10 times, preferably 1.2 to 5 times, and more preferably 1.5 to 3 times in each direction in uniaxial stretching or biaxial stretching. In the case of biaxial stretching, iso-stretching, for example, stretching of about 1.5 to 5 times in both the vertical and horizontal directions may be performed, and partial stretching, for example, about 1.1 to 4 times in the vertical direction and horizontal direction. It may be stretched about 2 to 6 times. Further, in the case of uniaxial stretching, longitudinal stretching, for example, stretching of about 2.5 to 8 times in the longitudinal direction may be performed, and lateral stretching, for example, stretching of about 1.2 to 5 times in the transverse direction. May be good.

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.

In addition, such a stretched film can be obtained by subjecting a film (or an unstretched film) after film formation to a stretching treatment. 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, a tenter method (flat method) or a tube method may be used. However, the tenter method, which is excellent in the uniformity of the stretched thickness, is preferable.

Further, the molded body may be bonded or adhered to another base material, and the type and material of the base material are not particularly limited. For example, a one-dimensional shape formed of a resin material, a ceramic material, a metal material, or the like. , It may be a base material having a two-dimensional shape or a three-dimensional shape. For example, when the molded body is in the form of a film, it may be combined with a base material having a two-dimensional shape such as a film to form a laminated body or a laminated film.

Typical examples of the two-dimensionally shaped substrate include a ceramic substrate such as a glass substrate, a resin film, and the like, and a transparent substrate is preferable. Examples of the resin forming the resin film include polyolefin resins such as chain olefin resins and cyclic olefin resins (or cycloolefin resins); (meth) acrylic resins; styrene resins; polyalkylene allylate resins. , Polyarylate resin, polyester resin such as polycarbonate resin; polyamide resin and the like, and among them, a resin film formed of cycloolefin resin, polyamide resin and the like may be used in combination.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The details of the evaluation method are shown below.

[Evaluation methods]
(HPLC)
The HPLC purity [area%] of the sample was calculated by high performance (or high performance) liquid chromatography (HPLC) based on the following measuring devices and conditions.

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

(FD-MS)
Mass spectrometry (MS) was performed based on the following measuring devices and conditions.

Equipment used: "JMS-T200GC" manufactured by JEOL Ltd.
Ionization method: FD (electric field desorption)
Emitter: Carbon Emitter current: 0 to 50 mA (25 mA / min).

(Melting point)
Measurement was performed using a differential scanning calorimeter (“EXSTAR DSC6200” manufactured by SI Nanotechnology Co., Ltd.) under a nitrogen atmosphere, a measurement temperature of 30 to 220 ° C., and a temperature rise rate of 10 ° C./min. From the obtained DSC chart (DSC curve), the temperature of the peak top of the endothermic peak due to melting was determined as the melting point.

(5% mass loss temperature)
Thermogravimetric analysis-using a differential thermal analyzer (TG-DTA) (“TG / DTA6200” manufactured by SI Nanotechnology Co., Ltd.) under a nitrogen atmosphere and a heating rate of 10 ° C./min. The temperature at which the mass of the sample was reduced by 5% by mass was measured.

( ^{1 1} H-NMR)
The sample is dissolved in a deuterated solvent (CDCl ₃ or DMSO-d ₆ ) containing tetramethylsilane as an internal standard substance, and ¹ H-NMR spectrum is used using a nuclear magnetic resonance apparatus (“AVANCE III HD” manufactured by BRUKER). Was measured.

Further, in the example in which the resin (polymer) was prepared, the integrated value of the peak derived from each monomer used for the polymerization was obtained from the obtained spectrum, and the ratio of each monomer component (constituent unit) introduced into the resin was obtained. (Polymer composition ratio) was calculated.

(Glass transition temperature Tg)
Measurement was performed using a differential scanning calorimeter (“EXSTAR6000 DSC6220 ASD-2” manufactured by SI Nanotechnology Co., Ltd.) at a heating rate of 10 ° C./min under a nitrogen gas atmosphere.

(Molecular weight)
The sample was dissolved in chloroform, and gel permeation chromatography (“HLC-8320GPC” manufactured by Tosoh Corporation) was used to determine the weight average molecular weight Mw in terms of standard polystyrene.

(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 using a refractive index meter (DR-M2 (circulating constant temperature water tank 60-C3) manufactured by Atago Co., Ltd.). Measured by D line). To calculate the refractive index, the sample was dissolved in dimethyl sulfoxide to prepare a solution having a concentration of 6.05% by mass, 10.94% by mass, and 30.30% by mass, and the refractive index of the obtained solution was measured. The concentration was extrapolated to 100% by mass in the calibration curve (approximate straight line) prepared by the above.

The refractive index of the resin sample was measured as follows. By hot pressing the sample at 200 to 240 ° C., a film having a thickness of 200 to 300 μm was formed. This film was cut into strips having a length of 20 to 30 mm and a width of 10 mm to obtain test pieces. Diiodomethane was used as the contact liquid for the obtained test piece using a multi-wavelength Abbe refractometer (“DR-M4 (circulating constant temperature water tank 60-C3)” manufactured by Atago Co., Ltd.) at a measurement temperature of 20 ° C. The refractive index nD of 589 nm (D line) was measured.

(Abbe number)
Using a test piece measuring the refractive index nD of 589 nm (D line), the refractive index nF, nC is the same as the refractive index nD except that the measurement wavelength is changed to 486 nm (F line) and 656 nm (C line). Were measured respectively. From the obtained refractive indexes nF, nD and nC at each wavelength, the Abbe number was calculated by the following formula.

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

(Birerefringence (3x stretched birefringence))
By hot pressing the sample at 200 to 240 ° C., a film having a thickness of 200 to 600 μm was formed. This film is cut into strips of 10 mm in width and 50 mm in length, and uniaxially stretched in the vertical direction so that the stretching ratio becomes 3 times at 25 mm / min under the temperature condition of the glass transition temperature Tg + 10 ° C. And obtained a test piece. The obtained test piece was subjected to a parallel Nicol rotation method under the conditions of a measurement temperature of 20 ° C. and a measurement wavelength of 600 nm using a retardation film / optical material inspection device (“RETS-100” manufactured by Otsuka Electronics Co., Ltd.). The retardation was measured and the value was divided by the thickness of the measurement site to calculate birefringence (or triple stretched birefringence).

[Resin raw material]
(Glycol component)
DNFPO: 2,7-di (2-naphthyl) -9,9-full orange fluorene [or 2,7-di (2-naphthyl) -9,9-bis (3-hydroxypropyl) fluorene], which will be described later. Synthesized according to Example 1 BNEF: 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene, synthesized according to Synthesis Example 1 described in JP-A-2018-59074 BPEF: 9,9-Bis [4- (2-Hydroxyethoxy) phenyl] fluorene, manufactured by Osaka Gas Chemical Co., Ltd. BINOL-2EO: 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthyl, special Synthesized according to Synthesis Example 2 described in Kai 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], in Example 1 described in JP-A-2005-89422. , Synthesized in the same manner 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.

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

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

^{1 1} H-NMR (CDCl ₃ , 300 MHz): 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)

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

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

(Preparation of DNFPO)
Under 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 mixture was cooled to 10 ° C. or lower in an ice water bath. Sodium borohydride (230 g, 6.08 mol) was added little by little over 13 minutes to the obtained solution, and then boron trifluoride ether complex (856 g, 6.09 mol) was added dropwise over 45 minutes. The temperature was raised to room temperature, and the mixture was stirred for 4 hours. The mixture was cooled in an ice-water bath, then acetone (1.0 kg, 17.2 mol) was added dropwise over 1 hour, and then the solvent was removed by concentration under reduced pressure. 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. Further, the operation of adding 4.0 kg of ion-exchanged water to remove the aqueous layer was performed twice (washed twice with ion-exchanged water), and only the organic layer was taken out. The obtained DNFPO represented by the following formula by concentration under reduced pressure, that is, 1.0 kg (white solid, yield 92) of 2,7-di (2-naphthyl) -9,9- (3-hydroxypropyl) fluorene. .1%, HPLC purity 99 area%) was obtained. ¹ The results of 1 H-NMR and FD-MS are shown below.

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

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

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

[Polycarbonate resin]
[Example 2]
Add 0.50 mol of DNFPO and 0.50 mol of BPEF as a diol component, 1.05 mol of DPC as a carbonate component (carbonate bond forming component), and 2 × 10 ^-4 mol of tetramethylammonium hydroxide as a transesterification catalyst, and nitrogen gas. In an atmosphere, the mixture was gradually heated and melted while stirring, the temperature was raised to 250 ° C., and the pressure was gradually reduced to 10,000 Pa. Phenol was removed by gradually raising the temperature and reducing the pressure until the temperature reached 270 ° C. and 130 Pa or less. After reaching the predetermined stirring torque, the contents were taken out from the reactor to obtain a polycarbonate resin. 50 mol% of the diol unit constituting the obtained polycarbonate resin was derived from DNFPO, and 50 mol% was derived from BPEF.

[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 component and 1.05 mol of DPC was used as the carbonate component. 30 mol% of the diol unit constituting the obtained polycarbonate resin was derived from DNFPO, and 70 mol% was derived from BPEF.

[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 unit constituting the obtained polycarbonate resin was derived from BPEF.

[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 component and 1.05 mol of DPC was used as the carbonate component. 50 mol% of the diol unit constituting the obtained polycarbonate resin was derived from DNFPO, and 50 mol% was derived from BNEF.

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

[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 unit constituting the obtained polycarbonate resin was derived from BNEF.

Table 1 shows the charging ratios of Examples and Comparative Examples in which the polycarbonate resin was prepared, and Table 2 shows the evaluation results.

As is clear from Table 2, the polycarbonate resin obtained in Examples can greatly improve the refractive index without excessively increasing Tg as compared with the corresponding Comparative Example, and achieves both high moldability and refractive index. did it. It should be noted that even if the refractive index increases by about 0.01, it is judged to have an advantage, so that it can be said to be a remarkable effect. Further, in the examples, the Abbe number could be significantly reduced and the absolute value of the triple-stretched birefringence could be reduced or kept low as compared with the comparative example. Among them, in Examples 4 to 5, especially in Example 5, high formability, high refractive index, low Abbe number, and low birefringence could be satisfied in a well-balanced manner at a higher level.

[Polyester carbonate resin]
[Example 6]
DNFPO 0.30 mol and BNEF 0.30 mol as the diol component, DPC 0.21 mol as the carbonate component, FDP-m 0.40 mol as the dicarboxylic acid component, and titanium (IV) as a catalyst for the transesterification reaction and the polycondensation reaction. Tetrabutoxide (2.7 mg (8 μmol)) was charged, heated and stirred at 210 ° C. for 1 hour under a nitrogen gas atmosphere, and then gradually heated and stirred up to 240 ° C. to carry out a transesterification reaction. After removing the alcohol component and the phenol component 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 completion of the reaction, the contents were taken out from the reactor to obtain a polyester carbonate resin. 50 mol% of the diol unit constituting the obtained polyester carbonate resin is derived from DNFPO, 50 mol% is derived from BNEF, 33 mol% of the carbonate unit and the dicarboxylic acid unit constituting the resin are derived from DPC, and 67 mol% is FDP-m. It was the origin.

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

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

Table 3 shows the charging ratios of Examples and Comparative Examples in which the polyester carbonate resin was prepared, and Table 4 shows the evaluation results.

As is clear from Table 4, the polyester carbonate resin obtained in the examples can greatly improve the refractive index without excessively increasing Tg as compared with the corresponding comparative examples, and has high moldability and a refractive index. I was able to achieve both. Further, in the examples, the Abbe number could be significantly reduced and the absolute value of the triple-stretched birefringence could be reduced as compared with the comparative example. In particular, in Example 7, high formability, high refractive index, low Abbe number, and low birefringence could be satisfied at a higher level in a well-balanced manner.

[Polyester resin]
[Example 8]
DNFPO 0.75 mol and EG 2.25 mol as the diol component, FDP-m 1 mol as the dicarboxylic acid component, and titanium (IV) tetrabutoxide (1.4 mg (4 μmol)) as a catalyst for the transesterification reaction and the polycondensation reaction. Dibutylphosphate (8.4 mg (40 μmol)) was charged as a heat stabilizer, 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 generated 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 while removing the EG until a predetermined stirring torque was reached. After completion of the reaction, the contents were taken out from the reactor to obtain a polyester resin. 75 mol% of the diol unit constituting the obtained polyester resin was derived from DNFPO, 25 mol% was derived from EG, and 100 mol% of the dicarboxylic acid unit constituting the resin was derived from FDP-m.

[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 component and 1 mol of FDP-m was used as the dicarboxylic acid component. 75 mol% of the diol unit constituting the obtained polyester resin was derived from BNEF, 25 mol% was derived from EG, and 100 mol% of the dicarboxylic acid unit constituting the resin was derived from FDP-m.

[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 component and 1 mol of DMN was used as the dicarboxylic acid component. 80 mol% of the diol unit constituting the obtained polyester resin was derived from BNEF, 20 mol% was derived from EG, and 100 mol% of the dicarboxylic acid unit constituting the resin was derived from DMN.

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

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

[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 component and 1 mol of DMT was used as the dicarboxylic acid component. 70 mol% of the diol unit constituting the obtained polyester resin was derived from DNFPO, 30 mol% was derived from EG, and 100 mol% of the dicarboxylic acid unit constituting the resin was derived from DMT.

[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 component and 1 mol of DMT was used as the dicarboxylic acid component. 70 mol% of the diol unit constituting the obtained polyester resin was derived from BPEF, 30 mol% was derived from EG, and 100 mol% of the dicarboxylic acid unit constituting the resin was derived from DMT.

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

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

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

Table 5 shows the charging ratios of the examples and comparative examples in which the polyester resin was prepared, and Table 6 shows the evaluation results.

As is clear from Table 6, the polyester resin obtained in the examples can greatly improve the refractive index without excessively increasing Tg as compared with the corresponding comparative example, and achieves both high moldability and a refractive index. did it. Further, in the examples, the Abbe number could be significantly reduced and the absolute value of the triple-stretched birefringence could be reduced or kept low as compared with the comparative example. In particular, in Example 9, high formability, high refractive index, low Abbe number, and low birefringence could be satisfied at a higher level in a well-balanced manner.

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

Further, the polyester resin of the example is easier to handle, probably because it has better mechanical properties such as flexibility (toughness) than the polycarbonate resin and the polyester carbonate resin, and the polycarbonate resin is also formed into a lens, a film, or the like. The moldability (or productivity) was particularly high as compared with the polyester carbonate resin and the polyester carbonate resin.

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 high refractive index and high moldability. Therefore, the resin obtained from the diol compound of the present invention can be used for various purposes by taking advantage of the above-mentioned characteristics, for example, a coating agent or a coating film, specifically, a paint, an ink, an electronic device, a liquid crystal member, or the like. Protective film, etc .; Adhesives, Adhesives; Resin fillers; Electrical / electronic materials or electrical / electronic parts (electrical / electronic equipment), specifically, antistatic agents, carrier transport agents, light emitters, organic photoconductors , Heat-sensitive recording material, photochromic material, hologram recording material, charging tray, conductive sheet, optical disk, inkjet printer, digital paper, color filter, organic EL element, organic semiconductor laser, dye-sensitized solar cell, sensor, EMI shield film, etc. It may be used for mechanical materials or mechanical parts (equipment), specifically, automobile materials or parts, aeronautical / space-related materials or parts, sliding members, and the like.

The resin of the present invention can be particularly effectively used as an optical member. Typical optical members include optical films (optical sheets) such as liquid crystal films and organic EL films; optical lenses such as glasses lenses and camera lenses; prisms, holograms, optical fibers and the like.

Examples of the optical film include a polarizing film, a polarizing element and a polarizing plate protective film constituting the polarizing film, a diffuser plate (film), a prism sheet, a light guide plate, a brightness improving film, a near infrared absorbing film, a reflective film, and antireflection. (AR) film, antireflection (LR) film, antiglare (AG) film, transparent conductive (ITO) film, eccentric conductive film (ACF), electromagnetic wave shielding (EMI) film, electrode substrate film, color filter substrate Examples thereof include a film, a barrier film, a color filter layer, a black matrix layer, an adhesive layer between optical films, or a mold release layer. These optical films can be effectively used as optical films for displays such as liquid crystal displays (LCDs), organic EL displays (OLEDs), plasma displays (PDPs), field emission displays (FEDs), and electronic papers. Devices or devices include televisions; personal computers (PCs) such as desktop PCs, notebook PCs or tablet PCs; smartphones, mobile phones; car navigation systems; flat panel displays (FPDs) such as touch panels. Examples include equipped devices or devices.

Examples of the optical lens include a lens for glasses, a contact lens, a lens for a camera, a VTR zoom lens, a pickup lens, a frennel lens, a solar condensing lens, an objective lens, a rod lens array, and the like, and among them, a lens for a camera and the like. It can be suitably used for lenses that require a low number of abbreviations. Devices or devices equipped with such optical lenses are typically small devices or mobile devices having camera functions such as smartphones, mobile phones, and digital cameras; in-vehicle devices such as drive recorders and back cameras (rear cameras). For example, a camera for use.

Claims (22)

The following formula (1)

[In the formula, Y ^1a and Y ^1b are independently represented by the following formula (Y1).

(In the formula, Z ¹ indicates an arene ring,
^R1 represents a substituent and m1 represents 0 or an integer greater than or equal to 1. )
Indicates a monovalent group represented by, 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 indicate a substituent, and m2a and m2b independently indicate an integer of 0 to 4, respectively.
k1a + m2a and k1b + m2b are independently 4 or less, respectively.
Y ^2a and Y ^2b are independently expressed by the following equation (Y2).

(In the equation, A ¹ and A ² independently represent a linear or branched alkylene group, and n2 represents 0 or an integer of 1 or more.)
Indicates a monovalent group represented by. ]
A diol compound represented by. In the above equation (1), Z ¹ is a C _6-12 arene ring, and k1a and k2b are integers of 1 to 2.
A ¹ is a linear or branched C _1-6 alkylene group.
The diol compound according to claim 1, wherein A ² is a linear or branched C _2-4 alkylene group, and n 2 is 0 or an integer of 1 to 10. In the formula (1), Z ¹ is a benzene ring or a naphthalene ring, and k1a and k2b are 1.
A ¹ is a linear or branched C _1-4 alkylene group.
The diol compound according to claim 1 or 2, wherein n2 is 0. The following formula (I)

[In the formula, Y ^3a and Y ^3b are independently represented by the following formula (Y3).

( ^In the formula, A3 represents a linear or branched alkylene group.
R ³ represents a hydrogen atom or an alkyl group. )
Indicates 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 the above formula (1), respectively. ]
The method for producing a diol compound according to any one of claims 1 to 3, which comprises a reduction step of reducing the compound represented by. The following formula (1P)

[In the formula, Y ^2c and Y ^2d are independently expressed in the following formula (Y2c).

(In the formula, A ¹ , A ² and n 2 are the same as the above formula (1) according to claim 1, respectively, and A ¹ is bonded to the 9-position of the fluorene ring.)
Indicates 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 the above formula (1) according to claim 1, respectively. ]
A resin containing a structural unit represented by. The resin according to claim 5, which is a polyester-based resin containing the first diol unit (A1) represented by the formula (1P) as the diol unit (A). The resin according to claim 6, wherein the ratio of the first diol unit (A1) represented by the formula (1P) is 5 to 100 mol% with respect to the entire diol unit (A). The resin according to claim 6 or 7, which is a polycarbonate resin. The diol unit (A) is the following formula (2).

(In the equation, Z ^2a and Z ^2b each independently represent an arene ring,
^R4 indicates a substituent, m4 indicates an integer of 0 to 8, and the m4 indicates an integer of 0 to 8.
R ^5a and R ^5b each independently indicate a substituent, and m5a and m5b independently indicate an integer of 0 or 1 or more, respectively.
A ^4a and A ^4b independently represent a linear or branched alkylene group, respectively, and n4a and n4b independently represent an integer of 0 or 1 or more, respectively. )
The resin according to claim 8, further comprising a second diol unit (A2) represented by. In the above formula (2), Z ^2a and Z ^2b are _C6-10 arene rings.
R ^5a and R ^5b are hydrocarbon groups, and m5a and m5b are integers from 0 to 2.
The resin according to claim 9, 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. The resin according to claim 9 or 10, wherein the 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. The resin according to claim 6 or 7, which is a polyester carbonate resin. The resin according to claim 12, wherein the diol unit (A) further contains the second diol unit (A2) according to claim 9 or 10. The following formula (4) is used as the dicarboxylic acid unit (B).

(In the formula, R ⁶ indicates a substituent, m 6 indicates an integer of 0 to 8, and
A ^6a and A ^6b independently represent a linear or branched chain alkylene group, respectively. The resin according to claim 12 or 13, further comprising a first dicarboxylic acid unit (B1) represented by). The ratio of the first diol unit (A1) to the second diol unit (A2) is the former / the latter (molar ratio) = 10/90 to 50/50.
The ratio of the dicarboxylic acid unit (B) is 0.5 to 0.85 mol with respect to 1 mol of the diol unit (A).
The resin according to claim 14, wherein the ratio of the first dicarboxylic acid unit (B1) is 50 to 100 mol% with respect to the entire dicarboxylic acid unit (B). The resin according to claim 6 or 7, which is a polyester resin. The diol unit (A) is the following formula (3).

( ^In the formula, A5 represents a linear or branched alkylene group, and n5 represents an integer of 1 or more.)
Further contains a third diol unit (A3) represented by
The resin according to claim 16, further comprising the first dicarboxylic acid unit (B1) according to claim 14 as the dicarboxylic acid unit (B). The dicarboxylic acid unit (B) is represented by the following formula (5).

(In the formula, Z ³ indicates an arene ring,
R ⁷ indicates a substituent, and m 7 indicates an integer of 0 or 1 or more. )
The resin according to claim 16 or 17, which comprises a second dicarboxylic acid unit (B2) represented by. The ratio of the first diol unit (A1) to the third diol unit (A3) is the former / the latter (molar ratio) = 70/30 to 95/5.
The ratio of the first dicarboxylic acid unit (B1) is 0.3 to 1.5 mol with respect to 1 mol of the first diol unit (A1).
The resin according to claim 18, wherein the 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. A molded product containing the resin according to any one of claims 5 to 19. The molded product according to claim 20, which is an optical member. The molded product according to claim 20 or 21, which is an optical film or an optical lens.