JP2023055339A - Polyester and compound - Google Patents

Abstract

To provide a polyester excellent in transparency, heat resistance, and weather resistance, suppressed in crystallization, furthermore, low in photoelastic coefficiency, and suitable for an optical material.SOLUTION: A polyester having a unit composed of a diol having a skeleton of the following formula (PI) and a dicarboxylic acid. (In formula (P1), a ring Z is a 6- to 15-membered alicyclic carbocyclic ring that may have a substituent. The alicyclic carbon ring is a monocyclic ring, a condensed ring, a bridged ring, or combinations thereof, and may contain a heteroatom. L1 and L2 are a direct bond or a divalent hydrocarbon group having 1 to 5 carbon atoms, R1 is a substituent. m is 0 to 4.)SELECTED DRAWING: None

Description

The present invention relates to polyesters. More specifically, it relates to a polyester suitable for optical materials having excellent transparency, heat resistance, weather resistance, etc., suppressed crystallization, low intrinsic birefringence and low photoelastic coefficient. The present invention also relates to compounds from which this polyester is produced.

Polyethylene terephthalate (PET), which is known as a representative example of polyester, has excellent transparency, mechanical strength, melt stability, solvent resistance, aroma retention, and recyclability, and is used in films, sheets, hollow containers, etc. It is a polyester that is widely used for However, PET cannot be said to have a sufficiently high glass transition temperature, and improvement in heat resistance is desired. In addition, since the crystallinity of polyesters may impair transparency, polyesters modified by copolymerization have been widely developed.

As an example of modified polyester, a polyester obtained by copolymerizing 1,4-cyclohexanedimethanol has been proposed (Patent Document 1). However, the polyester described in Patent Document 1 has a glass transition temperature of around 80° C. and cannot be said to have sufficient heat resistance.

New diols are being widely developed as raw materials for polyester copolymerization, but the development of raw material dicarboxylic acids that achieve high transparency, weather resistance, and low birefringence while maintaining a high glass transition temperature (Tg) is limited to diols. The number of reports is comparatively limited. Generally, an aromatic dicarboxylic acid such as terephthalic acid is used as a raw material for copolymerization due to its high Tg, but in this case, the intrinsic birefringence value increases and the optical properties deteriorate. Therefore, an aliphatic carboxylic acid having a rigid structure is desired as a raw dicarboxylic acid for polyester.

Patent Document 2 describes tricyclodecane or pentaphthalene as a polyester that is excellent in transparency, heat resistance, light resistance, etc., has a high refractive index, has a low intrinsic birefringence and a low water absorption rate, and is suitable as a material for manufacturing optical parts. A polyester having a cyclopentadecane skeleton has been proposed.
However, the polyester of Patent Document 2 has a glass transition temperature of at most 98° C. as shown in Comparative Examples 1 and 2 below, and further improvement in heat resistance is desired.

Japanese translation of PCT publication No. 2007-517926 JP 2007-238856 A

In view of the problems of the prior art, the present invention provides a polyester that is excellent in transparency, heat resistance, weather resistance, etc., is suppressed in crystallization, and has low intrinsic birefringence and photoelastic coefficient and is suitable for optical materials. The challenge is to

In order to solve the above problems, the present inventors have made intensive studies, and as a result, condensed cyclopentane ring and alicyclic carbocyclic ring Z having a specific carbon number are condensed via cyclobutane ring in polyester By introducing a ring structure, preferably the alicyclic carbocyclic ring Z itself also constitutes a condensed ring or has a rigid structure having a crosslinked structure, without introducing an aromatic ring for enhancing heat resistance. The present inventors have found that the polyester can improve heat resistance and weather resistance, can suppress crystallization, and can be made into a polyester having low birefringence and low photoelastic coefficient, and arrived at the present invention.
That is, the gist of the present invention is as follows.

[1] A polyester having a repeating unit represented by the following formula (1A).

(A ¹ in formula (1) represents the following formula (P1), B ¹ is a substituted or unsubstituted linear or branched divalent group having 2 to 30 carbon atoms, substituted or an unsubstituted monocyclic or polycyclic aliphatic divalent group, or a substituted or unsubstituted monocyclic or polycyclic aromatic divalent group having 6 to 30 carbon atoms.)

(In formula (P1), ring Z represents a 6- to 15-membered alicyclic carbocyclic ring that may have a substituent, and the alicyclic carbocyclic ring is a monocyclic ring, a condensed ring, a bridged ring, or a combination thereof, and the alicyclic carbocycle may contain heteroatoms.
L ¹ and L ² each independently represent a direct bond or a divalent hydrocarbon group having 1 to 5 carbon atoms. R ¹ represents a substituent and m is an integer of 0-4. )

[2] The polyester according to [1], wherein ^L1 and ^L2 in formula (P1) are each independently a direct bond or a methylene group.

[3] The polyester according to [1] or [2], wherein the alicyclic carbocyclic ring of Z in the formula (P1) has at least one ring with 4 or more members.

[4] A polyester comprising the structure according to any one of [1] to [3], wherein the formula (P1) is any one selected from the following formulas (P2) to (P11).

(In formulas (P2) to (P11), L ¹ , L ² and m are the same as in formula (P1) above. R ^1a and R ² are each independently a substituent having 1 to 12 carbon atoms. n2 is an integer of 0 to 6, n3 and n11 are integers of 0 to 11, n4 and n5 are integers of 0 to 9, n6 is an integer of 0 to 7, n7 is 0 is an integer of ~13, and n8~n10 is an integer of 0~5.)

[5] The polyester according to any one of [1] to [4], which is a resin for optical use.

[6] A polyester having a repeating unit represented by the following formula (1B).

(In formula (1B), B ² represents the following formula (P12), A ² is a substituted or unsubstituted linear or branched divalent group having 2 to 30 carbon atoms, a substituted or It is either an unsubstituted monocyclic or polycyclic aliphatic divalent group or a substituted or unsubstituted monocyclic or polycyclic aromatic divalent group having 6 to 30 carbon atoms.)

(In formula (P12), ring Z represents a 6- to 15-membered alicyclic carbocyclic ring that may have a substituent, and the alicyclic carbocyclic ring is a monocyclic ring, a condensed ring, a bridged ring, or a combination thereof, and the alicyclic carbocycle may contain heteroatoms.
L ³ and L ⁴ each independently represent a direct bond or a divalent hydrocarbon group having 1 to 5 carbon atoms. R ³ represents a substituent and m is an integer of 0-4. )

[7] The polyester according to [6], wherein ^L3 and ^L4 in the formula (P12) are each independently a direct bond or a methylene group.

[8] The polyester according to [6] or [7], wherein the alicyclic carbocyclic ring of Z in the formula (P12) has at least one ring with 4 or more members.

[9] The polyester according to any one of [6] to [8], wherein the formula (P12) is any one selected from the following formulas (P13) to (P22).

(In formulas (P13) to (P22), L ³ , L ⁴ and m are the same as in formula (P12). R ^3a and R ⁴ each independently represent a substituent having 1 to 12 carbon atoms. n13 is an integer of 0 to 6, n14 and n22 are integers of 0 to 11, n15 and n16 are integers of 0 to 9, n17 is an integer of 0 to 7, n18 is 0 to is an integer of 13, and n19 to n21 are integers of 0 to 5.)

[10] The polyester according to any one of [6] to [9], which is a resin for optical use.

[11] A compound represented by the following formula (P23).

(In formula (P23), ring Z represents a 6- to 15-membered alicyclic carbocyclic ring optionally having substituents other than -L ⁶ -C(=O)-Y ² , and the alicyclic Cyclic carbocycles are single rings, fused rings, bridged rings, or combinations thereof, and the alicyclic carbocycles may contain heteroatoms.
L ⁵ and L ⁶ each independently represent a direct bond or a divalent hydrocarbon group having 1 to 5 carbon atoms. R ⁵ represents a substituent and m is an integer of 0-4.
Y ¹ and Y ² are each independently a hydroxy group, an optionally substituted alkoxy group, an optionally substituted phenoxy group, a chlorine atom, a bromine atom, or an iodine atom. )

[12] The compound according to [11], wherein ^L5 and ^L6 in formula (P23) are each independently a direct bond or a methylene group.

[13] The compound according to [11] or [12], wherein the alicyclic carbocyclic ring of Z in the formula (P23) has at least one ring with 4 or more members.

[14] The compound according to any one of [11] to [13], wherein the formula (P23) is any one selected from the following formulas (P24) to (P33).

(In formulas (P24) to (P33), L ⁵ , L ⁶ , m, Y ¹ and Y ² have the ^same definitions as ⁱⁿ formula (23). represents an integer of 0 to 12. n24 is an integer of 0 to 6, n25 and n33 are integers of 0 to 11, n26 and n27 are integers of 0 to 9, and n28 is an integer of 0 to 7. , n29 is an integer from 0 to 13, and n30 to n32 are integers from 0 to 5.)

[15] The compound according to [14], wherein m and n24 to n33 in formulas (P24) to (P33) are each independently 0 or 1.

[16] The compound according to [14] or [15], wherein the formula (P23) is any one selected from the formulas (P24) to (P29).

[17] The compound according to [16], wherein the formula (P23) is the formula (P26).

[18] A polyester is produced through an esterification step of performing an esterification reaction or a transesterification reaction using a dicarboxylic acid component and a diol component, and a melt polycondensation reaction step of performing a polycondensation reaction of the oligomer obtained by the esterification step. A method for producing a polyester, wherein the compound according to any one of [11] to [17] is used as at least part of the dicarboxylic acid component.

INDUSTRIAL APPLICABILITY The polyester of the present invention is excellent in transparency, heat resistance, weather resistance, etc., is inhibited from crystallization, has low intrinsic birefringence and low photoelastic coefficient, and is suitable for optical materials. The polyester of the present invention is a material that can be used as an optical material for lenses, optical films such as retardation films, lighting equipment members, optical fibers, and the like.
The compound of the present invention is useful as a raw material monomer for producing the polyester of the present invention. In addition, the compound of the present invention can be widely used in applications requiring improved heat resistance and the like.

Although the embodiments of the present invention will be described in detail below, the descriptions of the configurations and the like described below are examples of the embodiments of the present invention, and the present invention is limited to the following contents as long as the gist thereof is not exceeded. not. In addition, when the expression "~" is used in this specification, it is used in the sense of including the numerical values or physical values described before and after it. Numerical values or physical values described as the upper limit and the lower limit are used in the sense of including those values. Also, "ppm" and "%" mean "weight ppm" and "weight %", respectively, unless otherwise specified. Further, "parts by weight" and "parts by mass", and "% by weight" and "% by mass" are substantially synonymous.
Moreover, the “number of members” represents the number of atoms constituting a ring.

〔polyester〕
The polyester of the present invention includes a polyester having a repeating unit represented by formula (1A) described below and a polyester having a repeating unit represented by formula (1B).
Hereinafter, a polyester having a repeating unit represented by formula (1A) is referred to as "polyester (1A)", and a polyester having a repeating unit represented by formula (1B) is referred to as "polyester (1B)". are collectively referred to simply as "polyester".

The polyester of the present invention is excellent in transparency, heat resistance, weather resistance, and the like, and is characterized by suppressed crystallization and low intrinsic birefringence. That is, the polyester of the present invention has a rigid structure in which a cyclopentane ring and a 6- to 15-membered alicyclic carbocyclic ring are condensed via a cyclobutane ring, and therefore has high heat resistance. In addition, polyesters made from aliphatic condensed-ring monomers are hydrophobic, have low water absorbency, high moisture resistance, and excellent weather resistance.
In addition, since aliphatic compounds absorb less visible light than aromatic compounds and can be less oriented than planar structures such as aromatic compounds, they are resins with low intrinsic birefringence.
Furthermore, introduction of an aliphatic condensed ring or crosslinked structure makes the monomer molecular structure three-dimensional, suppresses crystallization, and provides high transparency.

[Polyester (1A)]
Polyester (1A) of the present invention has a repeating unit represented by the following formula (1A).

(A ¹ in formula (1) represents the following formula (P1), B ¹ is a substituted or unsubstituted linear or branched divalent group having 2 to 30 carbon atoms, substituted or an unsubstituted monocyclic or polycyclic aliphatic divalent group, or a substituted or unsubstituted monocyclic or polycyclic aromatic divalent group having 6 to 30 carbon atoms.)

(In formula (P1), ring Z represents a 6- to 15-membered alicyclic carbocyclic ring that may have a substituent, and the alicyclic carbocyclic ring is a monocyclic ring, a condensed ring, a bridged ring, or a combination thereof, and the alicyclic carbocycle may contain heteroatoms.
L ¹ and L ² each independently represent a direct bond or a divalent hydrocarbon group having 1 to 5 carbon atoms. R ¹ represents a substituent and m is an integer of 0-4. )

^{<About A1>}
In A ¹ represented by formula (P1), cyclopentane (specifically, cyclopentane skeleton) and ring Z (specifically, alicyclic hydrocarbon skeleton) are cyclobutane (specifically, cyclobutane Skeleton) are sandwiched therebetween to form condensed rings with cyclobutane (specifically, cyclobutane skeleton). In other words, cyclopentane and ring Z are condensed to this cyclobutane with cyclobutane interposed therebetween.

In formula (P1), ring Z represents a 6- to 15-membered alicyclic carbocyclic ring. An alicyclic carbocyclic ring means a cyclic skeleton of an alicyclic compound, and is a concept including not only an aliphatic hydrocarbon ring composed of carbon atoms but also an aliphatic heterocyclic ring having a heteroatom. Since the number of members of the alicyclic carbocyclic ring is 6 or more, the total length of ^A1 is increased to some extent. Therefore, the distance of the repeating unit of polyester can be lengthened. As a result, a polyester having excellent mechanical properties such as toughness can be obtained. Moreover, since the number of members of the alicyclic carbocyclic ring Z is 6 or more, the effect of becoming a polyester with low water absorption and excellent heat resistance can be obtained. From the viewpoint of improving such effects, the number of members of the alicyclic carbocyclic ring Z is preferably 7 or more, more preferably 9 or more. The number of members of the alicyclic carbocyclic ring Z specifically represents the number of atoms contiguous in the ring of the alicyclic carbocyclic ring Z, that is, the number of ring-constituting atoms. In the case of a heterocyclic ring, it means the number including atoms other than carbon atoms (specifically, heteroatoms).

In addition, since the number of members of the alicyclic carbon ring of the ring Z is 15 or less, the number of rigid bonds is suppressed, and the effect of achieving both heat resistance and toughness of the polyester can be obtained. From the viewpoint of enhancing such effects, the number of members of the alicyclic carbocyclic ring Z is preferably 12 or less, more preferably 10 or less.

The alicyclic carbocyclic ring of ring Z may have one or more substituents. Examples of substituents that the alicyclic carbocyclic ring of ring Z may have include a hydrocarbon group having 1 to 14 carbon atoms, an acyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a aryloxy groups having 3 to 14 carbon atoms, acyloxy groups having 1 to 10 carbon atoms, silyl groups, sulfinyl groups, sulfo groups, alkylthio groups, arylthio groups, amino groups, halogen atoms, nitro groups and cyano groups.
Specific examples of hydrocarbon groups having 1 to 14 carbon atoms include alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, or 3 to 14 carbon atoms. and the like.
The alkyl group having 1 to 12 carbon atoms includes methyl group, ethyl group, propyl group, isopropyl group and butyl group.
Examples of alkenyl groups having 2 to 10 carbon atoms include vinyl groups, allyl groups and butenyl groups.
The alkynyl group having 2 to 10 carbon atoms includes acetylene group and propynyl group. The aryl group having 3 to 14 carbon atoms includes phenyl group, tolyl group and naphthyl group. The acyl group having 1 to 10 carbon atoms includes an acetyl group.
The alkoxy group having 1 to 10 carbon atoms includes methoxy group, ethoxy group and propoxy group.
The aryloxy group having 3 to 14 carbon atoms includes a phenoxy group.
The acyloxy group having 1 to 10 carbon atoms includes methoxyacetyl group and phenoxyacetyl group.
Silyl groups include trimethylsilyl groups.
The sulfo group includes sulfo group, methylsulfonyl group and ethylsulfonyl group.
The sulfinyl group includes a methylsulfinyl group and an ethylsulfinyl group.
The alkylthio group includes a methylthio group and an ethylthio group.
An arylthio group includes a phenylthio group.
The amino group includes an amino group and a dimethylamino group.

The above-described substituents that the ring Z may have may further have one or more substituents, and examples of the substituents include halogen atoms, nitro groups, and cyano groups.

The upper limit of the number of substituents is determined by the ring Z structure. From the viewpoint of facilitating the synthesis of raw material monomers for producing polyester, and from the viewpoint that the increase in the number of substituents may reduce the proportion of the rigid skeleton in the polyester skeleton, resulting in a decrease in heat resistance. The number of substituents is preferably 0 or more and 4 or less, more preferably 0 or more and 2 or less, and even more preferably 0 or 1.

From the viewpoint of increasing the proportion of a rigid skeleton and making the polyester excellent in heat resistance, the alicyclic carbocyclic ring of the ring Z does not have a substituent and the atoms constituting the alicyclic carbocyclic ring are hydrogen atoms. is bonded, or the substituent is preferably a hydrocarbon group having 1 to 14 carbon atoms. The substituent is preferably an alkyl group having 5 to 12 carbon atoms from the viewpoint of improving the toughness of the polyester and obtaining a polyester having a low melt viscosity and excellent fluidity during molding. From the viewpoint of improving the heat resistance of the polyester, the substituent is preferably an alkyl group having 1 to 4 carbon atoms. From the viewpoint of further improving the heat resistance of the polyester and the ease of synthesis of the raw material monomer, the substituent is preferably an alkyl group having 1 to 2 carbon atoms, and an alkyl group having 1 carbon atom (specifically , methyl group). In addition, from the viewpoint that the heat resistance of the polyester is further improved and the raw material monomer can be obtained at a low cost, the alicyclic carbocyclic ring in the ring Z has one methyl group as a substituent and has an alicyclic carbocyclic ring. It is preferable that other constituent atoms (that is, atoms other than the atom to which the substituent is bonded) are not bonded to a substituent and are bonded to a hydrogen atom. Moreover, from the viewpoint that the polyester can have both excellent heat resistance and toughness and that the raw material monomer can be obtained at low cost, the alicyclic carbocyclic ring of the ring Z preferably does not have a substituent. However, "-L ² -" in formula (P1) is a linking group and is not included in the substituents.

From the viewpoint of improving the heat resistance of the polyester and improving the reactivity of the raw material monomer during the production of the polyester, the substituent of the alicyclic carbocyclic ring of the ring Z is preferably an alkoxy group having 1 to 10 carbon atoms. From the viewpoint of , an alkoxy group having 1 to 3 carbon atoms is more preferable, and a methoxy group is further preferable from the viewpoint of superior heat resistance.

For example, when a dihydroxy compound is used for polymerization as a raw material monomer, if the hydrogen atom at the β-position carbon of the hydroxy group is substituted with a substituent such as an alkyl group, the hydroxy group cannot be eliminated from the monomer during the production of the polyester. can be suppressed. Therefore, the polymerization temperature can be increased to obtain a polyester having a higher molecular weight. Therefore, for example, when ^L2 in formula (P1) is a methylene group, it is preferred that a substituent is further bonded to the atom of ring Z to which ^L2 is bonded.

The alicyclic carbocyclic ring of ring Z may contain a heteroatom as a ring-constituting atom. Examples of the heteroatom include oxygen atom, sulfur atom, nitrogen atom and the like. From the viewpoint of imparting polarity to A ¹ represented by formula (P1), the heteroatom is preferably an oxygen atom and/or a sulfur atom. In this case, polarity is imparted to the ^A1 portion of the repeating units that constitute the polyester. Therefore, for example, when polyester and a different material resin are mixed, the affinity between the polyester and the different material resin can be improved, and the compatibility when the different material resin and the polyester are blended can be improved.

The cycloaliphatic carbocyclic ring of ring Z can also contain heteroatoms, eg, as substituents as described above. Alicyclic carbocycles can also contain heteroatoms in the bridge structure described below. From the viewpoint of facilitating the synthesis of raw material monomers for polyester, from the viewpoint of hardly inhibiting the condensation polymerization reaction during the production of polyester, and from the viewpoint of suppressing the water absorption rate by lowering the polarity of the obtained polyester, the ring Z is a heteroatom. preferably does not contain

The alicyclic carbocyclic ring of ring Z preferably has at least one ring with 4 or more members (the number of atoms constituting the ring). In this case, the effect of forming a rigid skeleton and being excellent in heat resistance is exhibited.

In the present specification, alicyclic carbocyclic ring is a concept including those having a condensed ring, and the alicyclic carbocyclic ring of ring Z may have a condensed ring. In this case, the number of members of the alicyclic carbocyclic ring including the condensed ring is 6-15. When the alicyclic carbocyclic ring contains a condensed ring, the distance between the repeating units constituting the polyester can be lengthened. This improves mechanical properties such as toughness of the polyester.

An alicyclic carbocyclic ring is, for example, a norbornane skeleton in which a hydrocarbon group having 5 or less carbon atoms bonded to a carbon atom constituting an alicyclic carbocyclic ring is combined with another carbon atom constituting the alicyclic carbocyclic ring. It is preferable to have a structure in which they are bonded to form a ring. That is, it preferably has a structure in which a hydrocarbon group having 5 or less carbon atoms is crosslinked to an alicyclic carbocyclic skeleton. In this case, it becomes a rigid skeleton, and the effect that it is excellent in heat resistance and pencil hardness is acquired. From the viewpoint of improving this effect, the number of carbon atoms in the hydrocarbon group in the crosslinked structure is more preferably 3 or less, more preferably 2 or less. Here, the hydrocarbon group of the crosslinked structure may have a heteroatom in the crosslinked portion, and in this case, the number of carbon atoms is the number of atoms including the heteroatom.

In addition, the alicyclic carbocyclic ring of ring Z is such that an oxygen atom bonded to a carbon atom constituting the alicyclic carbocyclic ring is an alicyclic carbocyclic ring, such as oxabicyclo[2.2.1]heptane. It preferably has a structure in which it is bonded to other constituent carbon atoms to form a ring. That is, it preferably has a structure in which an oxygen atom bridges an alicyclic hydrocarbon skeleton (that is, a cyclic ether bond). In this case, since the polarity of the heteroatom is high, the effect of improving the compatibility with the heterogeneous polymer can be obtained. In addition, the alicyclic carbocyclic ring of ring Z may have a structure in which a sulfur atom bridges an alicyclic hydrocarbon skeleton (i.e., a cyclic thioether bond), such as thiabicyclo[2.2.1]heptane. preferable. In this case, since the polarity of the heteroatom is high, the effect of improving the compatibility with the heterogeneous polymer can be obtained.

L ¹ and L ² in formula (P1) each independently represent a direct bond or a divalent hydrocarbon group having 1 to 5 carbon atoms. The hydrocarbon group is, for example, an alkylene group and may have a substituent having 1 to 5 carbon atoms. Examples of substituents include methyl group, ethyl group, propyl group, butyl group, isopropyl group and the like.

From the viewpoint of facilitating the synthesis of raw material monomers for polyester, from the viewpoint of being less likely to inhibit the condensation polymerization reaction during the production of polyester, and from the viewpoint of the inclusion of substituents increasing mobility and lowering heat resistance. , L ¹ and L ² preferably have no substituents. In addition, from the viewpoint of further improving the polyester toughness and moldability (specifically, fluidity when melted during molding), the hydrocarbon groups of L ¹ and L ² have 3 to 5 carbon atoms. preferable. On the other hand, heat resistance is further improved by forming a rigid skeleton while ensuring the toughness of polyester, and molding processability (specifically, fluidity when melted during molding) is further improved. From this point of view, the number of carbon atoms in the hydrocarbon groups of L ¹ and L ² is preferably 1 to 2. Furthermore, L ¹ and L ² are preferably a direct bond or a methylene group from the viewpoint that raw materials for synthesizing raw material monomers for polyester become inexpensive. A methylene group is also called a methanediyl group.

The bonding site of ^L1 in formula (P1) is not limited as long as it is a carbon atom forming a cyclopentane skeleton, and may be a carbon atom at the condensed ring site of cyclopentane and cyclobutane. Similarly, the bonding site of L ² in formula (P1) is not limited as long as it is a carbon atom forming the alicyclic hydrocarbon skeleton of ring Z, and the condensed ring of the alicyclic carbocyclic ring of ring Z and cyclobutane It may be an atom at a site, or when the alicyclic carbocyclic ring of ring Z is itself fused, it may be a fused ring site within the alicyclic carbocyclic ring.

R ¹ in formula (P1) represents a substituent bonded to a cyclopentane ring (specifically, a cyclopentane skeleton), and m represents the number of substituents. When having multiple substituents R ¹ , each substituent may be the same or different. The bonding site of the substituent on the cyclopentane ring is not limited as long as it is a carbon atom forming the cyclopentane skeleton, and may be a carbon atom at the condensed site of the cyclopentane ring and the cyclobutane ring. If the hydrogen atom at the β-position carbon atom of the polymerizable substituent in the raw material monomer for the polyester is substituted with an alkyl group, the elimination of the polymerizable substituent from the raw material monomer can be suppressed during the production of the polyester. Therefore, the polymerization temperature can be increased to obtain a polyester having a higher molecular weight. Therefore, for example, when L ¹ is a methylene group, it is preferable that a substituent is further bonded to the carbon atom to which L ¹ is bonded among the carbon atoms constituting the cyclopentane skeleton. The details of the substituent R ¹ are the same as those of the substituent that the alicyclic carbocyclic ring of the ring Z may have.

m in formula (P1) is an integer of 0-4. From the standpoint of facilitating the procurement of raw materials for synthesizing polyester starting monomers, from the standpoint of facilitating the synthesis of starting polyester monomers, and from the standpoint of increasing the proportion of rigid skeletons in repeating units to improve heat resistance. , m are preferably 1 or 0. When m is 0, the cyclopentane ring has no substituent R ¹ and no substituents except for the linking group -L ¹ - in formula (P1). That is, in this case, hydrogen atoms are bonded to the carbon atoms constituting the cyclopentane ring, except for -L ¹ -.

The ring Z in the above formula (P1) preferably has an alicyclic skeleton other than a cyclopentane ring. That is, in A ¹ , the cyclopentane ring and the ring Z are preferably asymmetric with the cyclobutane ring interposed therebetween. In this case, the solubility can be improved, and the effect of being superior to the synthesis of raw material monomers for polyester and the production of polyester can be obtained. Moreover, the effect that the photoelastic coefficient of polyester can be made low is acquired.

Formula (P1) is preferably any one of formulas (P2) to (P11) below. In this case, the starting monomer for the polyester can be easily produced by the below-described production method. In this case, the heat resistance, toughness, and low water absorption of polyester can be obtained.

(In formulas (P2) to (P11), L ¹ , L ² and m are the same as in formula (P1) above. R ^1a and R ² are each independently a substituent having 1 to 12 carbon atoms. n2 is an integer of 0 to 6, n3 and n11 are integers of 0 to 11, n4 and n5 are integers of 0 to 9, n6 is an integer of 0 to 7, n7 is 0 is an integer of ~13, and n8~n10 is an integer of 0~5.)

Examples of substituents having 1 to 12 carbon atoms for R ^1a and R ² include substituents having 1 to 12 carbon atoms among those mentioned above as substituents which the alicyclic carbocyclic ring of ring Z may have. Preferred substituents are also as described above, and specific examples include methyl group, ethyl group, normal propyl group, isopropyl group and the like.

From the viewpoint of heat resistance, m and n2 to n11 in formulas (P2) to (P11) are each independently preferably 0 or 1.

A ¹ in formula (1A) may be of only one type, or two or more types of A ¹ may be contained in formula (1A).

<About ^B1 >
B ¹ in formula (1A) is a substituted or unsubstituted linear or branched divalent group having 2 to 30 carbon atoms, a substituted or unsubstituted monocyclic or polycyclic aliphatic 2 having 6 to 30 carbon atoms It is either a valent group or a substituted or unsubstituted monocyclic or polycyclic aromatic divalent group having 6 to 30 carbon atoms.

Examples of substituted or unsubstituted linear or branched divalent groups having 2 to 30 carbon atoms include ethanediyl, 1,2-propanediyl, 1,3-propanediyl, 1,2-butanediyl, 1,4-butanediyl, industrially readily available; From the viewpoint of imparting high heat resistance to the resin, ethanediyl, 1,3-propanediyl, and 1,4-butanediyl are preferred, ethanediyl and 1,3-propanediyl are more preferred, and ethanediyl is particularly preferred. be.

Examples of substituted or unsubstituted monocyclic or polycyclic aliphatic divalent groups having 6 to 30 carbon atoms include 1,3-cyclohexanediyl, 1,4-cyclohexanediyl, 1,4-trans-cyclohexanediyl, 2, 6-decalindiyl, dodecahydro-4,4'-biphenylenediyl, octahydro-2,5-indenediyl, octahydro-2,6-indenediyl, etc., which imparts industrial availability and heat resistance to the resin. From the viewpoint, 1,4-cyclohexanediyl, 1,4-trans-cyclohexanediyl, dodecahydro-4,4'-biephenylylenediyl, octahydro-2,5-indenediyl, and octahydro-2,6-indenediyl are preferable. , more preferably 1,4-cyclohexanediyl and 1,4-trans-cyclohexanediyl, and particularly preferably 1,4-trans-cyclohexanediyl.

Examples of substituted or unsubstituted monocyclic or polycyclic aromatic divalent groups having 6 to 30 carbon atoms include 1,3-phenylene, 1,4-phenylene, 2,6-naphthylene, 1,8-naphthylene, 9 , 10-anthracenediyl, 1,4'-biphenylene and the like, preferably 1,3-phenylene and 1,4-phenylene, more preferably 1,4-phenylene from the viewpoint of industrial availability. is.

Further, B ¹ in formula (1A) may contain a condensed alicyclic carbocyclic unit represented by formula (P1).

Only one type of B ¹ in formula (1A) may be used, or two or more types of B ¹ may be contained in formula (1A).

<Other repeating units>
Polyester (1A) may contain repeating units other than the repeating unit represented by formula (1A).
Other repeating units include those having the divalent group described above as B ¹ instead of the condensed alicyclic carbocyclic unit represented by formula (P1) as A ¹ in formula (1A). .

<Proportion of Condensed Alicyclic Carbocyclic Unit Represented by Formula (P1)>
The content of the condensed alicyclic carbocyclic unit represented by the formula (P1) contained in the polyester (1A) improves the heat resistance of the polyester with respect to the total number of moles of A ¹ and B ¹ in the polyester. From the viewpoint of reducing intrinsic birefringence and photoelastic coefficient, the content is preferably 5 mol % or more, more preferably 10 mol % or more, and particularly preferably 15 mol % or more. On the other hand, from the viewpoints of increasing the fluidity during hot molding and suppressing the cost of resin production, this ratio is preferably 45 mol % or less, more preferably 40 mol % or less.

[Polyester (1B)]
The polyester (1B) of the present invention has a repeating unit represented by the following formula (1B).

(In formula (1B), B ² represents the following formula (P12), A ² is a substituted or unsubstituted linear or branched divalent group having 2 to 30 carbon atoms, a substituted or It is either an unsubstituted monocyclic or polycyclic aliphatic divalent group or a substituted or unsubstituted monocyclic or polycyclic aromatic divalent group having 6 to 30 carbon atoms.)

(In formula (P12), ring Z represents a 6- to 15-membered alicyclic carbocyclic ring that may have a substituent, and the alicyclic carbocyclic ring is a monocyclic ring, a condensed ring, a bridged ring, or a combination thereof, and the alicyclic carbocycle may contain heteroatoms.
L ³ and L ⁴ each independently represent a direct bond or a divalent hydrocarbon group having 1 to 5 carbon atoms. R ³ represents a substituent and m is an integer of 0-4. )

<About ^B2 >
^B2 in formula (1B) is the same as ^A1 in formula (1A), that is, formula (P12) is the same as formula (P1).
Therefore, rings Z, L ³ , L ⁴ , R ³ and m in formula (P12) are respectively synonymous with ring Z, L ¹ , L ² , R ¹ and m in formula (P1); Since the preferred ones are also the same, redundant explanations are omitted.

For the same reason as the above formula (P1), the above formula (P12) is preferably any one of the following formulas (P13) to (P22).

(In formulas (P13) to (P22), L ³ , L ⁴ and m are the same as in formula (P12). R ^3a and R ⁴ each independently represent a substituent having 1 to 12 carbon atoms. n13 is an integer of 0 to 6, n14 and n22 are integers of 0 to 11, n15 and n16 are integers of 0 to 9, n17 is an integer of 0 to 7, n18 is 0 to is an integer of 13, and n19 to n21 are integers of 0 to 5.)

In formulas (P13) to (P22) above, R ^3a , R ⁴ and n13 to n22 have the same meanings as R ^1a , R ² and n2 to n11 in formulas (P2) to (P11).

^{<About A2>}
A ² in the formula (1B) is the same as B ¹ in the formula (1A), and preferable ones are also the same, so redundant description is omitted.
A ² in formula (1B) may contain a condensed alicyclic carbocyclic unit represented by formula (12P).

<Other repeating units>
Polyester (1B) may contain repeating units other than the repeating unit represented by formula (1B).
Other repeating units include those having the aforementioned divalent group as ^A2 instead of the condensed alicyclic carbocyclic unit represented by formula (P12) as ^B2 in formula (1B). .

<Proportion of Condensed Alicyclic Carbocyclic Ring Represented by Formula (P12)>
The content of ^the condensed alicyclic carbocyclic ring represented by the formula (P12) contained in the polyester ( ^1B ) improves the heat resistance of the polyester, increases the intrinsic From the viewpoint of reducing birefringence and photoelastic coefficient, the content is preferably 5 mol % or more, more preferably 10 mol % or more, and particularly preferably 15 mol % or more. On the other hand, this ratio is preferably 50 mol % or less, more preferably 40 mol % or less, because the fluidity during thermoforming can be increased.

[Method for producing polyester]
The polyester of the present invention undergoes an esterification step of performing an esterification reaction or a transesterification reaction using a dicarboxylic acid component and a diol component, and a melt polycondensation reaction step of performing a polycondensation reaction of the oligomer obtained by the esterification step. In the method for producing a polyester via a dicarboxylic acid component, the compound of the present invention described later is used as at least a part of the dicarboxylic acid component.
Further, in the polyester of the present invention, -C(=O)-Y ¹ and -C(=O)-Y ² are represented as at least a part of the diol component in the formula (P23) representing the compound of the present invention described later. It can also be produced by using a dihydroxy compound that is a hydroxy group.
Further, the polyester of the present invention uses the compound of the present invention described later as at least part of the dicarboxylic acid component, and at least part of the diol component includes -C(=O)-Y ¹ , -C It can also be prepared by using a dihydroxy compound in which (=O)-Y ² is a hydroxy group.
In any case, the raw material dicarboxylic acid component and/or Alternatively, the composition of the diol component may be adjusted.

As described above, the polyester of the present invention is a compound containing a condensed alicyclic carbocyclic ring represented by formula (P1) or formula (P12) (hereinafter referred to as "condensed alicyclic It may be referred to as a "carbocyclic ring-containing compound of the formula".

The method for producing the polyester of the present invention is described below.

In the present invention, the term "dicarboxylic acid component" refers to the dicarboxylic acid and its derivatives, which are used as starting materials for producing polyester, and the same applies to the "diol component." Further, the phrases "containing a structural unit derived from a dicarboxylic acid component in the molecular chain" and "containing a structural unit derived from a diol component in the molecular chain" mean that these raw material components are reacted in the polyester production process to form It means that the polymer chain that constitutes the polyester molecule contains the structural unit described above.

<Polyester raw material>
(Dicarboxylic acid component)
Specific examples of the dicarboxylic acid of the dicarboxylic acid component used as a raw material for producing the polyester of the present invention other than the condensed alicyclic carbocyclic ring-containing compound include terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4 aromatic dicarboxylic acids such as '-diphenyletherdicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 2,6-naphthalenedicarboxylic acid; Alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,3-norbornenedicarboxylic acid; malonic acid, succinic acid, glutaric acid, adipic acid , pimelic acid, suberic acid, azelaic acid, sebacic acid, and the like, and these may be used singly or in combination of two or more. Aromatic dicarboxylic acids are preferred from the viewpoint of the mechanical properties of the resulting polyester, the wide range of applications, and the availability of raw materials. Preferred aromatic dicarboxylic acids are terephthalic acid and isophthalic acid, and preferred aliphatic dicarboxylic acids are succinic acid and adipic acid.

The dicarboxylic acid component can be subjected to the reaction as a dicarboxylic acid, as a dicarboxylic anhydride, or as a dicarboxylic acid derivative such as an alkyl ester of a dicarboxylic acid, preferably a dialkyl ester, or an acid halide. may be used as a mixture of There are no particular restrictions on the alkyl group of the dicarboxylic acid alkyl ester, but if the alkyl group is long, the boiling point of the alkyl alcohol produced during the transesterification reaction will rise, and it will not volatilize from the reaction solution, resulting in it acting as a terminal terminator. An alkyl group having 4 or less carbon atoms is preferable, and a methyl group is particularly preferable, because it inhibits polycondensation.

In particular, as the dicarboxylic acid component other than the condensed alicyclic carbocyclic ring-containing compound, the main component is terephthalic acid and/or its ester-forming derivative from the viewpoint of industrial availability and the ability to achieve a high glass transition temperature. is preferred. In the present specification, the term “main component” means the component contained in the largest amount in terms of mol among the components containing this.

The ratio of the dicarboxylic acid (derivative), which is a condensed alicyclic carbocyclic ring-containing compound, to the total dicarboxylic acid component varies depending on whether a condensed alicyclic carbocyclic ring-containing compound is used as the diol component, and the polyester of the present invention to be produced The amount may be such that the alicyclic carbocyclic unit represented by the formula (P1) or the formula (P12) is contained therein in the above-mentioned suitable ratio.

<Diol component>
Other than the condensed alicyclic carbocyclic ring-containing compound, specific examples of diol components used as starting materials for producing the polyester of the present invention include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, and 1,3-propane. Diol, 1,4-butanediol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, dibutylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, etc. Aliphatic diols; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclo[5.2.1.0(2,6)]de Alicyclic diols such as candimethanol; 1,4-benzenedimethanol, 1,3-benzenedimethanol, 4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane, 2,2- Aromatic diols such as bis[4-(2-hydroxyethoxy)phenyl]propane, bis(4-hydroxyphenyl)sulfone, bis[4-(2-hydroxyethoxy)phenyl]sulfone; isosorbide, isomannide, isoidet, erythritan, etc. Oxygen-containing alicyclic diols derived from plant materials, ethylene glycol, 1,3-propanediol, 1,4-butanediol and the like can also be derived from plant materials. Among them, it is preferable to use ethylene glycol and 1,4-butanediol from the viewpoint of the mechanical properties of the obtained polyester, the wide range of applications, the availability of raw materials, and the like. These may be used individually by 1 type, and may be used in mixture of 2 or more types.

Among these, ethylene glycol and/or 1,4-butanediol are preferable as the diol component. Ethylene glycol and/or 1,4-butanediol are preferably used as the diol component.

The ratio of the condensed alicyclic carbocyclic ring-containing compound to the total diol component varies depending on whether or not the condensed alicyclic carbocyclic ring-containing compound is used as the dicarboxylic acid component. ) or the alicyclic carbocyclic unit represented by the formula (P12) is contained in the above-mentioned suitable ratio.

(Other copolymer components)
In addition to the carboxylic acid component and the diol component, a small amount of a copolymerization component can be added to the raw materials for producing the polyester of the present invention so as not to impair the effects of the present invention. Copolymer components that can be added include, for example, glycolic acid, p-hydroxybenzoic acid, hydroxycarboxylic acids such as p-β-hydroxyethoxybenzoic acid, alkoxycarboxylic acids, and stearyl alcohol, benzyl alcohol, stearic acid, Monofunctional components such as behenic acid, benzoic acid, t-butylbenzoic acid, benzoylbenzoic acid, tricarballylic acid, trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetetracarboxylic acid, gallic acid, trimethylolethane, trimethylol Trifunctional or higher polyfunctional components such as propane, glycerol, pentaerythritol, and sugar esters can be used.
These may be used individually by 1 type, and may be used in mixture of 2 or more types.

<Production of polyester>
The polyester of the present invention is produced by coexisting the above-mentioned dicarboxylic acid component, diol component, and optional copolymer component, conducting an esterification reaction or transesterification reaction, and subsequently performing a polycondensation reaction. can be manufactured. In the esterification reaction or transesterification reaction, a dicarboxylic acid component, a diol component, and an optional copolymer component are allowed to coexist, charged into an esterification reactor equipped with a stirrer and a distillation tube, and a catalyst added. The reaction is carried out under an inert gas atmosphere with stirring under normal pressure or reduced pressure while distilling off by-products such as water produced by the reaction from the reaction system. The ratio of raw materials used, that is, the molar ratio of the total moles of diol components to the total moles of dicarboxylic acid components {ratio of (diol acid component)/(dicarboxylic acid component)} is preferably 0.5 to 2.0.

In order to obtain a sufficient reaction rate in the esterification reaction or transesterification reaction and the subsequent polycondensation reaction, it is preferable to use a catalyst. The catalyst is not particularly limited as long as it is a catalyst normally used for esterification reaction or transesterification reaction, and examples thereof include titanium compounds, germanium compounds, antimony compounds, tin compounds and the like. Also, if necessary, compounds of alkali metals such as sodium, lithium, potassium, calcium and magnesium can be added.

Titanium compounds are preferred because they are highly active in both the esterification reaction or transesterification reaction and the subsequent polycondensation reaction.
Specific examples of titanium compounds include tetra-n-propyl titanate, tetra-i-propyl titanate, tetra-n-butyl titanate, hydrolysates of these organic titanates, titanium (oxy) acetylacetonate, titanium tetraacetylacetonate. titanium bis(ammonium lactate) dihydroxide, polyhydroxytitanium stearate, titanium lactate, butyl titanate dimer, titanium oxide, titania/silica composite oxide and the like.

A germanium compound is preferable because a polyester having a good color tone can be easily obtained. Specific examples of germanium compounds include inorganic germanium compounds such as germanium oxide and germanium chloride, and organic germanium compounds such as tetraalkoxygermanium. Germanium oxide, tetraethoxygermanium, tetrabutoxygermanium, and the like are preferred from the viewpoint of price and availability, and germanium oxide and its alcoholic and aqueous solutions are particularly preferred.

Two or more types of catalysts may be used in combination, and if necessary, the above catalysts may be used in combination with a magnesium compound, a phosphorus compound, or the like.

The amount of catalyst used is usually in the range of 5 to 2000 ppm with respect to the produced polyester. Among them, 10 to 1000 ppm is preferable. The catalyst for esterification reaction or transesterification reaction can also be used as it is as a polycondensation reaction catalyst. The reaction temperature is usually in the range of 150 to 300°C, preferably in the range of 180 to 250°C, although it depends on the type of catalyst and the amount used. The reaction time depends on the type of catalyst, amount used, reaction temperature, etc., but is usually in the range of 10 minutes to 10 hours, preferably in the range of 30 minutes to 5 hours. The reaction rate at the end of the esterification reaction or transesterification reaction is 90% to 100%. The term "reaction rate" as used herein refers to the ratio of the carboxylic acid component esterified or transesterified by the reaction to the total carboxylic acid component charged in the reaction system, expressed as a percentage.

In the polycondensation reaction, the reaction solution after the completion of the esterification reaction or the transesterification reaction is transferred to a polycondensation tank equipped with a stirrer, a distillation tube, a thermometer, a pressure gauge, a device for applying reduced pressure, and the like. , a catalyst is added, and the reaction proceeds while the pressure in the polycondensation tank is gradually reduced. A catalyst is preferably used to obtain a sufficient reaction rate. The catalyst is not particularly limited as long as it is a catalyst that is usually used for polycondensation reaction, and the catalysts exemplified as usable in the above esterification reaction or transesterification reaction are used as they are as polycondensation reaction catalysts. can do. Preferred catalysts are also the same as those described above. When a new catalyst is used in the polycondensation reaction, the amount used is usually in the range of 5 to 2000 ppm, preferably 10 to 1000 ppm, relative to the polyester produced.

The polycondensation reaction is carried out while gradually reducing the pressure in the reactor. The pressure in the reaction vessel is finally adjusted from the atmosphere to 1 kPa or less, preferably 0.5 kPa or less at the end of the reaction. Although the reaction temperature depends on the type of catalyst, the amount of the catalyst used, etc., it is in the range from the temperature at the end of the esterification reaction or transesterification reaction to 300°C, preferably in the range from the temperature at the end of the reaction to 275°C. The reaction time depends on the type of catalyst, amount used, reaction temperature, etc., but is usually 10 minutes to 10 hours, preferably 30 minutes to 5 hours. In addition, the esterification reaction or transesterification reaction and the polycondensation reaction can be carried out in one tank equipped with a vacuum addition device in the esterification reaction tank. Furthermore, these esterification reactions, transesterification reactions, polycondensation reactions, and the like can be carried out in either a batch system or a continuous system.

After completion of the polycondensation reaction, the desired polyester can be obtained by taking out the reaction product from the reaction tank. Generally, the polyester is pulled out from the bottom of the reaction tank in the form of strands, and the strands are cut while being cooled with water to obtain the polyester having the appearance of pellets. The obtained polyester having a pellet-like appearance may be further subjected to solid phase polymerization, if necessary. Solid phase polymerization can be performed by a known method.

Various additives such as heat stabilizers, antioxidants, crystal nucleating agents, flame retardants, and antistatic agents may be added to any stage of the polyester production process described above or to the resulting polyester, as long as the properties are not impaired. , a release agent, an ultraviolet absorber, and the like may be added.
Further, when molding polyester, in addition to the various additives described above, reinforcing agents and extenders such as glass fiber, carbon fiber, titanium whiskers, mica, talc, CaCO ₃ , TiO ₂ and silica are added and molded. can also

[Physical properties and characteristics of polyester]
<Glass transition temperature>
From the viewpoint of enhancing heat resistance, the glass transition temperature Tg of polyester is preferably 100° C. or higher, more preferably 105° C. or higher, still more preferably 110° C. or higher, and particularly preferably 115° C. or higher. is. On the other hand, if the glass transition temperature is too high, the polyester may be deteriorated due to heat generated by shear during extrusion. Therefore, the glass transition temperature Tg of polyester is preferably 190° C. or lower, more preferably 180° C. or lower, still more preferably 170° C. or lower, and particularly preferably 160° C. or lower. The glass transition temperature of the polyester can be adjusted within the above range by adjusting the type and blending ratio of raw material monomers during production, adjusting the polymerization temperature, and adjusting the amount of additive added.
The glass transition temperature of the polyester is measured by the method described in Examples below.

<Reduced viscosity>
If the reduced viscosity of the polyester is too low, the properties such as heat resistance, chemical resistance, abrasion resistance and mechanical strength of the molded article obtained after molding may be deteriorated. Therefore, the reduced viscosity of the polyester is preferably 0.20 dL/g or more, more preferably 0.30 dL/g or more. On the other hand, when the reduced viscosity is too high, the fluidity of the resin during molding is lowered, which may lead to deterioration in productivity and moldability, and increased distortion of the molded product. Therefore, the reduced viscosity of the polyester is preferably 1.50 dL/g or less, more preferably 1.20 dL/g or less, and even more preferably 1.00 dL/g or less. The reduced viscosity of the polyester can be adjusted within the above range by adjusting the type and blending ratio of the raw material monomers used in the production of the polyester, adjusting the polymerization temperature, and adjusting the amount of additive added.
The reduced viscosity of the polyester is measured by the method described in Examples below.

<Photoelastic coefficient>
If the photoelastic modulus of polyester is high, stress causes retardation, resulting in low optical reliability. Therefore, the photoelastic coefficient of polyester is preferably 18×10 ⁻¹² Pa ⁻¹ or less, more preferably 15×10 ⁻¹² Pa ⁻¹ or less, further preferably 12×10 ⁻¹² Pa ⁻¹ or less, and 9× It is more preferably 10 ⁻¹² Pa ⁻¹ or less, particularly preferably 4×10 ⁻¹² Pa ⁻¹ or less, and preferably 0 or more.
The photoelastic coefficient of polyester is measured by the method described in the section of Examples below.

<Refractive index/Abbe number>
When the polyester of the present invention is used for applications requiring a high refractive index and a high Abbe number, such as optical lenses, the refractive index of the polyester at the sodium D line is preferably 1.50 or more, more preferably 1.53 or more.
Also, the larger the Abbe number, the smaller the wavelength dependence of the refractive index.
The refractive index and Abbe number of the polyester are measured by the methods described in Examples below.

[Use]
INDUSTRIAL APPLICABILITY The polyester of the present invention is excellent in transparency, heat resistance, weather resistance, etc., is suppressed in crystallization, and has low intrinsic birefringence, and is suitable for optical materials.
The polyester of the present invention is useful, for example, as a material for producing optical parts such as various optical lenses, various optical films such as retardation films, optical fibers, and optical disc substrates.

〔Compound〕
The compound of the present invention is a polymerizable alicyclic compound represented by the following formula (P23), and is useful as a raw material monomer for the polyester of the present invention.

(In formula (P23), ring Z represents a 6- to 15-membered alicyclic carbocyclic ring which may have a substituent other than —L ⁶ —C(═O)—Y ² , and the alicyclic ring Formula carbocycles are single rings, fused rings, bridged rings, or combinations thereof, and the alicyclic carbocycles may contain heteroatoms.
L ⁵ and L ⁶ each independently represent a direct bond or a divalent hydrocarbon group having 1 to 5 carbon atoms. R ⁵ represents a substituent and m is an integer of 0-4.
Y ¹ and Y ² are each independently a hydroxy group, an optionally substituted alkoxy group, an optionally substituted phenoxy group, a chlorine atom, a bromine atom, or an iodine atom. )

In the compound represented by formula (P23), cyclopentane (specifically, a cyclopentane skeleton) and ring Z (specifically, an alicyclic hydrocarbon skeleton) are combined with cyclobutane (specifically, a cyclobutane skeleton). ) and form a condensed ring with cyclobutane (specifically, a cyclobutane skeleton). In other words, cyclopentane and ring Z are condensed to this cyclobutane with cyclobutane interposed therebetween.

In formula (P23), ring Z represents a 6- to 15-membered alicyclic carbocyclic ring. The alicyclic carbocyclic ring Z means a cyclic skeleton of an alicyclic compound, and is a concept including not only an aliphatic hydrocarbon ring composed of carbon atoms but also an aliphatic heterocyclic ring having a heteroatom. Since the alicyclic carbocyclic ring has 6 or more members, the total length of the compound is increased to some extent. Therefore, by using this compound as a monomer, the bond distance between structural units can be lengthened. As a result, a resin having excellent mechanical properties such as toughness can be produced. Moreover, since the number of members of the alicyclic carbocyclic ring Z is 6 or more, the effect of obtaining a resin having low water absorption and excellent heat resistance can be obtained. From the viewpoint of enhancing such effects, the number of members of the alicyclic carbocyclic ring Z is preferably 7 or more, more preferably 9 or more. The number of members of the alicyclic carbocyclic ring Z specifically represents the number of atoms contiguous in the ring of the alicyclic carbocyclic ring Z, that is, the number of ring-constituting atoms. In the case of a group heterocycle, it means the number including atoms other than carbon atoms (specifically, heteroatoms).

Ring Z, L ⁵ , L ⁶ , R ⁵ and m in the above formula (P23) are respectively synonymous with ring Z, L ¹ , L ² , R ¹ and m in the above formula (P1) and are preferred. Since they are the same, redundant explanations are omitted.

Y ¹ and Y ² are functional groups (specifically, polymerization reaction groups) bonded to L ⁵ and L ⁶ respectively, and are each independently a hydroxy group, an optionally substituted alkoxy group, a substituted a phenoxy group which may have a group, a chlorine atom, a bromine atom, or an iodine atom;
When Y ¹ and Y ² are hydroxy groups, the compound becomes a dicarboxylic acid, and the compound is used as a raw material monomer for producing polyesters and polyester carbonates. When Y ¹ and Y ² are alkoxy groups, the compound becomes an ester of dicarboxylic acid, and the compound is used as a raw material monomer for producing polyesters and polyester carbonates. When ^Y1 and ^Y2 are a phenoxy group, a chlorine atom, a bromine atom or an iodine atom, the same applies to the alkoxy group.

The number of carbon atoms in the alkoxy group is preferably from 1 to 11, more preferably from 1 to 5, even more preferably from 1 to 3, from the viewpoints of inexpensive raw material procurement and reactivity during polymerization.
Among the chlorine atom, the bromine atom and the iodine atom, the chlorine atom is preferable from the viewpoint of inexpensive production.
Examples of the substituent that the alkoxy group may have include an alkyl group having 12 or less carbon atoms and an alkoxy group. Examples of the substituent that the phenoxy group may have include an alkyl group having 12 or less carbon atoms, an alkoxy group, an alkylthio group, and the like.

When L ¹ and L ² in formula (P23) are direct bonds, Y ¹ and Y ² are preferably a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, or a phenoxy group. In this case, "-L ⁵ -C(=O)-Y ¹ " and "-L ⁶ -C(=O)-Y ² " in formula (P23) are a carboxy group, a methoxycarbonyl group, an ethoxy A carbonyl group, a propoxycarbonyl group, and a phenoxycarbonyl group. In this case, it is possible to obtain the effects of inexpensive raw material procurement, ease of synthesis, reactivity during polymerization, and heat resistance and toughness of the resulting resin.

The compound represented by (P23) is preferably any one selected from compounds represented by the following formulas (P24) to (P33). In this case, the compound can be easily produced by the below-described production method. Also, in this case, effects such as heat resistance, toughness, and low water absorption are obtained.

(In formulas (P24) to (P33), L ⁵ , L ⁶ , m, Y ¹ and ^{Y 2} have the ^same definitions as in formula (23). represents an integer of 0 to 12. n24 is an integer of 0 to 6, n25 and n33 are integers of 0 to 11, n26 and n27 are integers of 0 to 9, and n28 is an integer of 0 to 7. , n29 is an integer from 0 to 13, and n30 to n32 are integers from 0 to 5.)

In formulas (P24) to (P33) above, R ^5a , R ⁶ and n24 to n33 are synonymous with R ^1a , R ² and n2 to n11 in formulas (P2) to (P11), respectively.

When the compound of the present invention is represented by the formula (P24), it has a moderately rigid skeleton, so effects of minimal heat resistance and high toughness can be obtained.

When the compound of the present invention is represented by the formula (P25), it has two rigid norbornene skeletons, so effects such as high heat resistance, surface hardness, and low photoelastic coefficient can be obtained.

When the compound of the present invention is represented by formula (P26), it has a well-balanced ring having a bridged structure, which is a rigid skeleton, and a ring without a bridged structure, and is non-polar due to ring condensation. Since it contains a large amount of , it is possible to obtain the effect of coexistence of heat resistance, surface hardness, photoelastic coefficient and toughness.

When the compound of the present invention is represented by formula (P27), it has a well-balanced ring having a bridged structure, which is a rigid skeleton, and a ring without a bridged structure, and a carbon atom that is non-polar due to ring condensation. Since it contains a large amount of , it is possible to obtain the effect of coexistence of heat resistance, surface hardness, photoelastic coefficient and toughness.

When the compound of the present invention is represented by the formula (P28), it has a moderately rigid skeleton, so that the effects of minimum heat resistance and high toughness can be obtained.

When the compound of the present invention is represented by the formula (P29), it has two rigid norbornene skeletons, so that effects such as high heat resistance, surface hardness, and low photoelastic coefficient can be obtained.

When the compound of the present invention is represented by the formula (P30), since it is composed of a flexible alicyclic structure, the effects of minimal heat resistance and high toughness can be obtained.

When the compound of the present invention is represented by the formula (P31), it has a rigid skeleton and a highly polar heteroatom, so that heat resistance and improved compatibility when blended with a different polymer can be obtained.

When the compound of the present invention is represented by the formula (P32), it has a rigid skeleton and a highly polar heteroatom, so that heat resistance and improved compatibility when blended with different polymers can be obtained.

When the compound of the present invention is represented by the formula (P33), since it is composed of a flexible alicyclic structure, the effects of minimal heat resistance and high toughness can be obtained.

Both R ^5a and R ⁶ in formulas (P24) to (P33) are preferably alkyl groups having 1 to 5 carbon atoms, more preferably methyl groups. In this case, the ratio of the rigid skeleton in the compound skeleton is increased, so that the effect of high heat resistance can be obtained.

Further, m and n24 to n33 in formulas (P24) to (P33) are preferably 0 or 1. In this case, the ratio of the rigid skeleton in the compound skeleton is increased, so that the effect of high heat resistance can be obtained.

Among formulas (P24) to (P33), any one selected from compounds of (P24) to (P29) is preferable. In this case, it has a rigid norbornene skeleton and a flexible alicyclic structure, and the effect of achieving both heat resistance and toughness can be obtained. Furthermore, the formula (P26) is preferable from the viewpoint of easiness of synthesis and the viewpoint of compatibility between heat resistance and toughness.

The compound of the present invention is preferably any one selected from the following compound group (I), from the viewpoints that raw materials can be obtained at low cost and that the toughness and heat resistance of the resin can be improved.

In compound group (I), R is a hydrogen atom or a methyl group. Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group. Two R's are present in the compound group (I), and these may be the same or different. The two Rs in compound group (I) correspond to R ^5a and R ⁶ in formulas (P24) to (P27), formula (31) and formula (32), respectively.

From the viewpoint of obtaining a thermoplastic resin having excellent heat resistance, any one selected from the following compound group (I-1) among the compound group (I) is preferable.

[Method for synthesizing compound]
The method for producing the compound of the present invention is not particularly limited.
For example, in the formula (P23) representing the compound of the present invention, -C(=O)-Y ¹ , - Dihydroxy compounds can be prepared in which C(=O)-Y ² is a hydroxy group.

<Synthesis of dihydroxy compound>
Dihydroxy compounds in which -C(=O)-Y ¹ and -C(=O)-Y ² in formula (P23) are hydroxy groups are produced by the following production methods A to C.

In Production Methods A to C, compound (M1) is a compound having a cyclopentadiene skeleton (that is, cyclopentadienes) and has two double bonds in the five-membered alicyclic structure. The details of R ⁵ and m in compound M1 are the same as in formula (P23). Ring Z1 represents an alicyclic carbocyclic ring having 6 to 15 carbon atoms and two double bonds in the alicyclic carbocyclic skeleton. This alicyclic carbocyclic ring may have a substituent, may contain a heteroatom, or may have a condensed ring. The details of the substituent, heteroatom, and condensed ring are the same as those of the ring Z in the above formula (P23), that is, the formula (P1).

In production methods A to C, ring Z2 represents an alicyclic carbocyclic ring having 6 to 15 carbon atoms and having one double bond in the alicyclic carbocyclic skeleton. This alicyclic carbocyclic ring may have a substituent, may contain a heteroatom, or may have a condensed ring. The details of the substituent, heteroatom, and condensed ring are the same as those of the ring Z in the above formula (P23), that is, the formula (P1).

In Production Methods A to C, M ¹ and M ² are each independently a direct bond or a divalent hydrocarbon group having 1 to 4 carbon atoms. The hydrocarbon group may have a substituent having 1 to 5 carbon atoms. A divalent hydrocarbon group is specifically an alkylene group. The details of L ⁵ and L ⁶ are the same as in formula (P23) above.

As shown in Production Method A, compound (M3) is produced from compound (M1) having an unsaturated bond and compound (M2). Specifically, two unsaturated molecules having 2m and 2n π-electrons, such as the compound (M1) and the compound (M2), are prepared in the presence of a transition metal active species (specifically, a metal catalyst). , two metal-carbon bonds and one carbon-carbon bond are formed and cyclized to form a metallacycle (not shown). At this time, the oxidation state of the metal center is formally doubled. Carbon-carbon bonds are then formed via reductive elimination and the oxidation state of the transition metal center is reduced to regenerate the active species. As a result, multiple reactions such as multimerization of unsaturated molecules proceed. At this time, when Pd or Ni is used, a four-membered ring is formed (Kenji Ito, "Cycloaddition Reaction Utilizing Organic Transition Metal Complexes", 2002, vol.60, NO.1, See p.28-p.41). Also, in the case of using an Fe catalyst, a four-membered ring is formed from two unsaturated molecules (Jordan M. Hoyt et al., "Iron-Catalyzed Intermolecular [2+2] Cycloadiene Iron-catalyzed intermolecular [2+2] cycloadditions of unactivated alkenes", "Science", VOL.349, ISSUE6251, August 28, 2015, p.960-p .963). Also, in unsaturated structures with heteroatoms at bridgehead positions or other positions, such as 1,4-dihydro-epoxynaphthalene, the use of Ni leads to the formation of four-membered rings (Daw -Jen Huang) et al., "[2+2] Dimerization of norbornadiene and its derivatives in the presence of nickel complexes and zinc metal ([2+2] Dimerization of norbornadiene and its derivatives in the presence of nickel complexes and zinc metal", "Journal of Organometallic Chemistry", 490, 1995, C1-C7).

In the production methods shown in Production Methods A to C, compound (M1) is a cyclic diene compound having a cyclopentadiene skeleton. As the compound (M2), the compound (M5), and the compound (M8), compounds having a distorted unsaturated bond such as a norbornene skeleton can be used. By using a compound having a cyclopentadiene skeleton and a compound having a norbornene skeleton as raw materials, the reactivity of the raw materials is increased, and the four-membered ring structure of formula (P23) (specifically, cyclobutane) is easily formed. Become.

A compound having a distorted unsaturated bond such as a norbornene skeleton forms a four-membered ring by using a photocyclization reaction. In fact, dicyclopentadiene is known to dimerize by light irradiation in the presence of a metal catalyst (Robert G. Salomon et al.), "Copper Catalysis in Photocycloadditions - I. Norbornene (Copper(I) catalysis in photocycloadditions. I. Norbornene)" Journal of the American Chemical Society 1974, 96, 4, p. 1137). Therefore, the photocyclization reaction can also be used to prepare compounds having a four-membered ring structure.However, the photoreaction generally results in low yields, and a four-ring structure as shown in Processes A to C and FIG. It is not suitable for the synthesis of alicyclic compounds having asymmetric structures with respect to membered rings.

Production method A is a method in which compound (M1) and compound (M2) are used as starting materials for the cyclization reaction. In production method A, compound (M1) and compound (M2) undergo a cyclization reaction to obtain compound (M3). Then, an oxo reaction gives a compound (M4) in which an aldehyde is added to the compound (M3). Thereafter, a compound (P23-1) is obtained by a hydrogenation reaction (that is, reduction reaction) of the compound (M3).

In production method A, Pd(dba) ₂ , Pd(acac) ₂ , Pd(PPh ₃ ) ₄ and PdCl 2 (PPh ₃ ) are used as transition metal catalysts for the cyclization reaction between compound (M1) and compound ( _M2 ). ₂ , PdCl ₂ (dppp), PdCl ₂ (H ₂ NCH ₂ CH ₂ NH ₂ ), NiCl ₂ , NiBr ₂ , NiCl ₂ (PPh ₃ ) ₂ , Ni(Cod) ₂ and the like are used. As ligands, P(p-tolyl) ₃ , PPh ₃ , P[(p-MeO)Ph] ₃ , P(Cy) ₃ and the like are used, but ligands may not be used. Zinc, for example, can be used as the reducing agent. The reaction temperature is, for example, 60-200°C. Acetonitrile, tetrahydrofuran (that is, THF), toluene, xylene, trimethylbenzene, tetralin, decalin, and the like are used as solvents. When using a solvent with a low boiling point, pressure may be applied, and the reaction is carried out under pressure conditions of, for example, 0.5 MPa to 10 MPa. Acetic acid, propionic acid, 4-methoxybenzoic acid, benzoic acid, formic acid, chloroacetic acid, trifluoroacetic acid, pyridinium p-toluenesulfonate (i.e., PPTS), tosylic acid, methanesulfone were used to adjust the pH during the reaction. Acid or the like is used.

For example, by oxo reaction compound (M3) gives compound (M4) in which ^M1 and ^M2 in process A are a direct bond. The reaction temperature is, for example, 20-200°C. The rhodium compound used in this step does not depend on the form of its precursor as long as it forms a complex with an organophosphorus compound and exhibits hydroformylation activity in the presence of hydrogen and carbon monoxide. That is, catalyst precursor materials such as Rh(acac)(CO) ₂ , Rh ₂ O ₃ , Rh ₄ (CO) ₁₂ , Rh ₆ (CO) ₁₆ and Rh(NO ₃ ) ₃ are reacted together with organophosphorus compounds. It may be introduced into the mixture to form a rhodium metal hydridocarbonyl phosphorus complex having catalytic activity in the reaction vessel, or a rhodium metal hydridocarbonyl phosphorus complex catalyst may be prepared in advance and introduced into the reaction vessel. . A preferred amount of the rhodium catalyst is 50 to 50000 ppm, more preferably 50 to 2000 ppm, as rhodium metal relative to the raw material compound (M3). The molar ratio of ligand to rhodium metal (ligand/rhodium) ranges from 1-50. In addition, phosphines represented by P(-R ^a )(-R ^b )(-R ^c ) and phosphites represented by P(-OR ^a )(-OR ^b )(-OR ^c ) . Specific examples of R ^a , R ^b , and R ^c include an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted alicyclic alkyl group having 1 to 12 carbon atoms, and 1 to 1 carbon atoms. There are 12 optionally substituted aryl groups. Specific examples of suitable phosphites used in this step include tris(2-t-butylphenyl)phosphite, tris(3-methyl-6-t-butylphenyl)phosphite, tris(3-methoxy- 6-t-butylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, di(2-t-butylphenyl)t-butylphosphite and the like. It is not limited to these phosphines and phosphites. Moreover, these phosphites may be used alone, or two or more of them may be used in combination. Examples of the solvent include methylcyclohexane, cyclohexane, toluene, xylene, trimethylbenzene, aliphatic hydrocarbons having 5 or more carbon atoms, ethylbenzene, propanol, and butanol. The pressure conditions during the reaction are, for example, 1 MPa to 15 MPa. The molar ratio of hydrogen to carbon monoxide in the hydrogen/carbon monoxide mixed gas used for the reaction is preferably in the range of 0.2 to 5.0 as the introduced gas composition (hydrogen/carbon monoxide). (M4) containing an aldehyde group is in no way limited to the oxo reaction and may be carried out by other known reactions.

Compound (M4) can be converted to compound (P23-1) by reduction reaction. As transition metal catalysts, as catalysts for hydrogen reduction, preferred Rh catalysts in the above-mentioned oxo reaction, nickel, cobalt, ruthenium, palladium, platinum, etc. having a known hydrogen reduction ability Group VIII of the periodic table and copper chromite , copper-zinc can be used. These metal catalysts can be used in the form of simple metals, metal oxides, silica, alumina, diatomaceous earth, carbon, or other inorganic carriers, or in the form of metal complexes. Among these hydrogenation catalysts, Rh catalyst, Raney nickel, nickel/diatomaceous earth, copper chromite, ruthenium/carbon, and ruthenium/alumina catalyst are particularly preferably used from the viewpoint of hydrogen reduction reaction rate and catalyst separation after reaction. be. Examples of the solvent include methylcyclohexane, cyclohexane, toluene, xylene, trimethylbenzene, aliphatic hydrocarbons having 5 or more carbon atoms, ethylbenzene, propanol, and butanol. The pressure conditions during the reaction are, for example, 1 MPa to 15 MPa. As the ligand, a ligand preferable for the oxo reaction may be used, or no ligand may be used. The molar ratio of hydrogen to carbon monoxide in the carbon monoxide mixed gas is preferably in the range of 0.2 to 5.0 as the introduced gas composition (hydrogen/carbon monoxide), or only hydrogen gas is used. In addition, hydrogen reduction can also be performed without quenching after the oxo reaction. In that case the same catalyst as in the oxo reaction step or another preferred catalyst is added. Synthesis of (P23-1) from (M4) containing an aldehyde group is not limited to the above hydrogen reduction reaction, and may be carried out by other known reactions. Examples thereof include reduction reactions using a reducing agent such as sodium borohydride. A reducing agent such as sodium borohydride is used together with the solvent used in the reduction step described above or an alcoholic solvent such as methanol or ethanol.

Abbreviations for ligands have the following meanings.
dba: dibenzylideneacetone acac: acetylacetonate PPh: phenylphosphine dppp: diphenylphosphinopropane tolyl: methylphenyl group Cy: cyclohexyl group Me: methyl group Ph: phenyl group

Production method B is a method using compound (M1) and compound (M5) as starting materials for the cyclization reaction. Unlike the compound (M2) in the production method A, the compound (M5) in the production method B has only one unsaturated bond, so the excessive cyclization is suppressed in the production method B. In this respect, it is preferable to carry out the manufacturing method B. A compound (M6) is obtained by a cyclization reaction of the compound (M1) and the compound (M5). Then, compound (M7) is obtained by adding aldehyde to compound (M6) by, for example, an oxo reaction. Then, a compound (P23-1) is obtained by a hydrogenation reaction of the compound (M7). The reaction conditions for the cyclization reaction, the oxo reaction, and the hydrogenation reaction are the same as in the production method A.

Production method C is a method using compound (M1) and compound (M8) as starting materials for the cyclization reaction. Unlike compound (M2) of production method A, compound (M8) of production method C has only one unsaturated bond, so overcyclization is suppressed in production method C. In this respect, it is preferable to carry out manufacturing method C. Compound (M9) is obtained by cyclization reaction of compound (M1) and compound (M8). Then, compound (M10) is obtained by adding aldehyde to compound (M9) by, for example, an oxo reaction. Then, the compound (P23-1) is obtained by hydrogenation reaction of the compound (M10). The reaction conditions for the cyclization reaction, the oxo reaction, and the hydrogenation reaction are the same as in the production method A.

In production methods A to C, substituents that ring Z1, ring Z2, and ring Z may have are omitted. By using the compound, a compound (P23-1) in which a substituent is bonded to the alicyclic carbocyclic ring of ring Z can be produced.

<Synthesis of Dicarboxylic Acid>
When the compound represented by formula (P23) is dicarboxylic, that is, when Y ¹ and Y ² in formula (P23) are hydroxy groups, the compound can be produced, for example, by the reaction shown in the following reaction scheme. be. As shown in the reaction formula below, a compound composed of a dicarboxylic acid (specifically, compound (P23-2)) is, for example, compound (M4) in production method A, compound (M7) in production method B, compound (M7) in production method C ( M10) is obtained by oxidation.

The reaction conditions for obtaining the dicarboxylic acid are as follows. Potassium permanganate, chromic acid, hypochlorite, hypobromite, oxygen, peroxide and the like are used as the oxidizing agent. As the solvent, depending on the oxidizing agent, water, hydrocarbon solvents having 5 or more carbon atoms such as benzene, toluene, xylene, trimethylbenzene, methylcyclohexane, cyclohexane, nitrile solvents such as acetonitrile, acetone, acetic acid, N, N A highly polar solvent such as -dimethylformamide and N,N-dimethylacetamide, a halogen solvent such as methylene chloride, or the like may be used, or the reaction may be carried out without a solvent.

<Synthesis of diester>
When the compound represented by formula (P23) is a diester, that is, when Y ¹ and Y ² in formula (P23) are an alkoxy group or a phenoxy group, the compound is represented by, for example, the following reaction formula Manufactured by reaction. As shown in the reaction formula below, a compound composed of a diester (specifically, compound (P23-3)) can be, for example, compound (P23-2) in the above reaction formula and various alcohols (specifically, R ^d OH , R ^e OH). As a result, the dicarboxylic acid in compound (P23-2) is esterified to give compound (P23-3). R ^d and R ^e may be the same or different and represent a hydrocarbon group such as an alkyl group or a phenyl group.

The reaction conditions for esterification are as follows. As the condensing agent, Bronsted acids such as tosylic acid and sulfuric acid, carbonyldiimidazole, which is an imidazole-based condensing agent, and N,N'-dicyclohexylcarbodiimide, which is a carbodiimide-based condensing agent, are used. Examples of the solvent include water, hydrocarbon solvents having 5 or more carbon atoms such as benzene, toluene, xylene, trimethylbenzene, methylcyclohexane and cyclohexane, and nitrile solvents such as acetonitrile. As other reaction conditions, sulfonyl chloride is used, and after conversion to an acid chloride, esterification can be performed by adding an alcohol.

Examples of the compounds of the present invention represented by formula (P23) include compounds represented by the above formulas (P26), (P24), (P25), (P27), (P31) and (P32). The raw materials used are shown below. In the following, for convenience, R ^5a is described as "R ⁵ ", and n24 to n32 are described as "n".

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded. "%" indicates "% by mass" unless otherwise specified.
[Synthesis Example of Condensed Alicyclic Carbocyclic Ring-Containing Compound]
[Synthesis Example 1: Synthesis of DA13]
<Synthesis of decahydro-4,8-methanocyclopenta “3,4” cyclobuta “1,2-f” indene>

Under nitrogen atmosphere, cyclopentadiene (200 g, 3.03 mol), tris-p-tolylphosphine (41 g, 136 mmol), acetic acid (550 mL), acetonitrile (250 mL), Pd(dba) ₂ (26 g, 45.4 mmol) It was added to the autoclave, and the inside of the autoclave was stirred at 100° C. for 3 hours. Water (2000 mL) was added to the reaction solution in the autoclave, petroleum ether (1500 mL) was added, and extraction was repeated three times. The organic layer was then concentrated and purified by column chromatography. As a result, 110 g of an isomer mixture of decahydro-4,8-methanocyclopenta "3,4" cyclobuta "1,2-f" indene was obtained. The analysis results of ¹ H NMR are as follows.

¹ H NMR (400 MHz, CDCl ₃ ): δ=5.70-5.75 (m, 2H), 5.63-5.70 (m, 2H), 5.54 (dd, J=5.6, 2.0 Hz, 2H), 5.37-5.45 (m, 2H), 2.97 (dqt, J = 10.4, 5.2, 5.2, 5.2, 2.4, 2. 4Hz, 2H), 2.74 (br, J = 3.2Hz, 1H), 2.63-2.69 (m, 1H), 2.53-2.63 (m, 2H), 2.46- 2.53 (m, 2H), 2.14-2.28 (m, 6H), 2.12 (td, J = 4.8, 2.4Hz, 6H), 1.99-2.06 (m , 2H), 1.94 (br, J = 6.4 Hz, 1H), 1.78-1.88 (m, 2H), 1.67-1.73 (m, 1H), 1.46 (tt , J=2.4, 1.2 Hz, 1 H) 1.44 (dt, J=3.6, 1.2 Hz, 1 H)

<Synthesis of tetradecahydro-4,8-methanocyclopenta “3,4” cyclobuta “1,2-f” indene-dicarbaldehyde>

In a stainless steel autoclave (reactor) with an internal volume of 300 mL, decahydro-4,8-methanocyclopenta "3,4" cyclobuta "1,2-f" indene 45.7 g (230 mmol), Rh (acac) (CO) ₂ 0.12 g (0.47 mmol), tris(2,4-di-t-butylphenyl)phosphite 1.37 g (2.1 mmol) and methylcyclohexane 145 mL were charged, and the reactor was sealed. After replacing the inside of the reactor with nitrogen, it is replaced with water gas (specifically, a mixed gas with a molar ratio of CO/H ₂ =1/1), and the water gas is added so that the internal pressure in the reactor becomes 1 MPa. filled up to The contents of the reactor were heated and stirred to bring the internal temperature to 70° C., and water gas was injected until the internal pressure reached 5 MPa. The water gas consumed in the reaction was continuously supplied from a pressure accumulator through a pressure regulator, and the reaction was carried out at 70° C. for 6 hours while maintaining the internal pressure at 5 MPa.

The recovered reaction liquid was extracted four times with 100 ml of a mixed liquid of methanol and water. The blending ratio of the mixed liquid is methanol/water=4/1 by volume. Methanol was distilled off under reduced pressure from the recovered aqueous solution containing methanol to obtain an aqueous phase. The aqueous phase was extracted three times with 100 mL of toluene. The toluene solution was dried over anhydrous Na ₂ SO ₄ , the drying agent was filtered off and the filtrate was concentrated to give a pale yellow oil. ¹ H NMR confirmed that this oil was an isomer mixture of tetradecahydro-4,8-methanocyclopenta "3,4" cyclobuta "1,2-f" indene-dicarbaldehyde. The yield was 58.0 g (224 mmol) and the yield was 97.6%. The analysis results of ¹ H NMR analysis are as follows.

¹ H NMR (400 MHz, CDCl ₃ ): δ=9.9-9.4 (m, 2H), 3.2-3.0 (m, 0.5H), 2.7-2.35 (m, 4H), 2.3-1.9 (m, 5.5H), 1.9-1.3 (m, 10H)

<Synthesis of tetrahydro-4,8-methanocyclopenta “3,4” cyclobuta “1,2-f” indene-diyl)dimethanol>

(Synthesis by hydrogenation reaction)
70.6 g (274 mmol) of tetradecahydro-4,8-methanocyclopenta "3,4" cyclobuta "1,2-f" indene-dicarbaldehyde, Ru/C2. 6 g (0.13 g as Ru, 1.2 mmol) and 100 mL of methanol were charged and the reactor was sealed. After the inside of the reactor was replaced with nitrogen, it was replaced with hydrogen, and the reactor was further filled with hydrogen until the internal pressure reached 1 MPa. The contents of the reactor were heated and stirred to bring the internal temperature to 90° C., and hydrogen was injected until the internal pressure reached 8 MPa. Hydrogen consumed in the reaction was continuously supplied from a pressure accumulator through a pressure regulator, and the reaction was carried out at 100° C. for 12 hours while maintaining the internal pressure at 8 MPa. The reaction solution was filtered through Celite to remove the catalyst, and the filtrate was concentrated using an evaporator. The residue was purified by column chromatography (filler: silica gel, solvent: hexane/ethyl acetate=1/1 (volume ratio)) to give a pale yellow oil. From the analysis results by ¹ H NMR and GC-MS, the oil was (tetradecahydro-4,8-methanocyclopenta "3,4" cyclobuta "1,2-f" indene-diyl) dimethanol (DA13). It was confirmed to be an isomer mixture. The yield was 19.0 g (72 mmol) and the yield was 26.3%.

¹ H NMR (400 MHz, CDCl ₃ ): δ=3.8-3.2 (m, 4H), 2.7-2.2 (m, 2H), 2.1-1.0 (m, 20H)
GC-MS (CI+, _NH3 ) [M+ _NH4 ] ⁺ m/z: 280, M ⁺ = 262
_{C17H26O2 molecular} weight _262.4

GC-MS (gas chromatography-mass spectrometry) measurements were carried out as follows. Note that ionization was performed by the CI method, and ammonia was used as a reagent gas. The injection temperature was 250°C, and the analysis temperature was raised from 50°C at a rate of 10°C/min, maintained at 220°C for 10 minutes, and then raised at a rate of 15°C/min to 300°C. The GC used was Agilent Technology 7890, and the column was DB-1 (0.25 mmφ×30 m, film thickness 0.25 μm) manufactured by Agilent Technologies.

(Synthesis with _NaBH4 reduction)
A dropping funnel was attached to a 500 mL three-necked flask containing a rotor. 31.1 g (120 mmol) of tetradecahydro-4,8-methanocyclopenta "3,4" cyclobuta "1,2-f" indene-dicarbaldehyde and 150 mL of methanol were placed in a flask and stirred, followed by adding ice. The flask was cooled in a bath so that the internal temperature of the flask reached 0°C. From the dropping funnel, 3.6 g (90 mmol) of sodium borohydride (95% purity) was dissolved in 20 mL of a 1% NaOH aqueous solution, and the aqueous solution was added dropwise into the flask over 40 minutes. Stirred. The reaction solution in the flask was cooled in an ice bath, and 30 mL of 15% sulfuric acid was added to the reaction solution to decompose sodium borohydride remaining in the reaction solution. The reaction solution was concentrated under reduced pressure to obtain a residue. 300 mL of ethyl acetate and 100 mL of water were added to the residue to separate and recover the oil phase, and the aqueous phase was extracted twice with 100 mL of ethyl acetate. Anhydrous Na ₂ SO ₄ (ie, desiccant) was added to the oil phase for dehydration, followed by filtration to remove the desiccant. Then, the oil phase was concentrated with an evaporator to obtain a concentrate. Inorganics were removed from the concentrate by chromatography using SiO ₂ as filler and acetone as solvent, and the concentrate was concentrated on an evaporator to give a pale yellow oil.

From the results of ¹ H NMR analysis, this oil was (tetradecahydro-4,8-methanocyclopenta "3,4" cyclobuta "1,2-f" indene-diyl) dimethanol (DA13). confirmed. The yield was 30.2 g (115 mmol) and the yield was 96.0%. The results of ¹ H NMR analysis of the above oil are as follows.

¹ H NMR (400 MHz, CDCl ₃ ): δ=3.8-3.2 (m, 4H), 2.7-2.2 (m, 2H), 2.1-1.0 (m, 20H)

[Synthesis Example 2: Synthesis of TCPDC]

A three-way cock connected to an N2 line was attached to a 1000 mL three-necked flask, and a rotor was placed. 10.0 g (38.7 mmol) of the above dialdehyde compound and 400 mL of N,N-dimethylformamide were charged, the inside of the reactor was replaced with N ₂ , and the inside temperature was cooled to 5° C. with a cooling bath. 5.2 g (8.5 mmol, 16.9 mmol as potassium persulfate) of oxone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., monopersulfate compound) was added thereto as a solid. The ice bath was replaced with a water bath, and 36.4 g of oxone (59.2 mmol, 118.4 mmol as potassium persulfate) was added in 5 portions at an internal temperature of 15°C.

After completion of the reaction, a white solid produced by the reaction was filtered off by suction filtration. 5 mL of 1N-HCl, 400 mL of demineralized water and 100 mL of ethyl acetate were added to the filtrate to separate the phases, and the aqueous layer was extracted five times with 100 mL of ethyl acetate. The recovered oil phase was concentrated under reduced pressure using an evaporator and a rotary pump to obtain an oily concentrated residue. 50 mL of 1N-HCl and 100 mL of demineralized water were added, and the precipitated solid was collected by suction filtration, and this solid was repeatedly washed with demineralized water to remove inorganic salts. The solid washed with water was suspended in toluene, heated to azeotropically dehydrate to remove H ₂ O, and toluene was removed under reduced pressure to obtain a white suspension. A solid content in the suspension was collected by suction filtration and dried under reduced pressure to obtain a white solid. ¹ H NMR confirmed that this white solid was tetradecahydro-4,8-methanocyclopenta "3,4" cyclobuta "1,2-f" indene-dicarboxylic acid (TCPDC). The yield was 7.64 g (26.3 mmol) and the yield was 68.0%.

¹ H NMR (400 MHZ, CD ₃ COCD ₃ ): δ=11.5-9.5 (br, 2H), 3.26-3.14 (M, 0.5H), 2.72-2.40 ( M, 2H), 2.41-2.23 (M, 2.5H), 2.16-2.05 (M, 3H), 2.02-1.96 (M, 2H), 1.95- 1.77 (M, 6H), 1.60-1.50 (M, 2H), 1.50-1.25 (M, 2H)

<Synthesis Example 3: Synthesis of TCPDC- _Me2 >

A reflux condenser and a thermometer are attached to a 30 mL two-necked flask, a rotor is placed, TCPDC 0.1 g (0.34 mmol), methanol 20 mL, and concentrated sulfuric acid 0.1 mL are added, and the internal temperature is 70° C. for 1 hour in an oil bath. The mixture was heated and stirred. After completion of the reaction, the mixture was cooled in an ice bath and saturated sodium bicarbonate solution was added to adjust the mixture to pH=7. Methanol was distilled off with an evaporator, 10 mL of toluene and 10 mL of desalted water were added to the residue to separate the phases, and the aqueous phase was extracted twice with 10 mL of toluene. The recovered oil phase was washed with 10 mL of desalted water and 10 mL of saturated saline, dehydrated over anhydrous MgSO ₄ , and filtered to remove the dried material. The filtrate was distilled off under reduced pressure using an evaporator, and dried using a rotary pump to recover a pale yellow oil.

¹ H NMR confirmed that this oil was tetradecahydro-4,8-methanocyclopenta“3,4”cyclobuta“1,2-f”indene-dimethyldicarboxylate (TCPDC-Me ₂ ). The yield was 0.08 g (0.25 mmol) and the yield was 73.5%.

¹ H NMR (400 MHZ, CDCL ₃ ): δ=3.72-3.62, (S×6,6H), 3.2-3.1 (M, 0.5H), 2.68-2.38 (M, 3H), 2.30-1.90 (M, 5.5H), 1.85-1.45 (M, 10H), 1.43-1.30 (M, 1H)

[Production and Evaluation of Polyester]
[Evaluation method]
The physical properties and properties of the thermoplastic resin compositions and molded articles were evaluated by the following methods.

(1) Formation of press film A polyester resin was vacuum-dried at 90°C for 5 hours or longer. A spacer was prepared by hollowing out a metal plate (SUS) having an outer width of 10 cm long and 10 cm wide and a thickness of 0.5 mm or 0.2 mm, leaving a width of 1 cm and an inner width of 8 cm long and 8 cm wide. This spacer was sandwiched between two mirror-finished stainless steel plates measuring 10 cm long, 10 cm wide and 1.5 mm thick, and about 4 g of pellets were placed in the frame of the spacer and hot pressed. The hot press temperature was 200 to 230° C., the preheating time was 5 to 8 minutes, and the pressure during molding was 20 MPa. Pressurization time during molding is 3 minutes. After hot-pressing, the sheet-like sample was taken out together with the specular plate and the spacer, and cooled under pressure of 10 MPa for 3 minutes in a water tube cooling press to prepare a film.

(2) Production of extruded film The polyester resin was dried at 120°C for 12 hours in a nitrogen atmosphere, and a film was formed under the following conditions using a film forming apparatus (ME-20/26V2 & CR-7 & FS-5) (manufactured by OCS). .
Cylinder temperature (nozzle-under hopper): 260°C-290°C-290°C-290°C
Screw rotation speed: 68 rpm
Resin pressure: 28 MPa
Chill roll temperature: 45°C
Film thickness: 100 μm

(3) Glass transition temperature Tg
The glass transition temperature was measured using a differential scanning calorimeter "EXSTAR 6220" manufactured by SII Nanotechnology. Measured according to JISK7121:1987. Specifically, in the case of amorphous resin, about 10 mg of the measurement sample is heated from 20 ° C. at a temperature increase rate of 20 ° C./min, the sample heated to 250 ° C. is rapidly cooled with liquid nitrogen, and the temperature is raised again. The temperature was raised to 250°C at a rate of 10°C/min. A straight line equidistant in the vertical axis direction from the straight line obtained by extending the baseline on the lower temperature side and the baseline on the higher temperature side than the DSC data obtained in the second temperature rise, and the curve of the stepwise change portion of the glass transition. From the intersecting temperature, the midpoint glass transition start temperature is determined. This midpoint glass transition starting temperature is treated as the glass transition temperature Tg.
In the case of a crystalline resin, about 10 mg of the measurement sample is heated from 20 ° C. at a temperature increase rate of 10 ° C./min, heated to 290 ° C., cooled to 20 ° C. at a temperature decrease rate of 10 ° C./min, and raised again. The temperature was raised to 290°C at a temperature rate of 10°C/min. A straight line equidistant in the vertical axis direction from the straight line obtained by extending the baseline on the lower temperature side and the baseline on the higher temperature side than the DSC data obtained in the second temperature rise, and the curve of the stepwise change portion of the glass transition. From the intersecting temperature, the midpoint glass transition start temperature is determined. This midpoint glass transition starting temperature is treated as the glass transition temperature Tg.

(4) Reduced Viscosity A solution having a concentration of 1.00 g/dl was prepared by dissolving the polyester resin using a solvent. A mixed solvent of phenol and 1,1,2,2-tetrachloroethane was used as the solvent. The mixing ratio of phenol and 1,1,2,2-tetrachloroethane is 1:1 by mass. The dissolution in the mixed solvent was performed over 30 minutes while stirring at 110° C., and the solution after cooling was used for measurement of the reduced viscosity. The measurement of the reduced viscosity was performed at a temperature of 30.0°C ± 0.1°C using an Ubbelohde viscometer "DT-504 automatic viscometer" manufactured by Chuo Rika Co., Ltd. Relative viscosity η _rel is calculated by the following formula _{(α) from the passage time t of the solvent and the passage time t of the solution, and the specific viscosity η sp ( unit} : g cm ⁻¹ ·sec ⁻¹ ) was calculated. Note that η ₀ in the formula (β) is the viscosity of the solvent. Then, the reduced viscosity _η (η=η _sp /c) was calculated by dividing the specific viscosity η sp by the solution concentration c (g/dL). A higher value means a higher molecular weight.
η _rel =t/t ₀ (α)
η _sp = (η - η ₀ )/η ₀ = η _rel -1 (β)

(5) Photoelastic coefficient <Sample preparation>
A sample having a width of 5 mm and a length of 20 mm was cut from the pressed film prepared by the method (1) or the extruded film prepared by the method (2).
<Measurement>
Measured using a device that combines a birefringence measuring device consisting of a He—Ne laser, a polarizer, a compensator, an analyzer, and a photodetector and a vibrating viscoelasticity measuring device (manufactured by UBM) (for details, see Japan Rheology Society Vol.19, p93-97 (1991)). The cut sample was fixed to a viscoelasticity measuring device, and the storage elastic modulus E′ was measured at a room temperature of 25° C. and a frequency of 96 Hz. At the same time, the emitted laser light is passed through a polarizer, a sample, a compensator, and an analyzer in this order, picked up by a photodetector (photodiode), and passed through a lock-in amplifier to obtain a waveform with an angular frequency of ω or 2ω. A phase difference was determined, and a distortion optical coefficient O' was determined. At this time, the directions of the polarizer and the analyzer were orthogonal to each other, and adjusted to form an angle of π/4 with respect to the stretching direction of the sample. The photoelastic coefficient C was obtained from the following equation using the storage elastic modulus E' and the strain optical coefficient O'.
C=O'/E'

(6) Total Light Transmittance The press film prepared by the method (1) or the extruded film prepared by the method (2) was measured for total light transmittance using NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.). This machine complies with JIS K7361-1.

(7) Yellow Index (YI)
YI of the press film prepared by the method (1) or the extruded film prepared by the method (2) was measured according to ASTM D1925 using a colorimeter (ZE6000, manufactured by Nippon Denshoku Industries).

(8) Measurement of Refractive Index and Abbe Number A rectangular test piece having a length of 40 mm and a width of 8 mm was cut out from the film produced by the method of (1) to obtain a measurement sample. Using interference filters with wavelengths of 656 nm (C line), 589 nm (D line), 546 nm (e line), and 486 nm (F line), Atago Co., Ltd. Multi-wavelength Abbe refractometer DR-M4/1550 Each wavelength were measured for refractive indices nC, nD, ne and nF. The measurement was performed at 20° C. using monobromonaphthalene as the interfacial liquid. The Abbe number νD was calculated by the following formula.
νD = (1-nD)/(nC-nF)
The larger the Abbe number, the smaller the wavelength dependence of the refractive index.
In the following examples and comparative examples, those having a refractive index of 1.50 or more at a wavelength of 589 nm were evaluated as having a large refractive index and suitable for applications such as optical lenses.

[raw materials used]
The abbreviations and manufacturers of the compounds used in Production Examples and Examples are as follows.
<Dihydroxy compound>
・TCDDM: tricyclodecanedimethanol [manufactured by Oxair]
DA13: Dihydroxy compound synthesized in Synthesis Example 1 ((tetradecahydro-4,8-methanocyclopenta "3,4" cyclobuta "1,2-f" indene-diyl) dimethanol)
・Ethylene glycol: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

<Dicarboxylic acid ester>
・DMT: dimethyl terephthalate [manufactured by SK Chemicals]
・TCPDC: dicarboxylic acid compound synthesized in Synthesis Example 2 (tetradecahydro-4,8-methanocyclopenta “3,4” cyclobuta “1,2-f” indene-dicarboxylic acid)

<Catalyst>
・ CAA: Calcium acetate monohydrate [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]
・ TBT: Titanium tetrabutoxide [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]

<Comparative polyethylene terephthalate resin>
Homo polyethylene terephthalate resin (homo PET resin): "GM701Z" manufactured by Mitsubishi Chemical Corporation

[Example 1]
As raw materials, 6.36 g (0.0219 mol) of TCPDC, 4.02 g (0.0153 mol) of DA13, 2.04 g (0.0328 mol) of ethylene glycol (hereinafter abbreviated as “EG”), and After 2.13×10 ⁻³ g (6.26×10 ⁻⁶ mol) of titanium tetrabutoxide (hereinafter abbreviated as TBT) as a catalyst was charged into the reaction vessel as a 2% EG solution, the reaction vessel was purged with nitrogen. The reactor was immersed in a heating bath heated to 150° C. under a nitrogen atmosphere. As the first step of the reaction, the temperature was raised from 150° C. to 250° C. in 180 minutes under normal pressure while stirring, and the distilled water was collected. The raw materials were completely dissolved in the middle of the temperature rise. After the temperature was raised, the temperature was maintained at 250°C for 60 minutes to complete the first stage reaction. As the second step, the temperature of the heating bath was raised to 270° C. in 60 minutes. Simultaneously with the start of temperature rise, the pressure in the reaction vessel was gradually reduced while controlling the pressure from normal pressure to 0.200 kPa in 90 minutes, and the generated water was discharged out of the reaction vessel. The temperature was maintained at 270° C. and 0.200 kPa or less, and when a predetermined stirring torque was reached, the reaction was terminated, and the produced reactant was taken out from the reaction vessel to obtain a polyester copolymer.
The resulting polyester copolymer had a reduced viscosity of 0.357 dl/g and a glass transition temperature Tg of 121°C.
Using the press film prepared by the method of (1), when the refractive index is measured at 20 ° C., nC = 1.536, nD = 1.539, ne = 1.542, nF = 1.547, Abbe number νD is 49 Met. Further, the photoelastic coefficient was 12×10 ⁻¹² Pa ⁻¹ .

[Example 2]
As raw materials, 11.55 g (0.0595 mol) of DMT, 4.68 g (0.0178 mol) of DA13, 7.01 g (0.1130 mol) of EG, and 4.26×10 ⁻ of TBT as a catalyst. After charging ³ g (1.25×10 ⁻⁵ mol) of 2% EG solution into the reaction vessel, the reaction vessel was purged with nitrogen. The reactor was immersed in a heating bath heated to 150° C. under a nitrogen atmosphere. As the first step of the reaction, the temperature was raised from 150° C. to 250° C. in 180 minutes under normal pressure while stirring, and the distilled methanol was recovered. The raw materials were completely dissolved in the middle of the temperature rise. After the temperature was raised, the temperature was maintained at 250°C for 60 minutes to complete the first stage reaction. As the second step, the temperature of the heating bath was raised to 270° C. in 60 minutes. Simultaneously with the start of temperature rise, the pressure in the reaction vessel was gradually reduced while controlling the pressure from normal pressure to 0.200 kPa in 90 minutes, and the generated methanol was discharged out of the reaction vessel. The temperature was maintained at 270° C. and 0.200 kPa or less, and when a predetermined stirring torque was reached, the reaction was terminated, and the produced reactant was taken out from the reaction vessel to obtain a polyester copolymer.
The resulting polyester copolymer had a reduced viscosity of 0.907 dl/g and a glass transition temperature Tg of 101°C.
Using the press film prepared by the method of (1), when the refractive index is measured at 20 ° C., nC = 1.564, nD = 1.569, ne = 1.574, nF = 1.582, Abbe number νD is 32 Met. Further, the photoelastic coefficient was 85×10 ⁻¹² Pa ⁻¹ .

[Example 3]
As raw materials, 9.96 g (0.0513 mol) of DMT, 6.73 g (0.0257 mol) of DA13, 5.41 g (0.0872 mol) of EG, and calcium acetate (hereinafter abbreviated as CAA) as a catalyst. 6.59× ⁻³ g (3.74×10 ⁻⁵ mol) of TBT was added as a 2% aqueous solution, and 0.032 g (9.39×10 ⁻⁵ mol) of TBT was added directly to the reaction vessel. 2 was performed.
The optical properties were measured using the press film prepared by the method (1). The results are listed in Table 1.

[Example 4]
As raw materials, 8.76 g (0.0451 mol) of DMT, 8.29 g (0.0316 mol) of DA13, 4.20 g (0.0667 mol) of EG, and 6.59× ⁻³ of CAA as catalyst. g (3.74×10 ⁻⁵ mol) as a 2% aqueous solution and 3.20×10 ⁻³ g (9.39×10 ⁻⁶ mol) of TBT as a 2% EG solution were charged into the reaction vessel. It was carried out in the same manner as in Example 2.
The optical properties were measured using the press film prepared by the method (1). The results are listed in Table 1.

[Comparative Example 1]
As raw materials, 11.23 g (0.0579 mol) of DMT, 5.68 g (0.0289 mol) of TCDDM, 6.10 g (0.0983 mol) of EG, and 6.59× ⁻³ of CAA as catalyst. g (3.74×10 ⁻⁵ mol) as a 2% aqueous solution and 3.20×10 ⁻³ g (9.39×10 ⁻⁶ mol) of TBT as a 2% EG solution were charged into the reaction vessel. It was carried out in the same manner as in Example 2.
The optical properties were measured using the press film prepared by the method (1). The results are listed in Table 1.

[Comparative Example 2]
As raw materials, 12.32 g (0.0634 mol) of DMT, 4.11 g (0.0209 mol) of TCDDM, 7.36 g (0.1186 mol) of EG, and 6.59× ⁻³ of CAA as catalyst. g (3.74×10 ⁻⁵ mol) as a 2% aqueous solution and 3.20×10 ⁻³ g (9.39×10 ⁻⁶ mol) of TBT as a 2% EG solution were charged into the reaction vessel. It was carried out in the same manner as in Example 2.
The optical properties were measured using the press film prepared by the method (1). The results are listed in Table 1.

[Comparative Example 3]
Homo-PET resin: Optical properties were measured using an extruded film prepared by the method (2) using Mitsubishi Chemical's "GM701Z".
The results are listed in Table 1.

From Table 1, it can be seen that the polyester of the present invention has a high glass transition temperature, excellent heat resistance, a low photoelastic coefficient and excellent optical properties, does not have a melting point, and is inhibited from crystallization. Furthermore, since the diol and dicarboxylic acid have a three-dimensional structure, it is thought that the orientation of the polymer main chain is suppressed, resulting in a resin with low intrinsic birefringence.
In contrast, Comparative Examples 1 and 2 using tricyclodecanedimethanol as described in Patent Document 2 have a low glass transition temperature and poor heat resistance.
Comparative Example 3, which does not contain an alicyclic carbocyclic ring, is inferior in heat resistance, has a melting point, and is easily crystallized.

Claims (18)

A polyester having a repeating unit represented by the following formula (1A).

(A ¹ in formula (1) represents the following formula (P1), B ¹ is a substituted or unsubstituted linear or branched divalent group having 2 to 30 carbon atoms, substituted or an unsubstituted monocyclic or polycyclic aliphatic divalent group, or a substituted or unsubstituted monocyclic or polycyclic aromatic divalent group having 6 to 30 carbon atoms.)

(In formula (P1), ring Z represents a 6- to 15-membered alicyclic carbocyclic ring that may have a substituent, and the alicyclic carbocyclic ring is a monocyclic ring, a condensed ring, a bridged ring, or a combination thereof, and the alicyclic carbocycle may contain heteroatoms.
L ¹ and L ² each independently represent a direct bond or a divalent hydrocarbon group having 1 to 5 carbon atoms. R ¹ represents a substituent and m is an integer of 0-4. ) The polyester according to claim 1, wherein ^L1 and ^L2 in formula (P1) are each independently a direct bond or a methylene group. 3. The polyester according to claim 1, wherein the alicyclic carbocyclic ring of Z in the formula (P1) has at least one ring with 4 or more members. The polyester comprising the structure according to any one of claims 1 to 3, wherein the formula (P1) is any one selected from the following formulas (P2) to (P11).

(In formulas (P2) to (P11), L ¹ , L ² and m are the same as in formula (P1) above. R ^1a and R ² are each independently a substituent having 1 to 12 carbon atoms. n2 is an integer of 0 to 6, n3 and n11 are integers of 0 to 11, n4 and n5 are integers of 0 to 9, n6 is an integer of 0 to 7, n7 is 0 is an integer of ~13, and n8~n10 is an integer of 0~5.) The polyester according to any one of claims 1 to 4, which is a resin for optical applications. A polyester having a repeating unit represented by the following formula (1B).

(In formula (1B), B ² represents the following formula (P12), A ² is a substituted or unsubstituted linear or branched divalent group having 2 to 30 carbon atoms, a substituted or It is either an unsubstituted monocyclic or polycyclic aliphatic divalent group or a substituted or unsubstituted monocyclic or polycyclic aromatic divalent group having 6 to 30 carbon atoms.)

(In formula (P12), ring Z represents a 6- to 15-membered alicyclic carbocyclic ring that may have a substituent, and the alicyclic carbocyclic ring is a monocyclic ring, a condensed ring, a bridged ring, or a combination thereof, and the alicyclic carbocycle may contain heteroatoms.
L ³ and L ⁴ each independently represent a direct bond or a divalent hydrocarbon group having 1 to 5 carbon atoms. R ³ represents a substituent and m is an integer of 0-4. ) 7. The polyester according to claim 6, wherein ^L3 and ^L4 in formula (P12) are each independently a direct bond or a methylene group. 8. The polyester according to claim 6 or 7, wherein the alicyclic carbocyclic ring of Z in the formula (P12) has at least one ring with 4 or more members. The formula (P12) is any one selected from the following formulas (P13) to (P22),
The polyester according to any one of claims 6-8.

(In formulas (P13) to (P22), L ³ , L ⁴ and m are the same as in formula (P12). R ^3a and R ⁴ each independently represent a substituent having 1 to 12 carbon atoms. n13 is an integer of 0 to 6, n14 and n22 are integers of 0 to 11, n15 and n16 are integers of 0 to 9, n17 is an integer of 0 to 7, n18 is 0 to is an integer of 13, and n19 to n21 are integers of 0 to 5.) The polyester according to any one of claims 6 to 9, which is a resin for optical use. A compound represented by the following formula (P23).

(In formula (P23), ring Z represents a 6- to 15-membered alicyclic carbocyclic ring which may have a substituent other than —L ⁶ —C(═O)—Y ² , and the alicyclic ring Formula carbocycles are single rings, fused rings, bridged rings, or combinations thereof, and the alicyclic carbocycles may contain heteroatoms.
L ⁵ and L ⁶ each independently represent a direct bond or a divalent hydrocarbon group having 1 to 5 carbon atoms. R ⁵ represents a substituent and m is an integer of 0-4.
Y ¹ and Y ² are each independently a hydroxy group, an optionally substituted alkoxy group, an optionally substituted phenoxy group, a chlorine atom, a bromine atom, or an iodine atom. ) 12. The compound according to claim 11, wherein ^L5 and ^L6 in formula (P23) are each independently a direct bond or a methylene group. 13. The compound according to claim 11 or 12, wherein the alicyclic carbocyclic ring of Z in the formula (P23) has at least one ring with 4 or more members. The compound according to any one of claims 11 to 13, wherein the formula (P23) is any one selected from the following formulas (P24) to (P33).

(In formulas (P24) to (P33), L ⁵ , L ⁶ , m, Y ¹ and ^{Y 2} have the ^same definitions as in formula (23). represents an integer of 0 to 12. n24 is an integer of 0 to 6, n25 and n33 are integers of 0 to 11, n26 and n27 are integers of 0 to 9, and n28 is an integer of 0 to 7. , n29 is an integer from 0 to 13, and n30 to n32 are integers from 0 to 5.) The compound according to claim 14, wherein m and n24-n33 in formulas (P24)-(P33) are each independently 0 or 1. The compound according to claim 14 or 15, wherein said formula (P23) is any one selected from said formulas (P24) to (P29). 17. The compound according to claim 16, wherein said formula (P23) is said formula (P26). A method of producing a polyester through an esterification step of performing an esterification reaction or a transesterification reaction using a dicarboxylic acid component and a diol component, and a melt polycondensation reaction step of performing a polycondensation reaction of the oligomer obtained by the esterification step. 18. A method for producing a polyester, wherein the compound according to any one of claims 11 to 17 is used as at least part of the dicarboxylic acid component.