JP2022145644A - Thermoplastic resin, and production method and use for the same - Google Patents

Abstract

To provide a thermoplastic resin exhibiting a high refractive index and high heat resistance, and a production method and a use for the same.SOLUTION: A thermoplastic resin is a resin having a dicarboxylic acid unit (A) including at least a first dicarboxylic acid unit (A1) represented by the following formula (1), and is preferably thermoplastic polyester. In the formula, Z1 represents a monocyclic or condensed polycyclic arene ring, Z2 represents an arene ring, R1 and R2 represent substituents, k1 and k2 represent integers of 0 or more, and m represents an integer of 1 or more. In the formula (1), Z1 may be a monocyclic or condensed polycyclic C6-14 arene ring, Z2 may be a C6-14 arene ring, and m may be an integer of 1 to 3.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin containing a specific aromatic dicarboxylic acid component (arene dicarboxylic acid component) as a polymerization component, a method for producing the same, and uses thereof.

A method for producing a liquid crystalline polyester by melt polymerization or the like using an aromatic dicarboxylic acid component is known. As an aromatic dicarboxylic acid component, JP-A-2013-28700 (Patent Document 1) and JP-A-2013-28746 (Patent Document 2) describe an aromatic dicarboxylic acid component represented by the following formula (2). Have been described.

Formula (2): R ²¹ —CO—Ar ² —CO—R ²²
(wherein Ar ² represents a phenylene group, naphthylene group, biphenylylene group, etc., R ²¹ and R ²² represent a hydroxyl group, an alkoxyl group, an aryloxyl group, an acyloxyl group or a halogen atom, represented by Ar ¹ each hydrogen atom in said group may be substituted with a halogen atom, an alkyl group or an aryl group).

Further, Japanese Patent Application Laid-Open No. 2013-7004 (Patent Document 3) describes an aromatic dicarboxylic acid component represented by the following formula (2').

Formula (2′): G ² —CO—Ar ² —CO—G ²
(wherein Ar ² is a 2,6-naphthylene group, 1,4-phenylene group, 1,3-phenylene group or 4,4′-biphenylylene group; G ² is a hydroxyl group, an alkoxy group, an aryl an oxy group, an alkylcarbonyloxy group, or a halogen atom; one or more hydrogen atoms in said Ar ² may be independently substituted with a halogen atom, an alkyl group, or an aryl group).

Japanese Unexamined Patent Application Publication No. 2013-28700 JP 2013-28746 A Japanese Unexamined Patent Application Publication No. 2013-7004

In Examples of Patent Documents 1 to 3, liquid crystalline polyesters are prepared using terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, etc. as aromatic dicarboxylic acid components, and specific aromatic compounds having aryl groups are prepared. The use of dicarboxylic acid components is not envisioned. Moreover, Patent Documents 1 to 3 neither describe nor suggest that the obtained liquid crystalline polyester is used for optical applications such as optical members.

With the recent development of small or mobile devices (information terminals) such as smartphones and tablet PCs, the performance of optical members responsible for optical functions such as image display functions and camera functions of these devices is progressing. . Therefore, optical materials for forming such optical members are also required to have higher performance.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a thermoplastic resin exhibiting a high refractive index and high heat resistance, a method for producing the same, and uses thereof.

The inventors of the present invention have made intensive studies to achieve the above objects, and as a result, prepared a thermoplastic resin by using a specific aromatic dicarboxylic acid component having an aryl group (arene dicarboxylic acid component) as a polymerization component as the aromatic dicarboxylic acid component. As a result, the inventors have found that the resulting resin exhibits a high refractive index and high heat resistance, and completed the present invention.

That is, the thermoplastic resin of the present invention is a thermoplastic resin containing a dicarboxylic acid unit (A), wherein the dicarboxylic acid unit (A) is at least a first dicarboxylic acid represented by the following formula (1) It has the unit (A1).

(Wherein, Z ¹ represents a monocyclic or condensed polycyclic arene ring,
Z ² represents an arene ring, R ¹ represents a substituent, k1 represents an integer of 0 or more, m represents an integer of 1 or more,
^R2 represents a substituent and k2 represents an integer of 0 or more).

In the above formula (1), Z ¹ is a monocyclic or condensed polycyclic C _6-14 arene ring,
Z ² may be a C _6-14 arene ring and m may be an integer of 1-3.

In the formula (1), Z ¹ is a benzene ring or a naphthalene ring,
Z ² may be at least one arene ring selected from a benzene ring, a naphthalene ring and a biphenyl ring, and m may be an integer of 1-2. Also, the proportion of the first dicarboxylic acid units (A1) may be about 1 to 50 mol % with respect to the entire dicarboxylic acid units (A).

The dicarboxylic acid unit (A) may contain a second dicarboxylic acid unit (A2) represented by the following formula (2).

(Wherein, R ³ represents a substituent, k3 represents an integer of 0 to 8,
A ^1a and A ^1b independently represent a divalent hydrocarbon group optionally having a substituent).

In the formula (2), R ³ may be an aryl group, k3 may be an integer of 0 to 4,
A ^1a and A ^1b may be linear or branched alkylene groups.

The second dicarboxylic acid unit (A2) may contain at least a dicarboxylic acid unit (A2-2) in which R3 is an aryl group and ^k3 is an integer of 1 or more in the formula (2). good. The ratio of the dicarboxylic acid units (A2-2) may be, for example, about 1 to 100 mol % with respect to the entire second dicarboxylic acid units (A2).

The ratio of the first dicarboxylic acid unit (A1) to the second dicarboxylic acid unit (A2) may be about the former/latter (molar ratio)=5/95 to 90/10.

The dicarboxylic acid unit (A) may contain an aliphatic dicarboxylic acid unit as the third dicarboxylic acid unit (A3).

The third dicarboxylic acid unit (A3) may contain a structural unit derived from a linear or branched alkanedicarboxylic acid having 2 to 20 carbon atoms.

The ratio of the first dicarboxylic acid unit (A1) and the third dicarboxylic acid unit (A3) may be about the former/latter (molar ratio) = 5/95 to 90/10,
The ratio of the second dicarboxylic acid unit (A2) to the third dicarboxylic acid unit (A3) may be about the former/latter (molar ratio)=10/90 to 95/5.

The thermoplastic resin may be a polyester resin further containing a diol unit (B). The diol unit (B) is at least one selected from a first diol unit (B1) represented by the following formula (3) and a second diol unit (B2) represented by the following formula (4). may contain a diol unit of

(Wherein, R ⁴ represents a substituent, k4 represents an integer of 0 to 8,
Z ^3a and Z ^3b independently represent an arene ring,
R ^5a and R ^5b independently represent a substituent, k5a and k5b independently represent an integer of 0 or more,
A ^2a and A ^2b independently represent a linear or branched alkylene group, and n2a and n2b independently represent an integer of 0 or 1 or more. )

( ^In the formula, A3 represents a linear or branched alkylene group, and n3 represents an integer of 1 or more.)

In the formula (3), Z ^3a and Z ^3b are monocyclic or condensed polycyclic arene rings,
A ^2a and A ^2b are linear or branched C _2-6 alkylene groups, n2a and n2b may be integers of about 0 to 10,
In the above formula (4), A ³ may be a linear or branched C _2-6 alkylene group, and n3 may be an integer of about 1-4.

The diol unit (B) may contain both the first diol unit (B1) and the second diol unit (B2). Also, the ratio of the first diol unit (B1) to the second diol unit (B2) may be about the former/latter (molar ratio)=1/99 to 99/1. The weight average molecular weight Mw of the thermoplastic resin may be, for example, about 6,000 to 250,000, preferably about 10,000 to 200,000.

The present invention provides a method for producing the thermoplastic resin by polymerizing a polymerization component containing at least a first dicarboxylic acid component corresponding to the first dicarboxylic acid unit (A1); and a molded article containing the thermoplastic resin. encompasses The molded article may be an optical member such as an optical lens.

In addition, in the present invention, the following problems may be solved as secondary objects.

That is, another object of the present invention is to achieve both high refractive index and low birefringence (low absolute value of birefringence), which are optical characteristics that are trade-offs, in a well-balanced manner, and to achieve high heat resistance, which is in a trade-off relationship. It is an object of the present invention to provide a thermoplastic resin, a method for producing the same, and a use of the same, which are compatible with high moldability (or productivity) in a well-balanced manner.

Still another object of the present invention is to provide a thermoplastic resin that can be easily or efficiently prepared to have a high molecular weight even if it contains a polymer component with low reactivity (polymerization reactivity), a method for producing the same, and uses thereof. It is in.

In the present specification and claims, "dicarboxylic acid unit" and "structural unit derived from dicarboxylic acid component" are units (or divalent group), and "dicarboxylic acid component" (including compounds exemplified as dicarboxylic acid components) may be used synonymously with the corresponding "dicarboxylic acid unit". Similarly, the terms "diol unit" and "structural unit derived from a diol component" mean units (or divalent groups) obtained by removing hydrogen atoms from two hydroxyl groups of the corresponding diol component. "Diol component" (including compounds exemplified as diol components) may be used synonymously with the corresponding "diol unit."

In addition, in the present specification and claims, the term "dicarboxylic acid component" is used to include not only dicarboxylic acids but also ester-forming derivatives thereof. Examples of ester-forming derivatives include alkyl esters, acid halides such as acid chlorides, and acid anhydrides. The alkyl esters include lower alkyl esters such as C _1-4 alkyl esters such as methyl ester, ethyl ester and t-butyl ester. The ester-forming derivative may be monoester (half ester) or diester.

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

The thermoplastic resin of the present invention contains a specific arenedicarboxylic acid component having an aryl group as a polymerization component, and therefore has a high refractive index and high heat resistance. In general, as the number of aromatic ring skeletons (benzene ring skeletons) in the chemical structure increases, not only does the birefringence tend to increase, but also the glass transition point Tg tends to increase, resulting in a decrease in moldability (productivity). Therefore, high refractive index and low birefringence, as well as high heat resistance and high formability, are mutually exclusive properties. However, in the present invention, these characteristics can be satisfied in a well-balanced manner. Furthermore, although the specific arenedicarboxylic acid component having the aryl group is expected to have low polymerization reactivity due to the effects of steric hindrance due to the rigidity and bulkiness of the chemical structure, it can be easily or efficiently It can be well polymerized.

1 is a ¹ H-NMR spectrum of diethyl 2,5-di(2-naphthyl)terephthalate (DNTPA-E) obtained in Synthesis Example 1. FIG. 2 is a ¹ H-NMR spectrum of dimethyl 2-(2-naphthyl)terephthalate (MNTPA-M) obtained in Synthesis Example 1. FIG.

[Thermoplastic resin]
The thermoplastic resin may contain at least the first dicarboxylic acid unit (A1) represented by the following formula (1) as the dicarboxylic acid unit (A). Examples of such thermoplastic resins include polyamide-based resins and polyester-based resins. Polyester-based resins are preferable because they have low water absorbency and can be effectively used as optical members. Examples of polyester-based resins include polyester resins and polyester carbonate resins, and polyester resins are preferable from the viewpoint of moldability.

(Dicarboxylic acid unit (A))
First dicarboxylic acid unit (A1)

(Wherein, Z ¹ represents a monocyclic or condensed polycyclic arene ring,
Z ² represents an arene ring, R ¹ represents a substituent, k1 represents an integer of 0 or more, m represents an integer of 1 or more,
^R2 represents a substituent, and k2 represents an integer of 0 or more. )

In formula (1), the arene ring (aromatic hydrocarbon ring) represented by Z ¹ may be a monocyclic arene ring such as a benzene ring or a condensed polycyclic arene ring.

Condensed polycyclic arene rings include, for example, condensed bicyclic to tetracyclic arene rings such as condensed bicyclic arene rings and condensed tricyclic arene rings. The condensed bicyclic arene ring includes condensed bicyclic C _10-16 arene rings such as naphthalene ring and indene ring, and the condensed tricyclic arene ring includes anthracene ring and phenanthrene ring. A preferred fused polycyclic arene ring is a fused polycyclic C _10-16 arene ring, more preferably a fused polycyclic C _10-14 arene ring, with a naphthalene ring being particularly preferred.

Preferred Z ¹ is a monocyclic or condensed polycyclic C _6-14 arene ring, more preferably a benzene ring or a naphthalene ring, and has optical properties such as high refractive index, low Abbe number, low birefringence, high heat resistance, etc. A benzene ring is particularly preferred because it satisfies properties, high moldability and polymerization reactivity (or high molecular weight) in a well-balanced manner.

The binding position (substitution position) of the two carbonyl groups [-C(=O)-] (or two carboxyl groups in the corresponding dicarboxylic acid) forming the main chain of the thermoplastic resin to Z ¹ is not particularly limited, When Z ¹ is a benzene ring, for example, it may be in a 1,2-position (o-position), 1,3-position (m-position) or 1,4-position (p-position) relationship. The 1,4-position (p-position) is preferred from the viewpoint of satisfying properties, high heat resistance, high moldability and polymerization reactivity in a well-balanced manner.

The arene ring represented by Z ² includes, for example, monocyclic arene rings such as benzene ring, polycyclic arene rings, etc. Polycyclic arene rings include condensed polycyclic arene rings and ring assemblies An arene ring and the like are included.

Examples of the condensed polycyclic arene ring include rings similar to the condensed polycyclic arene rings exemplified in the section ^Z1 above. A preferred fused polycyclic arene ring is a fused polycyclic C _10-16 arene ring, more preferably a fused polycyclic C _10-14 arene ring, with a naphthalene ring being particularly preferred.

Examples of ring-assembled arene rings include biarene rings (or biaryl rings), tellarene rings (or teraryl rings), and the like. The biarene ring includes, for example, biC _6-12 arene rings such as biphenyl ring, binaphthyl ring and phenylnaphthalene ring. The phenylnaphthalene ring includes 1-phenylnaphthalene ring, 2-phenylnaphthalene ring and the like. The tellarene ring includes a tell C _6-12 arene ring such as a terphenyl ring. A preferred ring-assembled arene ring is a biC _6-10 arene ring such as a biphenyl ring.

In the present specification and claims, the term “ring-aggregated arene ring” means that two or more ring systems (monocyclic or condensed polycyclic arene ring system) are single bonds (single bonds) or double bonds. It means that the number of bonds directly connecting the rings is one less than the number of ring systems directly connected by a bond. Therefore, for example, a phenylnaphthalene ring, a binaphthyl ring, and the like are classified as ring-assembled arene rings as described above, and even if they have a condensed polycyclic arene ring skeleton, naphthalene rings (non-ring-assembled arene rings), etc. fused polycyclic arene ring”.

Preferred Z ² is a C _6-14 arene ring, specifically at least one arene ring selected from benzene ring, naphthalene ring and biphenyl ring, and has optical properties such as high refractive index, low Abbe number and low birefringence. A condensed polycyclic arene ring such as a naphthalene ring is more preferable because it can satisfy physical properties, high heat resistance, high moldability and polymerization reactivity (or high molecular weight) in a well-balanced manner. ^The size of Z2, that is, the ^number of carbon atoms (or the ^number of benzene ring skeletons) of Z2 may be the same as or smaller ^than Z1, but is preferably larger than Z1. If it is too large, the polymerization reactivity may decrease, but it seems that the one larger than Z ¹ tends to satisfy each property in a well-balanced manner, and the number of benzene ring skeletons constituting Z ² is preferably ^{one more than Z 1} . Among many embodiments, the embodiment in which Z ² is a naphthalene ring and Z ¹ is a benzene ring is preferred. In general, birefringence tends to increase as the number of benzene ring skeletons constituting the arene ring increases. It seems that properties such as a high refractive index, a low Abbe number, and high heat resistance can be improved in a well-balanced manner while effectively suppressing an excessive increase in birefringence.

^The bonding position of Z ² with ^{Z 1} is not particularly limited. may be attached to Z ¹ , preferably at the 2-position (2-naphthyl group).

In addition, the bonding position of Z ¹ with Z ² (that is, the substitution position of the group [-Z ² -(R ¹ ) _k1 ]) is a position other than the two carbonyl groups [-C(=O)-]. Z ¹ is a benzene ring, and the two carbonyl groups [--C(=O)--] are bonded to this benzene ring Z ¹ in a 1,4-position (p-position) relationship. , and when the number of substitutions m is ² , Z ² is at the 2,5-position ( It is preferable that Z ² are bonded to each other in a p-position) relationship.

R ¹ is preferably a substituent (non-polymerizable group) inert to the polymerization reaction, such as an alkyl group, specifically a methyl group, an n-propyl group, an isopropyl group, an n-butyl group, linear or branched C _1-10 alkyl groups such as t-butyl group and hexyl group; cycloalkyl groups optionally having an alkyl group such as propylcyclohexyl group and pentylcyclohexyl group; fluorine atom and chlorine atom , a halogen atom such as a bromine atom; haloalkyl groups (or halogenated alkyl groups), such as mono- to perhaloalkyl groups such as a trifluoromethyl group and a bromomethyl group; haloalkoxy groups such as a trifluoromethoxy group; alkoxy groups, such as Linear or branched C _1-10 alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, pentyloxy, hexyloxy, heptyloxy; benzyloxy; aralkyloxy group such as; acyl group such as acetyl group; dialkylaminocarbonyl group such as dimethylaminocarbonyl group and diethylaminocarbonyl group; alkylthio group such as methylthio group and isopropylthio group; alkylsulfonyl group such as methylsulfonyl group; groups such as mono- or dialkylamino groups such as dimethylamino group and diethylamino group, mono- or diarylamino groups such as diphenylamino group, mono- or diacylamino groups such as acetylamino group; dialkylaminoalkyl groups such as dimethylaminomethyl group a trialkylsilyl group such as a trimethylsilyl group; a cyano group; a cyanoalkyl group such as a cyanomethyl group; and a nitro group.

When k1 is 1 or more, representative R ¹ includes an alkyl group, a halogen atom, a haloalkyl group, an alkoxy group, an aralkyloxy group, an acyl group, etc., preferably an alkyl group such as a C _1-4 alkyl group. , straight or branched chain C _1-4 alkoxy groups.

The substitution number k1 of R ¹ may be an integer of 0 or more and can be appropriately selected according to the type of ring Z ^2. For example, it may be an integer of about 0 to 7. It is an integer from 0 to 5, an integer from 0 to 3, an integer from 0 to 2, more preferably 0 or 1, especially 0. When k1 is 2 or more, the two or more types of ^R1 may be the same or different. Also, the substitution position of R ¹ is not particularly limited.

The substitution number m of the group [-Z ² -(R ¹ ) _k1 ] may be an integer of 1 or more and can be appropriately selected depending on the type of ring Z ¹ , and may be an integer of about 1 to 6, for example. , preferably an integer of 1 to 4, an integer of 1 to 3, and an integer of 1 to 2 in the following steps, and can satisfy optical properties, high heat resistance, high moldability, polymerization reactivity, etc. in a well-balanced manner. and m is 2 is particularly preferred. If m is too small, it may not be possible to achieve well-balanced optical properties such as a high refractive index and high heat resistance. As described above, in general, birefringence tends to increase as the number of benzene ring skeletons increases. It seems that properties such as a high refractive index, a low Abbe number, and a high heat resistance can be improved in a well-balanced manner while effectively suppressing the On the other hand, if m is too large, the glass transition temperature Tg may be excessively increased, resulting in deterioration in moldability, and the polymerization reactivity may decrease, making it impossible to increase the molecular weight. or high molecular weight), m may be 1.

When m is 2 or more, the types of the two or more groups [-Z ² -(R ¹ ) _k1 ] (that is, the types of each Z ² , R ¹ and k1, and combinations thereof) are the same or different. may be the same, but are preferably the same.

R ² is a substituent different from R ¹ and is preferably a non-polymerizable group inert to the polymerization reaction, for example, a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aralkyl group , excluding aryl groups). The alkyl group includes linear or branched C _1-6 alkyl groups such as methyl group, ethyl group, isopropyl group and n-butyl group. Cycloalkyl groups include C _5-10 cycloalkyl groups such as cyclohexyl groups. Aralkyl groups include C _6-10 aryl C _1-6 alkyl groups such as benzyl group. When k2 is 1 or greater, R ² is preferably an alkyl group, preferably a linear or branched C _1-4 alkyl group such as a methyl group.

The substitution number k2 of R ² may be an integer of 0 or more and can be appropriately selected depending on the type of ring Z ^1. For example, it may be an integer of about 0 to 3, preferably an integer of 0 to 2, More preferably 0 or 1, especially 0. When k2 is 2 or more, two or more types of ^R2 may be the same or different. Also, the substitution position of ^R2 is not particularly limited.

The total value of the substitution numbers m and k2 (also referred to as m + k2) may be 1 or more, and the upper limit of m + k2 is a hydrogen atom that can be substituted (or bonded) to Z ¹ depending on the type of ring Z ¹ Any value obtained by subtracting 2 from the number may be used. That is, the upper limit of m+k2 is 4 when Z1 is ^a benzene ring, and 6 when it is a naphthalene ring.

As a typical first dicarboxylic acid component (A1) corresponding to the first dicarboxylic acid unit (A1), for example, Z ¹ in the above formula (1) is a monocyclic or condensed polycyclic C _{6- 10} arene ring, Z ² is a C _6-12 arene ring, and m is an integer of 1 to 2 _. polycyclic C _6-10 arene-dicarboxylic acid moieties], specifically 2-phenyl-terephthalic acid, 2,5-diphenyl-terephthalic acid, 2-(1-naphthyl)-terephthalic acid, 2,5- mono- or di(C _6-10 aryl)benzenedicarboxylic acids such as di(1-naphthyl)-terephthalic acid, 2-(2-naphthyl)-terephthalic acid, 2,5-di(2-naphthyl)-terephthalic acid and Examples thereof include ester-forming derivatives thereof.

The first dicarboxylic acid units (A1) may be contained alone or in combination of two or more. Among the first dicarboxylic acid units (A1), mono- or di-naphthyl terephthalic acid is preferable in that optical properties, heat resistance, moldability, polymerization reactivity, etc. can be satisfied in a well-balanced manner, and 2-(2-naphthyl)- More preferred are mono- or di(2-naphthyl)terephthalic acids such as terephthalic acid, 2,5-di(2-naphthyl)-terephthalic acid, especially di( Units derived from 2-naphthyl)-terephthalic acid are preferred.

In addition, when the first dicarboxylic acid unit (A1) contains these preferred first dicarboxylic acid units (A1), the proportion thereof is, for example, 10 to 100 mol with respect to the entire first dicarboxylic acid unit (A1). %, preferably 50 mol % or more, 70 mol % or more, 90 mol % or more, more preferably 100 mol %. That is, the first dicarboxylic acid unit (A1) is the above preferred first dicarboxylic acid unit (A1) only, especially a unit derived from mono- or di(C _6-10 aryl)benzenedicarboxylic acid such as mono- or dinaphthyl terephthalic acid It is preferable to form substantially only by.

Moreover, the first dicarboxylic acid component (A1) may be a commercially available product, or may be synthesized by a conventional method such as a coupling reaction. The coupling reaction is not particularly limited, and when the Suzuki-Miyaura cross-coupling reaction is used, for example, the group [-Z ² -(R ¹ ) _k1 ] in the formula (1) is replaced with a coupling-reactive group such as a halogen atom. a group-substituted dicarboxylic acid component, specifically a halogenated _{arenedicarboxylic} acid component such as dimethyl ^{bromoterephthalate} and diethyl ^2,5 -dibromoterephthalate; boron compounds such as boronic acids, boronate esters, specifically areneboronic acids such as 2-naphthylboronic acid; bases such as metal carbonates, specifically alkali metal carbonates such as potassium carbonate; and in the presence of a transition metal catalyst such as a palladium catalyst or a precursor thereof, specifically a palladium catalyst precursor such as palladium acetate [Pd(OAc) ₂ ]; A phase transfer catalyst and a solvent may be added, and the coupling reaction may be performed under an inert gas atmosphere such as a nitrogen atmosphere.

Second dicarboxylic acid unit (A2)
The dicarboxylic acid unit (A) may or may not contain a second dicarboxylic acid unit (A2) represented by the following formula (2), if necessary. When the second dicarboxylic acid unit (A2) is included, the birefringence tends to be reduced while maintaining a relatively high refractive index, and the polymerization reactivity tends to be easily improved even if it has a rigid fluorene skeleton. There is

(Wherein, R ³ represents a substituent, k3 represents an integer of 0 to 8,
A ^1a and A ^1b independently represent a divalent hydrocarbon group optionally having a substituent).

In the above formula (2), the substituent represented by R ³ is preferably a substituent (non-polymerizable group) inert to the polymerization reaction, such as a cyano group; a fluorine atom, a chlorine atom, a bromine halogen atoms such as atoms; hydrocarbon groups such as alkyl groups and aryl groups;

Examples of the alkyl group include linear or branched C _1-12 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and t-butyl group. . The aryl group includes C _6-12 aryl groups such as phenyl group and naphthyl group.

Of these substituents R ³ , when the number of substituents k3 is 1 or more, a cyano group, a halogen atom, an alkyl group or an aryl group is preferable, an alkyl group or an aryl group is more preferable, and an aryl group is particularly preferable. Preferred alkyl groups are linear or branched C _1-8 alkyl groups, more preferably linear or branched C _1-4 alkyl groups such as methyl groups. Preferred aryl groups are phenyl or naphthyl groups, more preferably naphthyl groups, especially 2-naphthyl groups.

The substitution number k3 may be, for example, an integer of about 0 to 6, and a preferred range is an integer of 0 to 4, an integer of 0 to 3, and an integer of 0 to 2, more preferably is preferably 0 or 1, especially 0. When R ³ is an aryl group, the substitution number k3 may be an integer of 1 to 6, preferably an integer of 1 to 4, an integer of 1 to 3, an integer of 1 to 2, and an integer of 1 to 2. It is an integer, preferably 2.

When the substitution number k3 of the group R ³ is 2 or more, the types of the 2 or more groups R ³ may be the same or different, but are preferably the same. The bonding position (substitution position) of R ³ is not particularly limited, and examples thereof include positions 2, 7 and 2,7 of the fluorene ring, with positions 2,7 being preferred.

Hydrocarbon groups represented by groups A ^1a and A ^1b include linear or branched alkylene groups such as methylene, ethylene, trimethylene, propylene, 1,2-butanediyl, 2-methyl Linear or branched C _1-8 alkylene groups such as propane-1,3-diyl groups are included. Preferred alkylene groups include linear or branched C _1-6 alkylene groups such as methylene, ethylene, trimethylene, propylene and 2-methylpropane-1,3-diyl groups, more preferably is a linear or branched C _1-4 alkylene group.

The substituent that the hydrocarbon group may have is preferably a non-polymerizable group that is inert to the polymerization reaction, and examples thereof include an aryl group such as a phenyl group and a cycloalkyl group such as a cyclohexyl group. be done. The hydrocarbon groups A ^1a and A ^1b having substituents may be, for example, a 1-phenylethylene group, a 1-phenylpropane-1,2-diyl group, and the like.

The groups A ^1a and A ^1b are preferably linear or branched C _2-4 alkylene groups, especially linear or branched C _2-3 alkylene groups such as ethylene groups, propylene groups, An ethylene group is particularly preferred. The types of A ^1a and A ^1b may be different from each other, but are preferably the same.

Typical second dicarboxylic acid components (A2) corresponding to the second dicarboxylic acid units (A2) represented by the formula (2) include a dicarboxylic acid component (A2-1) in which k3 is 0, dicarboxylic acid components (A2-2) having k3 of ¹ or more and containing an aryl group as R3 ^, for example, A1a and ^A1b are linear or branched _C2-6 alkylene groups, Examples include dicarboxylic acid components in which k3 is 0 to 2 and R ³ is an aryl group.

Specific dicarboxylic acid components (A2-1) include components in which A ^1a and A ^1b are linear or branched C _2-6 alkylene groups and k3 is 0. For example, 9, 9,9-bis(carboxyC _2-6 alkyl)fluorene such as 9-bis(2-carboxyethyl)fluorene and 9,9-bis(2-carboxypropyl)fluorene; and ester-forming derivatives thereof. be done.

As a specific dicarboxylic acid component (A2-2), A ^1a and A ^1b are linear or branched C _2-6 alkylene groups, k3 is 1 or more, preferably 1 to 3, especially 2, and R ³ corresponds to an aryl group, such as 9,9-bis(2-carboxyethyl)-2,7-diphenylfluorene, 9,9-bis(2-carboxyethyl)-2,7-di (2-naphthyl)fluorene, 9,9-bis(2-carboxypropyl)-2,7-di(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-2,7-di(1 -naphthyl)fluorene, 9,9-bis(carboxyC _2-6 alkyl) _{-diC 6-10} aryl such as 9,9-bis(2-carboxyethyl)-3,6-di(2-naphthyl)fluorene -fluorene; and ester-forming derivatives thereof.

The second dicarboxylic acid units (A2) derived from these second dicarboxylic acid components (A2) may be contained alone or in combination of two or more. For example, a second dicarboxylic acid unit (A2) containing a dicarboxylic acid component (A2-1) and a dicarboxylic acid component (A2-2) can satisfy all of optical properties, heat resistance, and moldability in a well-balanced manner. is preferably combined with the first dicarboxylic acid unit (A1).

Preferred second dicarboxylic acid units (A2) include 9,9-bis(carboxyC _2-4 alkyl) such as 9,9-bis(2-carboxyethyl)fluorene, which is the dicarboxylic acid component (A2-1). Fluorene; 9,9-bis(carboxy C _2-4 alkyl) such as 9,9-bis(2-carboxyethyl)-2,7-di(2-naphthyl)fluorene which is a dicarboxylic acid component (A2-2) - 9,9-bis(carboxy C _2-3 alkyl) fluorenes, such as 9,9-bis(2-carboxyethyl) fluorene, which is dinaphthylfluorene; 9,9-bis(carboxy C _2-3 alkyl)- Units derived from dinaphthylfluorene are more preferable, and 9,9-bis(2 9,9-Bis(carboxyC _2-3 alkyl)-dinaphthylfluorenes such as -carboxyethyl)-2,7-di(2-naphthyl)fluorene are particularly preferred.

When the second dicarboxylic acid unit (A2) contains these preferred second dicarboxylic acid units (A2), the proportion thereof is, for example, 10 to 100 with respect to the entire second dicarboxylic acid unit (A2). About mol %, preferably 50 mol % or more, 70 mol % or more, 90 mol % or more, more preferably 100 mol % or more in a stepwise manner. That is, the second dicarboxylic acid unit (A2) is the above preferred second dicarboxylic acid unit (A2) only, particularly 9,9-bis(carboxyC _2- It is preferably formed substantially only by units derived from ₄ -alkyl)fluorene.

The ratio of the dicarboxylic acid component (A2-1) is, for example, about 10 to 100 mol%, preferably 50 mol% or more and 70 mol% or more, relative to the entire second dicarboxylic acid unit (A2). , 90 mol % or more, more preferably 100 mol %.

Further, when the second dicarboxylic acid unit (A2) containing at least the dicarboxylic acid component (A2-2) is combined with the first dicarboxylic acid unit (A1), optical properties, heat resistance, moldability, etc. are all balanced. It seems to be easy to satisfy. The ratio of the dicarboxylic acid component (A2-2) is, for example, about 1 to 100 mol%, preferably 3 to 80 mol%, 5 to 50 mol%, relative to the entire second dicarboxylic acid unit (A2). mol %, 8-40 mol %, 10-30 mol %, 15-25 mol %. When the proportion of the dicarboxylic acid component (A2-2) is within this range, optical properties such as high refractive index, low Abbe number, and low birefringence, heat resistance, moldability, etc., can all be satisfied in a well-balanced manner. It seems

The ratio of the dicarboxylic acid component (A2-1) and the dicarboxylic acid component (A2-2) is not particularly limited and can be selected from the former/latter (molar ratio) = 0/100 to 100/0, but for example 1/99 to 99/1, preferably stepwise below, 20/80 to 97/3, 50/50 to 95/5, 60/40 to 92/8, 70/30 to 90/10, 75/25 to 85/15 is. When the second dicarboxylic acid unit (A2) containing at least both dicarboxylic acid components (A2-1) and (A2-2) is combined with the first dicarboxylic acid unit (A1), optical properties, heat resistance, molding In particular, when the ratio of (A2-1) and (A2-2) is within the above range, optical properties such as a high refractive index, a low Abbe number, and a low birefringence can be achieved. It seems that all of properties, heat resistance, moldability, etc. can be satisfied with a better balance.

Third dicarboxylic acid unit (A3)
The dicarboxylic acid unit (A) may or may not contain a third dicarboxylic acid unit (A3), which is a structural unit derived from an aliphatic dicarboxylic acid component, as necessary. When the third dicarboxylic acid unit (A3) is included, it seems that an excessive increase in the glass transition temperature can be suppressed and the formability can be improved.

Also, the third dicarboxylic acid unit (A3) in combination with the first dicarboxylic acid unit (A1), preferably in combination with the first dicarboxylic acid unit (A1) and the second dicarboxylic acid unit (A2) , More preferably, when combined with the first dicarboxylic acid unit (A1) and the dicarboxylic acid unit (A2-2), despite containing a structural unit derived from an aliphatic dicarboxylic acid that tends to lower the refractive index, surprisingly It seems that a resin with a high refractive index, a low Abbe number, and a low birefringence can be obtained. Therefore, a resin having an excellent balance of optical properties, heat resistance and moldability can be easily or efficiently prepared.

Aliphatic dicarboxylic acid components for forming the third dicarboxylic acid unit (A3) include, for example, linear or branched alkanedicarboxylic acids, specifically succinic acid, adipic acid, suberic acid, sebacine acids, such as C _2-12 alkane-dicarboxylic acids such as decanedicarboxylic acid; linear or branched unsaturated aliphatic dicarboxylic acids, specifically C _2- , such as maleic acid, fumaric acid, itaconic acid; ₁₀ alkene-dicarboxylic acids; and ester-forming derivatives thereof. The aliphatic dicarboxylic acid component may be linear or branched, preferably linear.

These third dicarboxylic acid units (A3) can be used alone or in combination of two or more. Among these third dicarboxylic acid units (A3), structural units derived from straight-chain or branched-chain alkanedicarboxylic acids are preferred, and more preferably, the number of carbon atoms (including the carbon atoms of the carboxyl group Number) is preferably 2 to 20, 4 to 18, 6 to 16, 7 to 14, 8 to 12 alkanedicarboxylic acids, particularly structural units derived from alkanedicarboxylic acids having 9 to 11 carbon atoms such as sebacic acid.

The proportion of constituent units derived from an alkanedicarboxylic acid such as sebacic acid (preferred proportion of third dicarboxylic acid units (A3)) is, for example, about 10 to 100 mol% of the total third dicarboxylic acid units (A3). , preferably 50 mol % or more, 70 mol % or more, 90 mol % or more, and more preferably 100 mol % in a stepwise manner.

Fourth dicarboxylic acid unit (A4)
Note that the dicarboxylic acid unit (A) is optionally different from the first dicarboxylic acid unit (A1), the second dicarboxylic acid unit (A2) and the third dicarboxylic acid unit (A3) [first It may or may not contain a fourth dicarboxylic acid unit (A4) that does not belong to the category of 1 to 3 dicarboxylic acid units (A1) to (A3)].

Examples of the fourth dicarboxylic acid unit (A4) include, for example, an aromatic dicarboxylic acid component [excluding the first dicarboxylic acid unit (A1) and the second dicarboxylic acid unit (A2)], an alicyclic dicarboxylic acid Structural units derived from components and the like can be mentioned.

Examples of aromatic dicarboxylic acid components include monocyclic aromatic dicarboxylic acids, polycyclic aromatic dicarboxylic acids, and ester-forming derivatives thereof. Monocyclic aromatic dicarboxylic acids include, for example, benzenedicarboxylic acids such as phthalic acid, terephthalic acid and isophthalic acid; alkylbenzenedicarboxylic acids, specifically C _1-4 alkyl-benzenedicarboxylic acids such as 4-methylisophthalic acid; acid and the like.

Examples of polycyclic aromatic dicarboxylic acids include condensed polycyclic aromatic dicarboxylic acids, specifically condensed polycyclic C _10-24 arene-dicarboxylic acids such as naphthalenedicarboxylic acid, anthracenedicarboxylic acid, and phenanthenedicarboxylic acid. acids, preferably fused polycyclic C _10-14 arene-dicarboxylic acids and the like; biaryl dicarboxylic acids, specifically 2,2′-biphenyldicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 3,3′- BiC _6-10 aryl-dicarboxylic acids such as dicarboxy-1,1′-binaphthyl; bis(carboxyalkoxy)biC _6-10 aryl, specifically 2,2′-bis(carboxymethoxy)- bis(carboxyC _1-4 alkoxy) _{biC 6-10} aryl such as 1,1′-binaphthyl; bis[(carboxyC _1-4 alkoxy)-C _6-10 aryl)C _1-6 alkanes such as carboxymethoxy)-1-naphthyl]methane; diarylalkanedicarboxylic acids, specifically 4,4′- di-C _6-10 aryl C _1-6 alkane-dicarboxylic acids such as diphenylmethane dicarboxylic acid; diaryl ketone dicarboxylic acids, specifically di(C _6-10 aryl) such as 4.4′-diphenyl ketone dicarboxylic acid; ketone-dicarboxylic acids and the like; diaryletherdicarboxylic acids, specifically di(C _6-10 aryl)ether-dicarboxylic acids such as 4.4′-diphenyletherdicarboxylic acid; diarylsulfonedicarboxylic acids and the like; and di(C _6-10 aryl)sulfone-dicarboxylic acids such as 4,4′-diphenylsulfonedicarboxylic acid.

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

Alicyclic dicarboxylic acid components include, for example, cycloalkanedicarboxylic acids, specifically C _5-10 cycloalkane-dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; C _{5- 10} cycloalkene-dicarboxylic acids and the like; bridged cyclic cycloalkene dicarboxylic acids, specifically bi- or tricycloalkene dicarboxylic acids such as norbornene dicarboxylic acid; and ester-forming derivatives thereof.

The proportion of the fourth dicarboxylic acid unit (A4) is, for example, less than 50 mol%, preferably 30 mol% or less, more preferably 10 mol% or less, relative to the total dicarboxylic acid unit (A), and substantially It is preferable not to contain the fourth dicarboxylic acid unit (A4), and when the fourth dicarboxylic acid unit (A4) is contained, the ratio may be, for example, about 0.1 to 5 mol %.

The proportion of the first dicarboxylic acid unit (A1) may be selected from a range of, for example, about 1 to 100 mol%, specifically about 1 to 50 mol%, relative to the total dicarboxylic acid unit (A). , high refractive index, low Abbe number, optical properties such as low birefringence, high heat resistance, high moldability and polymerization reactivity (or high molecular weight) in a well-balanced manner. 5 to 75 mol%, 10 to 60 mol%, 15 to 50 mol%, 17 to 40 mol%, 20 to 30 mol%; applications where the balance of optical properties, high heat resistance and high moldability is particularly important Then, it is preferably 50 to 100 mol %, 60 to 95 mol %, 70 to 90 mol %, and 75 to 85 mol % in the following steps. If the proportion of the first dicarboxylic acid unit (A1) is too large, the polymerization reactivity may decrease, making it difficult to obtain a high molecular weight, or the Tg may excessively increase, resulting in a decrease in moldability (productivity). Conversely, if it is too small, it may become difficult to obtain optical properties such as a high refractive index and a low Abbe number, and high heat resistance.

The ratio of the total amount of the first dicarboxylic acid unit (A1) and the second dicarboxylic acid unit (A2) is, for example, 1 mol% or more, specifically 10 to 100 mol, relative to the total dicarboxylic acid unit (A). %, preferably 30 mol % or more, 50 mol % or more, 70 mol % or more, 90 mol % or more, and particularly preferably 100 mol %.

The ratio of the total amount of the first dicarboxylic acid unit (A1), the second dicarboxylic acid unit (A2) and the third dicarboxylic acid unit (A3) is, for example, 1 mol% with respect to the entire dicarboxylic acid unit (A). Above, specifically, it may be selected from a range of about 10 to 100 mol%, preferably 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more in a stepwise manner, 100 mol % is particularly preferred.

The ratio of the first dicarboxylic acid unit (A1) to the second dicarboxylic acid unit (A2) (also referred to as A1/A2) is, for example, A1/A2 (molar ratio) = about 1/99 to 100/0, Specifically, it may be selected from a range of about 5/95 to 90/10, and optical properties such as high refractive index, low Abbe number, low birefringence, high heat resistance, high moldability and high polymerization reactivity (or high molecular weight), etc. in a well-balanced manner, preferably the following stepwise: /60, 20/80 to 30/70, but more preferably 5/95 to 30/70, 8/92 to 25 in a stepwise manner in terms of satisfying the above characteristics in a more balanced manner. /75, 10/90 to 20/80; while satisfying the balance of optical properties, high heat resistance and high moldability, especially in applications where a high refractive index is important, preferably the following stepwise, 50/ 50 to 100/0, 60/40 to 95/5, 70/30 to 90/10, 75/25 to 85/15, more preferably 1/99 to 50/ 50, 5/95 to 40/60, 10/90 to 30/70, 15/85 to 25/75. If the proportion of the second dicarboxylic acid unit (A2) is too low, it may become difficult to increase the molecular weight, resulting in reduced moldability and insufficient reduction in birefringence. Conversely, if the ratio of the second dicarboxylic acid unit (A2) is too high, optical properties such as a high refractive index and a low Abbe number may not be obtained, or the heat resistance may be lowered.

The ratio of the first dicarboxylic acid unit (A1) to the third dicarboxylic acid unit (A3) (also referred to as A1/A3) is, for example, A1/A3 (molar ratio) = about 1/99 to 100/0, Specifically, it may be selected from a range of about 5/95 to 90/10. 55, 35/65 to 40/60. If the proportion of the third dicarboxylic acid unit (A3) is too high, there is a possibility that the optical properties may deteriorate or the heat resistance may deteriorate. On the other hand, if the proportion of the first dicarboxylic acid unit (A1) is too large, the polymerization reactivity may decrease, making it difficult to obtain a high molecular weight product, or the Tg may excessively increase, resulting in a decrease in moldability (productivity). be.

The ratio of the second dicarboxylic acid unit (A2) to the third dicarboxylic acid unit (A3) (also referred to as A2/A3) is, for example, A2/A3 (molar ratio) = about 0/100 to 100/0, Specifically, it may be selected from a range of about 10/90 to 95/5, preferably 30/70 to 90/10, 55/45 to 85/15, 65/35 to 75/ 25. If the proportion of the second dicarboxylic acid unit (A2) is too large, the optical properties may deteriorate or the heat resistance may deteriorate. may decrease, or the heat resistance may decrease. Within the above preferable range, it is easy to satisfy optical properties, heat resistance and moldability in a well-balanced manner.

The ratio of the dicarboxylic acid unit (A) [the total amount of the first to fourth dicarboxylic acid units (A1) to (A4)] is the entire structural unit of the thermoplastic resin (derived from all monomer components constituting the thermoplastic resin (Total amount of units of 40 to 50 mol %.

[Diol unit (B)]
The thermoplastic resin is preferably a polyester resin containing diol units (B) in addition to dicarboxylic acid units (A). The diol unit (B) is not particularly limited, but is selected from the first diol unit (B1) represented by the following formula (3) and the second diol unit (B2) represented by the following formula (4). It preferably contains at least one diol unit, more preferably both.

First diol unit (B1)
The diol unit (B) may or may not contain a first diol unit (B1) represented by the following formula (3), if necessary. When the first diol unit (B1) is included, the heat resistance can be improved while improving the optical properties (high refractive index, low Abbe number and low birefringence) in a well-balanced manner.

(Wherein, R ⁴ represents a substituent, k4 represents an integer of 0 to 8,
Z ^3a and Z ^3b independently represent an arene ring,
R ^5a and R ^5b independently represent a substituent, k5a and k5b independently represent an integer of 0 or more,
A ^2a and A ^2b independently represent a linear or branched alkylene group, and n2a and n2b independently represent an integer of 0 or 1 or more).

In the above formula (3), the arene ring (aromatic hydrocarbon ring) represented by Z ^3a and Z ^3b includes, for example, monocyclic arene rings such as benzene ring, polycyclic arene rings, etc. Polycyclic arene rings include condensed polycyclic arene rings, ring-assembled arene rings, and the like.

Examples of the condensed polycyclic arene ring include rings similar to the condensed polycyclic arene rings exemplified in the section ^Z1 above. A preferred fused polycyclic arene ring is a fused polycyclic C _10-16 arene ring, more preferably a fused polycyclic C _10-14 arene ring, with a naphthalene ring being particularly preferred.

Examples of ring-assembled arene rings include rings similar to the ring ^- assembled arene rings exemplified in the section Z2 above. Preferred ring-assembled arene rings include biC _6-10 arene rings, with biphenyl rings being particularly preferred.

The types of Z ^3a and Z ^3b may be the same or different, and are preferably the same. Preferred Z ^3a and Z ^3b are C _6-12 arene rings such as benzene ring, naphthalene ring and biphenyl ring, more preferably C _6-10 arene rings such as benzene ring and naphthalene ring, especially naphthalene ring.

The substitution position of Z ^3a and Z ^3b bonded to the 9-position of the ^fluorene ring is not particularly ^{limited .} When Z ^3b is a naphthalene ring, it is at the 1- or 2-position, preferably at the 2-position; when Z ^3a and Z ^3b are a biphenyl ring, it is at the 2-, 3-, or 4-position , preferably at the 3rd position.

The substituent represented by R ⁴ is preferably a non ^- polymerizable group that is inert to the polymerization reaction. A substituent etc. are mentioned.

The substitution number k4 of R ⁴ is the same as k3 described in the formula (2) above, including preferred embodiments, and 0 is particularly preferred. When the substitution number k4 is 2 or more, the types of the 2 or more groups ^R4 may be the same or different, and are preferably the same. The bonding position (substitution position) of the group R ⁴ with respect to the two benzene rings constituting the fluorene ring is not particularly limited. position is preferred.

The substituents represented by R ^5a and R ^5b are preferably non-polymerizable groups that are inert to the polymerization reaction, such as halogen atoms such as fluorine, chlorine, bromine and iodine atoms; , a cycloalkyl group, an aryl group, an aralkyl group, and the like (or a group R ^h ) ^; (wherein R ^h represents the above hydrocarbon group); a group —SR ^h corresponding to the above hydrocarbon group such as an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group (wherein R ^h represents the above hydrocarbon group); a hydrogen group); an acyl group; a nitro group; a cyano group;

Examples of the alkyl group represented by R ^h include straight-chain or Branched C _1-10 alkyl groups, preferably linear or branched C _1-6 alkyl groups, more preferably linear or branched C _1-4 alkyl groups, and the like.

The cycloalkyl group represented by R ^h includes, for example, C _5-10 cycloalkyl groups such as cyclopentyl group and cyclohexyl group.

Examples of the aryl group represented by R ^h include C _6-12 aryl groups such as phenyl group, alkylphenyl group, biphenylyl group and naphthyl group. Examples of alkylphenyl groups include methylphenyl groups (tolyl groups) and dimethylphenyl groups (xylyl groups).

Aralkyl groups represented by R ^h include, for example, C _6-10 aryl-C _1-4 alkyl groups such as benzyl group and phenethyl group.

The group —OR ^h includes groups corresponding to the above-exemplified hydrocarbon groups R ^h including preferred embodiments, such as linear or branched C _1-10 alkoxy groups such as a methoxy group, cyclohexyloxy groups, and the like. C _5-10 cycloalkyloxy group, C _6-10 aryloxy group such as phenoxy group, C _6-10 aryl-C _1-4 alkyloxy group such as benzyloxy group, and the like.

The group —SR ^h includes groups corresponding to the above-exemplified hydrocarbon groups R ^h including preferred embodiments, such as linear or branched C _1-10 alkylthio groups such as methylthio groups, cyclohexylthio groups and the like. C _5-10 cycloalkylthio group, C _6-10 arylthio group such as thiophenoxy group (phenylthio group), C _6-10 aryl-C _1-4 alkylthio group such as benzylthio group, and the like.

Acyl groups include, for example, C _1-6 acyl groups such as an acetyl group.

Substituted amino groups include, for example, mono- or dialkylamino groups, mono- or bis(alkylcarbonyl)amino groups, and the like. Examples of mono- or dialkylamino groups include mono- or di-C _1-4 alkylamino groups such as dimethylamino group, and examples of mono- or bis(alkylcarbonyl)amino groups include mono- or dialkylamino groups such as diacetylamino group. or a bis(C _1-4 alkyl-carbonyl)amino group.

Representative R ^5a and R ^5b include, for example, halogen atoms; hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups; alkoxy groups; acyl groups; nitro groups; is mentioned. When the number of substitutions k5a and k5b is 1 or more, preferred R ^5a and R ^5b include an alkyl group, a cycloalkyl group, an aryl group and an alkoxy group, more preferably a linear or branched chain such as a methyl group. C _1-6 alkyl groups, C _5-8 cycloalkyl groups such as cyclohexyl groups, C _6-14 aryl groups such as phenyl groups, and linear or branched C _1-4 alkoxy groups such as methoxy groups. be done. Among them, an alkyl group and an aryl group are preferable, and a linear or branched C _1-4 alkyl group such as a methyl group and a C _6-10 aryl group such as a phenyl group are particularly preferable. When the groups R ^5a and R ^5b are aryl groups, R ^5a and R ^5b may form the ring-assembled arene rings together with rings Z ^3a and Z ^3b respectively.

The substitution numbers k5a and k5b of R ^5a and R ^5b may each be an integer of 0 or more and can be appropriately selected depending on the type of rings Z ^3a and Z ^3b , and may be an integer of about 0 to 6, for example. , preferably an integer from 0 to 4, more preferably an integer from 0 to 2, more preferably 0 or 1, especially 0. k5a and k5b may be different from each other, but are preferably the same. In addition, when k5a is 2 or more, the types of 2 or more ^R5a may be the same or different, and the same applies to ^k5b and R5b. Also, the types of R ^5a and R ^5b may be the same or different. The substitution ^positions of R ^5a and ^{R 5b} are not particularly limited. For example, it may be substituted at the ortho position (the carbon atom adjacent to the bonding position of the ether bond) with respect to the ether bond (--O--) in Z ^3a and Z ^3b .

Examples of the alkylene groups A ^2a and A ^2b include linear or branched C groups such as ethylene group, propylene group (1,2-propanediyl group), trimethylene group, 1,2-butanediyl group and tetramethylene group. _2-6 alkylene groups, etc., preferably linear or branched C _2-4 alkylene groups, more preferably linear or branched C _2-3 alkylene groups such as ethylene and propylene groups; An ethylene group is particularly preferred.

The number of repetitions (number of added moles) n2a and n2b of the alkyleneoxy groups [-(A ^2a O)-] and [-(A ^2b O)-] may be 0 or more, for example, in the range of about 0 to 15. , preferably 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, 0 to 1 in the following steps. Further, when the repeating numbers n2a and n2b are 1 or more, the polymerization reactivity tends to be improved. , 1 to 6, 1 to 4, 1 to 3, 1 to 2, and 1 is particularly preferred.

In the present specification and claims, the "repeating number (number of moles added)" may be an average value (arithmetic mean value, arithmetic mean value) or an average number of moles added, and a preferred embodiment is It may be similar to the preferred integer ranges described above. If n2a and n2b are too large, the heat resistance and refractive index may decrease. Also, n2a and n2b may be the same or different. When n2a is 2 or more, the types of the 2 or more alkyleneoxy groups [-(A ^2a O)-] may be different from each other, but are preferably the same, and n2b and the group [-(A ^2b O) -] is the same. Also, the types of A ^2a and A ^2b may be the same or different.

The substitution positions of the groups [—O—(A ^2a O) _n2a —] and [—O—(A ^2b O) _n2b —] (that is, the ether bond forming the main chain) with respect to the rings Z ^3a and Z ^3b are There are no particular restrictions, and Z ^3a and Z ^3b may be substituted at appropriate positions. The substitution positions of the groups [--O--(A ^2a O) _n2a -] and [--O--(A ^2b O) _n2b -] with respect to rings Z ^3a and Z ^3b are, when Z ^3a and Z ^3b are benzene rings, Substitution at any one of the 2-, 3- and 4-positions of the phenyl group bonded to the 9-position of the fluorene ring, preferably the 3- or 4-position, particularly preferably the 4-position. In addition, when Z ^3a and Z ^3b are naphthalene rings, they are often substituted at any of the 5-8 positions of the naphthyl group bonded to the 9-position of the fluorene ring. 1-position or 2-position of the naphthalene ring is substituted (substituted in a 1-naphthyl or 2-naphthyl relationship) for this substitution position, 1,5-position, 2,6-position relationship, especially 2 , 6-position relationship is preferred. Further, when Z ^3a and Z ^3b are ring-assembled arene rings, the substitution positions of the groups [—O—(A ^2a O) _n2a —] and [—O—(A ^2b O) _n2b —] are not particularly limited. For example, the arene ring bonded to the 9-position of fluorene or the arene ring adjacent to this arene ring may be substituted. For example, when Z ¹ and Z ² are biphenyl rings (or Z ^3a and Z ^3b are benzene rings, k5a and k5b are 1, R ^5a and R ^5b are phenyl groups), the 3- or 4-position of the biphenyl ring, preferably The 3-position may be attached to the 9-position of the fluorene, and when the 3-position of the biphenyl ring is attached to the 9-position of the fluorene, the groups [—O—(A ^2a O) _n2a —], [—O—(A ^2b O) _n2b -] may be, for example, any of the 2-, 4-, 5-, 6-, 2'-, 3'- and 4'-positions of the biphenyl ring, preferably is preferably at the 6- or 4'-position, especially at the 6-position.

Examples of the first diol component (B1) corresponding to the first diol unit (B1) include 9,9-bis(hydroxyaryl)fluorenes in which n2a and n2b are 0 in the above formula (3); 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes in which n2a and n2b are 1 or more, for example about 1 to 10, and the like.

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

9,9-bis(hydroxyaryl)fluorenes include, for example, 9,9-bis(hydroxyphenyl)fluorene, 9,9-bis(alkyl-hydroxyphenyl)fluorene, 9,9-bis(aryl-hydroxyphenyl ) fluorene, 9,9-bis(hydroxynaphthyl)fluorene, and the like.

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

9,9-bis(alkyl-hydroxyphenyl)fluorenes include, for example, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl ) 9,9-bis[(mono- or di)C _1-4 alkyl-hydroxyphenyl]fluorene such as fluorene.

9,9-bis(aryl-hydroxyphenyl)fluorenes include, for example, 9,9-bis(C _6-10 aryl-hydroxyphenyl) such as 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene fluorene and the like.

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

9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes include, for example, 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorene, 9,9-bis[alkyl-hydroxy(poly)alkoxyphenyl] fluorene, 9,9-bis[aryl-hydroxy(poly)alkoxyphenyl]fluorene, 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorene and the like.

Examples of 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxypropoxy ) 9,9-bis[hydroxy(mono to deca)C _2-4 alkoxy-phenyl]fluorene such as phenyl]fluorene.

Examples of 9,9-bis[alkyl-hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4 -(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene, 9,9-bis[4-(2-hydroxypropoxy)-3-methylphenyl]fluorene and the like. ) C _1-4 alkyl-hydroxy(mono to deca)C _2-4 alkoxy-phenyl]fluorene and the like.

Examples of 9,9-bis[aryl-hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-bis(4 9,9-bis[C _6-10 aryl-hydroxy(mono to deca)C _2-4 alkoxy-phenyl]fluorene such as -(2-hydroxypropoxy)-3-phenylphenyl)fluorene;

Examples of 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorene include 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, 9,9-bis[5-(2 -hydroxyethoxy)-1-naphthyl]fluorene, 9,9-bis[6-(2-hydroxypropoxy)-2-naphthyl]fluorene, etc. 9,9-bis[hydroxy(mono or deca)C _2-4 alkoxy -naphthyl]fluorene and the like.

These first diol units (B1) may be contained alone or in combination of two or more. Preferred first diol units (B1) include 9,9-bis[hydroxy(poly)alkoxyaryl such as 9,9-bis[hydroxy(mono- to penta)C _2-4 alkoxyC _6-10 aryl]fluorene ] fluorenes, more preferably 9,9-bis[hydroxy C _2-4 alkoxy C _6-10 aryl]fluorene, still more preferably 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene 9,9-bis[hydroxy C _2-3 alkoxy-naphthyl]fluorene-derived units such as

When the first diol unit (B1) contains these preferred first diol units (B1), the ratio thereof is, for example, about 10 to 100 mol% with respect to the entire first diol unit (B1). It is preferably 50 mol % or more, 70 mol % or more, 90 mol % or more, and more preferably 100 mol % in a stepwise manner. That is, the first diol unit (B1) is replaced with the above preferred first diol unit (B1) only, particularly 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene such as 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene. -Bis[hydroxy-C _2-3 alkoxy-naphthyl]fluorene-derived units are preferably formed substantially only.

Second diol unit (B2)
The diol unit (B) may or may not contain a second diol unit (B2) represented by the following formula (4), if necessary. When the second diol unit (B2) is included, the polymerization reaction proceeds efficiently to facilitate adjustment to a high molecular weight, and flexibility or toughness can be imparted to the thermoplastic resin to improve moldability and handleability.

( ^In the formula, A3 represents a linear or branched alkylene group, and n3 represents an integer of 1 or more).

Examples of the alkylene group represented by A ³ in the formula (4) include ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, 1,3-butanediyl group, tetramethylene group, 1,5 -Pentanediyl group, 1,6-hexanediyl group, 1,8-octanediyl group, 1,10-decanediyl group and other C _2-12 alkylene groups. Preferable linear or branched alkylene group A ³ is a C _2-10 alkylene group, a C _2-8 alkylene group, a C _2-6 alkylene group, a C _2-4 alkylene group, and further C _2-3 alkylene groups such as ethylene group and propylene group are preferred, and ethylene group is particularly preferred.

The repeating number n3 of the alkyleneoxy group [-(A ³ O)-] may be selected, for example, from a range of about 1 to 10, preferably 1 to 4, 1 to 3, 1 to 2 and 1 is particularly preferred. Note that the number of repetitions n3 may be an average value (arithmetic average value or arithmetic average value), and the preferred embodiment is the same as the integer range. When n3 is 2 or more, the types of the two or more alkyleneoxy groups (-A ³ O-) may be different from each other, but are preferably the same.

Examples of the second diol component (B2) corresponding to the second diol unit (B2) represented by the formula (4) include alkanediol (or alkylene glycol) and polyalkanediol (or polyalkylene glycol). etc.

Examples of the alkylene glycol include compounds in which n3 is ¹ and A3 corresponds to the above-exemplified alkylene group in the above formula (4), specifically ethylene glycol, propylene glycol, trimethylene glycol, and 1,2-butane. Diol, 1,3-butanediol, tetramethylene glycol (or 1,4-butanediol), 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,10 - linear or branched C _2-12 alkylene glycols such as decanediol, etc., and preferred embodiments are the same as those corresponding to the above alkylene group A ³ .

As the polyalkylene glycol, for example, in the formula (4), n3 is 2 or more, preferably 2 to 10, more preferably 2 to 6, more preferably 2 to 4, and A ³ is the alkylene group illustrated above. Corresponding compounds, specifically, di- or deca-linear or branched C _2-12 alkylene glycols such as diethylene glycol, dipropylene glycol, triethylene glycol, etc., preferably di- to hexa-linear or Branched C _2-6 alkylene glycols, more preferably di- or tetra-linear or branched C _2-4 alkylene glycols.

The second diol units (B2) formed from these second diol components (B2) may be contained singly or in combination of two or more. A preferable second diol unit (B2) is an alkylene glycol such as a linear or branched C _2-6 alkylene glycol, preferably a linear or branched chain, because it is easy to maintain high heat resistance. C _2-4 alkylene glycols, more preferably linear or branched C _2-3 alkylene glycols such as ethylene glycol, propylene glycol, especially units derived from ethylene glycol.

When the second diol unit (B2) contains these preferred second diol units (B2), the ratio thereof is, for example, about 10 to 100 mol% with respect to the entire second diol unit (B2). It is preferably 50 mol % or more, 70 mol % or more, 90 mol % or more, and more preferably 100 mol % in a stepwise manner. That is, it is preferred that the second diol units (B2) are substantially formed only of the above-mentioned preferred second diol units (B2), particularly only units derived from alkylene glycol such as ethylene glycol.

Third diol unit (B3)
The diol unit (B) does not necessarily have to be contained, but if necessary, a third diol unit ( B3) may or may not be included.

Examples of the third diol unit (B3) include aromatic diols [excluding the first diol unit (B1)], alicyclic diols, and alkylene oxides (or alkylene carbonates, halo diols) of these diol components. structural units derived from alkanol) adducts, and the like.

Examples of aromatic diols include dihydroxyarene such as hydroquinone and resorcinol; araliphatic diols such as benzenedimethanol; bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol C, bisphenol G and bisphenol S; Biphenols such as p'-biphenol and the like can be mentioned.

Examples of the alicyclic diol include cycloalkanediols such as cyclohexanediol; bis(hydroxyalkyl)cycloalkanes such as cyclohexanedimethanol; hydrogenated products of the above aromatic diols such as hydrogenated products of bisphenol A; .

Alkylene oxide (or corresponding alkylene carbonate, haloalkanol) adducts of these diol components include, for example, C _2-4 alkylene oxide adducts, preferably C _2-3 alkylene oxide adducts such as ethylene oxide adducts and propylene oxide adducts. Examples include oxide adducts, and the number of added moles is not particularly limited. Specifically, adducts obtained by adding about 2 to 10 mol of ethylene oxide to 1 mol of bisphenol A may be mentioned.

The diol unit (B) may contain these third diol units (B3) singly or in combination of two or more.

The proportion of the third diol units (B3) is, for example, less than 50 mol%, preferably 30 mol% or less, more preferably 10 mol% or less, relative to the total diol units (B). It is preferable not to contain the diol unit (B3) of the third diol unit (B3).

The ratio of the total amount of the first diol units (B1) and the second diol units (B2) is, for example, 1 mol% or more, specifically about 10 to 100 mol% of the total diol units (B). It can be selected from a range, and a preferred range is 30 mol % or more, 50 mol % or more, 70 mol % or more, 90 mol % or more, and particularly 100 mol % in a stepwise manner.

The diol unit (B) preferably contains at least one selected from the first diol unit (B1) and the second diol unit (B2), more preferably both. The ratio of the first diol unit (B1) to the second diol unit (B2) (also referred to as B1/B2) is, for example, the former/latter (molar ratio) = about 1/99 to 99/1, Specifically, it may be about 10/90 to 90/10, optical properties such as high refractive index, low Abbe number, low birefringence, high heat resistance, high moldability and polymerization reactivity (or high molecular weight ), etc. in a well-balanced manner, preferably in the following stages, 40/60 to 95/5, 50/50 to 90/10, 60/40 to 85/15, 70/30 to 80/20 while maintaining a balance of optical properties, high heat resistance and high moldability, especially in applications where a high refractive index is important, preferably the following stepwise, 10/90 to 75/25, 15/85 to 65/ 35, 25/75 to 55/45, 35/65 to 45/55, more preferably 20/80 to 95/5, 30/70 to 90/10, 40/ 60-80/20, 50/50-70/30, 55/45-65/35. If the ratio of the first diol units (B1) is too low, a decrease in refractive index, an increase in Abbe number, a decrease in heat resistance, etc. may occur. , there is a possibility that the moldability (or productivity) will be lowered, or that it will be difficult to increase the molecular weight.

Carbonate unit (C)
When the thermoplastic resin is a polyester resin containing a diol unit (B), it does not necessarily contain the diol unit (B). good too.

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

Therefore, the carbonate bond-forming component (C) may be any compound capable of forming a carbonate bond by reacting with the diol component. Typical carbonate bond-forming components (C) include, for example, phosgene and triphosgene and carbonic acid diesters such as diphenyl carbonate.

These carbonate bond-forming components (C) can be used alone or in combination of two or more. Of these carbonate bond-forming components (C), carbonic acid diesters such as diphenyl carbonate are preferred from the viewpoint of safety.

The ratio of the total amount of dicarboxylic acid units (A) and carbonate units (C) in the thermoplastic resin to the diol units (B) is the former/latter (molar ratio)=1/0.8 to 1/1.2. , preferably 1/0.9 to 1/1.1, preferably approximately equimolar. Further, the ratio (also referred to as A/C) of the dicarboxylic acid unit (A) and the carbonate unit (C) is A/C (molar ratio) = about 99/1 to 1/99, for example, 90/10 to 10/ It may be selected from a range of 90, preferably 80/20 to 20/80, 70/30 to 30/70, 60/40 to 40/60 in steps below. If the ratio of the carbonate unit (C) is too high, the refractive index and heat resistance may decrease.

Other structural units (D)
The thermoplastic resin may not contain other structural units (D) different from the dicarboxylic acid units (A), the diol units (B) and the carbonate units (C). It may be contained within a range that does not impair the effects of the invention.

Other structural units (D) include, for example, structural units derived from hydroxycarboxylic acid components, corresponding lactone components, multifunctional polymerization components having 3 or more polymerizable groups (carboxyl groups and/or hydroxyl groups), and the like. is mentioned.

Examples of hydroxycarboxylic acid components include aromatic hydroxycarboxylic acids such as hydroxybenzoic acid; aliphatic hydroxycarboxylic acids (hydroxyalkanoic acids) such as lactic acid, 3-hydroxybutyric acid and 6-hydroxyhexanoic acid; derivatives and the like. Examples of corresponding lactone components include lactones corresponding to hydroxyalkanoic acids such as ε-caprolactone. The thermoplastic resin may be a crystalline polymer, but since it is easy to reduce birefringence, it is derived from aromatic hydroxycarboxylic acids such as hydroxybenzoic acid, especially in applications such as optical members such as optical lenses. A non-liquid crystalline polymer containing no units is preferred, and an amorphous polymer is particularly preferred.

Polyfunctional polymerizable components having a total of 3 or more polymerizable groups (carboxyl groups and/or hydroxyl groups) include, for example, trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid; Polyhydric alcohols having a valence of 3 or more, such as erythritol, and the like.

The ratio of such other structural units (D) is relative to the total amount of structural units (dicarboxylic acid units (A), diol units (B), carbonate units (C) and other structural units (D)). , for example, 50 mol% or less, preferably 0 to 30 mol%, 0 to 10 mol%, 0.01 to 5 mol% in stages below, and substantially free of other structural units (D) is preferred.

[Method for producing thermoplastic resin]
The production method (or polycondensation) of the thermoplastic resin is not particularly limited except that the dicarboxylic acid component (A) containing at least the first dicarboxylic acid component (A1) is used as a polymerization component, and the type of resin and other A conventional method can be used depending on the polymerized component (copolymerized component) of the above. For example, in the case of a polyester resin such as a polyester resin, a dicarboxylic acid component (A) corresponding to each dicarboxylic acid unit described above, a diol component (B) corresponding to the diol unit described above, and, if necessary, It may be produced by reacting it with a carbonate bond-forming component (C) or the like, and is prepared by a conventional method, specifically, a transesterification method, a melt polymerization method such as a direct polymerization method, a solution polymerization method, an interfacial polymerization method, or the like. A melt polymerization method is preferred.

The reaction may be carried out in the presence or absence of a solvent depending on the polymerization method. For example, in the solution polymerization method and the interfacial polymerization method, a commonly used solvent such as a polar solvent having a high boiling point or a halogen-based solvent such as halogenated hydrocarbons may be used. If the solvent remains in the resulting thermoplastic resin, it may corrode the mold during molding. polymerization is preferred.

In addition, in the interfacial polymerization method, salts as by-products, such as inorganic salts such as sodium chloride, are generated, and this salt may cause turbidity in the obtained thermoplastic resin or its molded product. In particular, in applications such as optical members that require a high degree of transparency, it is preferable to produce by a method that does not produce salts as by-products.

Therefore, from the viewpoint of reducing troubles and defects during molding and improving moldability (productivity), especially the moldability of optical members such as optical lenses, it is possible to effectively suppress the remaining or contamination of solvents, salts, etc. Most preferred is the polymerization method (or melt polymer). In the present invention, a high-molecular-weight thermoplastic resin can be prepared even by a melt polymerization method. high molecular weight thermoplastics can be readily or efficiently prepared.

The charging ratio of the dicarboxylic acid component (A) and the diol component (B) is usually the former/latter (molar ratio)=for example, 1/1.2 to 1/0.8, preferably 1/1.1 to 1/0.9, but not necessarily within this range, and at least one component selected from each dicarboxylic acid component (A) and each diol component (B) is An excess may be used to react. For example, the second diol component (B2) such as ethylene glycol that can be distilled from the reaction system may be used in excess of the ratio (or introduction ratio) introduced into the polyester resin.

When the carbonate bond-forming component (C) is used, the ratio of the total amount of the dicarboxylic acid component (A) and the carbonate bond-forming component (C) to the diol component (B) is, for example, the former/latter (molar ratio )=1/1.2 to 1/0.8, preferably 1/1.1 to 1/0.9. Considering volatilization and decomposition in the reaction, the carbonate bond-forming component (C) may be used in a slightly excessive amount relative to the planned introduction ratio. The carbonate bond-forming component (C) may be used in excess of, for example, 0.1 to 5 mol %, preferably 2 to 3 mol %, relative to (the total amount to be introduced into the resin).

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

These catalysts can be used alone or in combination of two or more. When using a plurality of catalysts, each catalyst can be added according to the progress of the reaction. Among these catalysts, manganese acetate tetrahydrate, calcium acetate monohydrate, germanium dioxide, titanium (IV) tetrabutoxide and the like are preferred. The amount of the catalyst used is, for example, 0.01×10 ⁻⁴ to 100×10 ⁻⁴ mol, preferably 0.1×10 ⁻⁴ to 40×10 ⁻⁴ mol, per 1 mol of the dicarboxylic acid component (A). Mole.

The reaction may also be carried out in the presence of stabilizers such as heat stabilizers and antioxidants, if desired. Heat stabilizers are commonly used, and include phosphorus compounds such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dibutyl phosphate (or dibutyl phosphate), phosphorous acid, trimethyl phosphite, triethyl phosphite, and the like. . Among these, dibutyl phosphate is often used. The amount of the heat stabilizer used is, for example, 0.01×10 ⁻⁴ to 100×10 ⁻⁴ mol, preferably 0.1×10 ⁻⁴ to 40×10 mol, per 1 mol of the dicarboxylic acid component (A). ⁻⁴ mol.

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

After completion of the reaction, the produced thermoplastic resin is separated by a conventional method, for example, separation and purification means such as washing, extraction, concentration, reprecipitation, centrifugation, filtration, column chromatography, adsorption, or a combination thereof. It can be refined.

[Characteristics and uses of thermoplastic resin]
(Characteristic)
Since the thermoplastic resin contains the first dicarboxylic acid unit (A1), it has a higher refractive index and a higher Tg (heat resistance) than conventional thermoplastic resins containing an arenedicarboxylic acid unit such as a terephthalic acid unit. show. In addition, optical properties such as high refractive index, low Abbe number, and low birefringence, high heat resistance, high moldability, high polymerization reactivity (or high molecular weight), and the like can be satisfied in a well-balanced manner.

The thermoplastic resin has a high refractive index, and its refractive index nD can be selected, for example, from a range of about 1.65 to 1.75 at a temperature of 20° C. and a wavelength of 589 nm, preferably from 1.66 to 1.7, 1.67 to 1.69, 1.675 to 1.685, for applications where a higher refractive index is important, for example 1.68 to 1.7, preferably 1.685 to 1.695 more preferably 1.69 to 1.72, particularly 1.7 to 1.71.

The Abbe number of the thermoplastic resin may be, for example, about 20 or less at a temperature of 20° C., preferably 17 to 19.5, 17.5 to 19, 17.5 to 18.5 in steps below, More preferably, it is 13 to 18, 13 to 17.5, 13.3 to 17, 13.4 to 16, and 13.5 to 15 in the following steps. Since thermoplastic resins can effectively reduce the Abbe number, they reduce (or cancel out) chromatic aberration (bleeding) that occurs in applications that require a low Abbe number, such as camera lenses and other optical members in various cameras, especially convex lenses. (concave lenses in optical systems of various cameras configured by combining a plurality of convex lenses and concave lenses).

The birefringence of a thermoplastic resin is the birefringence of a stretched film (3 Double birefringence) may be used for evaluation. The absolute value of the 3-fold birefringence of the stretched film can be selected, for example, from a range of 75×10 ⁻⁴ or less at a measurement temperature of 20° C. and a wavelength of 600 nm, preferably 0 to 60×10 ⁻⁴ , 10×10 ⁻⁴ to 50×10 ⁻⁴ , 20×10 ⁻⁴ to 45×10 ⁻⁴ , 30×10 ⁻⁴ to 40×10 ⁻⁴ , more preferably 0 ˜30×10 ⁻⁴ , 0˜20×10 −4 , 0˜15×10 ⁻⁴ , 0˜10×10 ⁻⁴ , ^0˜5 ×10 ⁻⁴ . Although the thermoplastic resin contains many benzene ring skeletons (arene ring skeletons), it unexpectedly exhibits low birefringence. compatible.

Thermoplastic resins have high heat resistance, and their glass transition temperature Tg is, for example, about 120 to 200°C, preferably 140 to 180°C. 145-175°C, 150-170°C and 155-165°C in stages. If the Tg is too low, the heat resistance is lowered, and discoloration (or coloring) is likely to occur during production and/or use, or deformation in a high-temperature environment after molding into a predetermined shape is likely, requiring high thermal stability. There is a possibility that it cannot be used for the intended purpose. On the other hand, if the Tg is too high, the moldability or fluidity will decrease, and it will be difficult to form a smooth surface of the molded body when molding by a method such as injection molding, and it cannot be used as an optical member such as an optical lens. There is a risk. Although the thermoplastic resin contains many benzene ring skeletons (arene ring skeletons), it can suppress an excessive increase in Tg and has high moldability. and heat resistance.

Although the thermoplastic resin has a rigid and bulky skeleton such as the first dicarboxylic acid unit (A1) represented by the formula (1), it can be prepared to have a high molecular weight unexpectedly easily or efficiently. . The weight average molecular weight Mw of the thermoplastic resin can be measured by gel permeation chromatography (GPC) or the like, and is, for example, about 5,000 to 300,000, specifically 6,000 to 250,000, preferably 10,000 to 200,000 in terms of polystyrene. From such viewpoints, it is more preferably 25,000 to 150,000, 30,000 to 120,000, 40,000 to 100,000, 50,000 to 80,000, and 60,000 to 70,000 in the following steps. If the weight-average molecular weight Mw is too low, the moldability (productivity) may decrease, or the application may be limited.

In the present specification and claims, the refractive index nD, Abbe number, 3-fold birefringence, glass transition temperature Tg, and weight average molecular weight Mw can be measured by methods described in Examples below.

(Molded body)
The molded article should contain at least the thermoplastic resin, and should have excellent optical properties (high refractive index, low Abbe number, low birefringence, etc.), high heat resistance, high moldability, high molecular weight, etc. in a well-balanced manner. Since it is provided, it can be effectively used as an optical member such as an optical film (optical sheet) or an optical lens, especially as an optical lens.

The molded article may contain conventional additives such as fillers or reinforcing agents, colorants such as dyes and pigments, conductive agents, flame retardants, plasticizers, lubricants, release agents, antistatic agents, dispersants, flow control agents, Leveling agents, antifoaming agents, surface modifiers, hydrolysis inhibitors, carbon materials, stabilizers, stress reducing agents and the like may also be included. Stabilizers include antioxidants, ultraviolet absorbers, heat stabilizers, and the like. Examples of stress reducing agents include silicone oil, silicone rubber, various plastic powders, various engineering plastic powders, and the like. These additives may be used alone or in combination of two or more. The total proportion of these additives is, for example, 50 parts by mass or less, preferably 30 parts by mass or less, 0 to 10 parts by mass, based on 100 parts by mass of the thermoplastic resin. It may be about 5 parts by mass.

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

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

Thermoplastic resins are useful for forming optical films (or optical sheets) because they have excellent optical properties. The film (optical film) can be produced by forming (or molding) the thermoplastic resin using a conventional film-forming method such as casting (solvent casting), melt extrusion, calendering, and the like. .

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

The films may be unstretched or stretched films, and even stretched films can maintain low birefringence. Incidentally, such a stretched film may be either a uniaxially stretched film or a biaxially stretched film.

The draw ratio is, for example, 1.1 to 10 times, preferably 1.2 to 8 times, more preferably 1.5 to 6 times in each direction in uniaxial stretching or biaxial stretching. In the case of biaxial stretching, it may be equally stretched, for example, 1.5 to 5 times in both the longitudinal and transverse directions, or unevenly stretched, for example, 1.1 to 4 times in the longitudinal direction and 2 to 6 times in the transverse direction. It may be double stretched. In the case of uniaxial stretching, the film may be longitudinally stretched, for example, by 2.5 to 8 times in the longitudinal direction, or laterally stretched, for example, by 1.2 to 5 times in the horizontal direction.

The stretched film has an average thickness of, for example, 1 to 150 μm, preferably 3 to 120 μm, more preferably 5 to 100 μm.

In addition, such a stretched film can be obtained by subjecting a film after film formation (or an unstretched film) to a stretching treatment. The stretching method is not particularly limited, and in the case of uniaxial stretching, it may be either a wet stretching method or a dry stretching method, and in the case of biaxial stretching, it may be a tenter method (flat method) or a tube method. However, the tenter method is preferable because it is excellent in the uniformity of the stretched thickness.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited by these examples. Details of evaluation items and raw materials are shown below.

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

Regarding the resin sample, based on the obtained spectrum, the integrated value of the peaks derived from each monomer used in the polymerization was calculated, and the ratio of each monomer component (structural unit) introduced into the polymer (polymer composition ratio) was calculated.

(Glass transition temperature Tg)
Using a differential scanning calorimeter ("EXSTAR6000 DSC6220 ASD-2" manufactured by SII Nanotechnology Co., Ltd.), the temperature was measured in a nitrogen atmosphere at a heating rate of 10°C/min.

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

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

(Abbe number)
Using a test piece for measuring the refractive index nD at 589 nm (D line), the refractive index nF, nC were measured respectively. The Abbe number was calculated from the obtained refractive indices nF, nD and nC at each wavelength by the following formula.

(Abbe number)=(nD−1)/(nF−nC).

(Birefringence (stretched 3 times))
A film having a thickness of 200 to 600 μm was formed by hot-pressing the sample at 200 to 240°C. This film was cut into strips of 10 mm×50 mm, and was uniaxially stretched at 25 mm/min at a temperature condition of glass transition temperature Tg+10° C. at a draw ratio of 3 to obtain a test piece. Using a retardation film/optical material inspection device (manufactured by Otsuka Electronics Co., Ltd. "RETS-100"), the obtained test piece is subjected to a parallel Nicol rotation method under the conditions of a measurement temperature of 20 ° C. and a measurement wavelength of 600 nm. The retardation was measured, and the value was divided by the thickness of the measurement site to calculate the birefringence (or triple birefringence).

[material]
(Dicarboxylic acid component)
DNTPA-E: diethyl 2,5-di(2-naphthyl)terephthalate, synthesized according to Synthesis Example 1 described later MNTPA-M: dimethyl 2-(2-naphthyl)terephthalate, synthesized according to Synthesis Example 2 described later DMT: dimethyl terephthalate FDP-m: 9,9-bis(2-methoxycarbonylethyl)fluorene [or dimethyl ester of 9,9-bis(2-carboxyethyl)fluorene or fluorene-9,9-dipropionic acid ], synthesized in the same manner as in Example 1 described in JP-A-2005-89422, except that methyl acrylate [37.9 g (0.44 mol)] is used instead of t-butyl acrylate. DNFDP-m: 2,7-di(2-naphthyl)-9,9-bis(2-methoxycarbonylethyl)fluorene, according to Example 1B (2-DNFDP-m) described in WO 2020/213470 SA-m: dimethyl sebacate (diol component)
BNEF: 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, synthesized according to Synthesis Example 1 described in JP-A-2018-59074 1,5-PDO: 1,5 -Pentanediol EG: Ethylene glycol (carbonate bond forming component)
DPC: diphenyl carbonate

[Synthesis Example 1]
Synthesis of diethyl 2,5-di(2-naphthyl)terephthalate (DNTPA-E) In a 300 mL three-necked flask, 49.4 g (130 mmol) of diethyl 2,5-dibromoterephthalate, 45.9 g of 2-naphthylboronic acid (260mmol), 36.9g (260mmol) of potassium carbonate and 1.5g (7mmol) of palladium acetate were added, and after nitrogen substitution, 420mL of 2-methoxyethanol and 140mL of water were added and reacted at 25°C for 3 hours. rice field. 700 mL of chloroform was added to the resulting gray suspension for extraction. The organic layer was washed with 200 mL of distilled water three times and dried over anhydrous magnesium sulfate. After that, celite filtration was performed, and the organic layer was concentrated. 700 mL of methyl isobutyl ketone was added to the obtained crude crystals, heated to 120° C. for dissolution, and allowed to cool to 20° C. to precipitate crystals. The precipitated crystals were collected by filtration, dissolved again in 700 mL of methyl isobutyl ketone, and recrystallized under the same temperature conditions to obtain 44.0 g of DNTPA-E represented by the following formula (yield: 71%). . The ¹ H-NMR spectrum results of the obtained DNTPA-E are shown below and in FIG.

¹ H-NMR (300 MHz, CDCl ₃ ); δ (ppm) 7.97 (s, 2H), 7.91-7.88 (m, 8H), 7.54-7.49 (m, 6H), 4.10 (q, J=7.0 Hz, 4H), 0.92 (t, J=7.5 Hz, 6H).

[Synthesis Example 2]
Synthesis of Dimethyl 2-(2-naphthyl)terephthalate (MNTPA-M) Into a 1000 mL three-necked flask were added 25.1 g (92 mmol) of dimethyl bromoterephthalate, 16.7 g (97 mmol) of 2-naphthylboronic acid, and 13.7 g (97 mmol) of potassium carbonate. After adding 4 g (97 mmol) and 1.0 g (4.5 mmol) of palladium acetate and performing nitrogen substitution, 300 mL of 2-methoxyethanol and 100 mL of water were added and reacted at 25° C. for 3 hours. 300 mL of chloroform was added to the resulting gray suspension for extraction. The organic layer was washed twice with 300 mL of distilled water and dried over anhydrous magnesium sulfate. After that, celite filtration was performed, and the organic layer was concentrated. 100 mL of methyl isobutyl ketone was added to the resulting crude crystals, heated to 120° C. to dissolve, and allowed to cool to 20° C. to precipitate crystals, thereby obtaining 16.0 g of MNTPA-M represented by the following formula. (54% yield). The ¹ H-NMR spectrum results of the obtained MNTPA-M are shown below and in FIG.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) 8.17-7.92 (m, 2H), 7.89-7.83 (m, 5H), 7.53-7.42 (m , 3H), 3.96(s, 3H), 3.62(s, 3H).

[Comparative Example 1]
A reactor was charged with DMT (5.83 g (30 mmol)) and FDP-m (23.69 g (70 mmol)) as dicarboxylic acid components, BNEF (40.40 g (75 mmol)) and EG (13.97 g (225 mmol) as diol components. )), titanium (IV) tetrabutoxide (8.5 mg (15 μmol)) was charged as a catalyst for the transesterification and polycondensation reactions, and the mixture was gradually heated to 240°C under a nitrogen atmosphere and stirred to conduct the transesterification reaction. rice field. After removing the alcohol component generated by the transesterification reaction, dibutyl phosphate (12.6 mg (60 µmol)) was added as a heat stabilizer, and the temperature was gradually raised to 280°C and 130 Pa, the pressure was reduced, and EG was removed. A polycondensation reaction was carried out. After completion of the reaction, the content was taken out from the reactor to obtain a polyester resin.

[Example 1]
In the reactor, DNTPA-E (14.22 g (30 mmol)) and FDP-m (23.69 g (70 mmol)) as dicarboxylic acid components, BNEF (40.40 g (75 mmol)) and EG (13.97 g) as diol components (225 mmol)), and titanium (IV) tetrabutoxide (8.5 mg (15 μmol)) was charged as a catalyst for transesterification and polycondensation reactions, and gradually heated to 240°C under a nitrogen atmosphere with stirring to effect transesterification. did After removing the alcohol component generated by the transesterification reaction, dibutyl phosphate (12.6 mg (60 µmol)) was added as a heat stabilizer, and the temperature was gradually raised to 280°C and 130 Pa, the pressure was reduced, and EG was removed. A polycondensation reaction was carried out. After completion of the reaction, the content was taken out from the reactor to obtain a polyester resin.

[Example 2]
A reactor was charged with MNTPA-M (9.60 g (30 mmol)) and FDP-m (23.69 g (70 mmol)) as dicarboxylic acid components, BNEF (40.40 g (75 mmol)) and EG (13.97 g) as diol components. (225 mmol)), and titanium (IV) tetrabutoxide (8.5 mg (15 μmol)) was charged as a catalyst for transesterification and polycondensation reactions, and gradually heated to 240°C under a nitrogen atmosphere with stirring to effect transesterification. did After removing the alcohol component generated by the transesterification reaction, dibutyl phosphate (12.6 mg (60 µmol)) was added as a heat stabilizer, and the temperature was gradually raised to 280°C and 130 Pa, the pressure was reduced, and EG was removed. A polycondensation reaction was carried out. After completion of the reaction, the content was taken out from the reactor to obtain a polyester resin.

[Example 3]
In the reactor, DNTPA-E (37.92 g (80 mmol)) and FDP-m (6.77 g (20 mmol)) as dicarboxylic acid components, BNEF (21.55 g (40 mmol)) and EG (16.14 g) as diol components (260 mmol)), and titanium (IV) tetrabutoxide (8.5 mg (15 μmol)) was charged as a catalyst for the transesterification reaction and polycondensation reaction. did After removing the alcohol component generated by the transesterification reaction, dibutyl phosphate (12.6 mg (60 µmol)) was added as a heat stabilizer, and the temperature was gradually raised to 280°C and 130 Pa, the pressure was reduced, and EG was removed. A polycondensation reaction was carried out. After completion of the reaction, the content was taken out from the reactor to obtain a polyester resin.

Table 1 shows the evaluation results of the polymer composition ratio (ratio (molar ratio) of structural units derived from each polymerization component used for preparation) and each physical property value of each polyester resin obtained in Comparative Example 1 and Examples 1 to 3. shown in The values in parentheses in the column of polymer composition ratio in Table 1 indicate the charged composition ratio (molar ratio) of the corresponding polymerization components.

As is clear from the results in Table 1, Examples 1 to 3 were superior to Comparative Example 1 in the balance between optical properties and heat resistance. That is, in Examples 1 and 2 in which DNTPA-E or MNTPA-M was used instead of DMT in Comparative Example 1, the refraction The rate could be improved and the Abbe number could be reduced. Moreover, although the aromatic ring skeleton generally tends to increase birefringence, the birefringence is surprisingly low. I was able to achieve both refraction and refraction in a well-balanced manner. Therefore, it can be effectively used for optical lenses. In addition, although the rigid aromatic ring skeleton tends to increase Tg, the examples show relatively high heat resistance without excessively increasing Tg, and the balance between heat resistance and moldability is excellent. was

In addition, Example 3 is an example using DNTPA-E in a high proportion, and probably because the proportion of the aromatic ring skeleton is large, compared to Examples 1 and 2 and Comparative Example 1, a higher refractive index and a lower Abbe number were obtained. On the other hand, Tg did not increase excessively, and the balance between heat resistance and moldability was also excellent. However, probably because DNTPA-E has low polymerization reactivity due to the influence of two naphthyl groups, it seems difficult to increase the molecular weight when used in large amounts. Therefore, in applications where a high molecular weight is required, Examples 1 and 2, which have an excellent balance of properties and are capable of increasing the molecular weight, are preferred.

[Example 4]
DNTPA-E (7.12 g (15 mmol)), DNFDP-m (8.86 g (15 mmol)), FDP-m (23.69 g (70 mmol)) as a dicarboxylic acid component, BNEF (40 .40 g (75 mmol)), EG (13.97 g (225 mmol)), and titanium (IV) tetrabutoxide (8.5 mg (15 μmol)) as a catalyst for the transesterification and polycondensation reactions were charged under a nitrogen atmosphere at 240 The mixture was gradually heated to °C and stirred to carry out the transesterification reaction. After removing the alcohol component generated by the transesterification reaction, dibutyl phosphate (12.6 mg (60 µmol)) was added as a heat stabilizer, and the temperature was gradually raised to 280°C and 130 Pa, the pressure was reduced, and EG was removed. A polycondensation reaction was carried out. After completion of the reaction, the content was taken out from the reactor to obtain a polyester resin.

[Example 5]
DNTPA-E (7.12 g (15 mmol)), DNFDP-m (35.44 g (60 mmol)), SA-m (5.76 g (25 mmol)) as a dicarboxylic acid component, BNEF (32 .32 g (60 mmol)), EG (14.90 g (240 mmol)), and titanium (IV) tetrabutoxide (8.5 mg (15 μmol)) as a catalyst for the transesterification and polycondensation reactions were charged, under a nitrogen atmosphere, at 240 The mixture was gradually heated to °C and stirred to carry out the transesterification reaction. After removing the alcohol component generated by the transesterification reaction, dibutyl phosphate (12.6 mg (60 µmol)) was added as a heat stabilizer, and the temperature was gradually raised to 280°C and 130 Pa, the pressure was reduced, and EG was removed. A polycondensation reaction was carried out. After completion of the reaction, the content was taken out from the reactor to obtain a polyester resin.

[Example 6]
DNTPA-E (7.12 g (15 mmol)), DNFDP-m (20.67 g (35 mmol)) as a dicarboxylic acid component, DPC (10.71 g (50 mmol)) as a carbonate bond-forming component, and BNEF as a diol component were placed in a reactor. (40.40 g (75 mmol)), 1,5-PDO (2.60 g (25 mmol)), and titanium (IV) tetrabutoxide (8.5 mg (15 μmol)) as a catalyst for transesterification and polycondensation reactions. , Under a nitrogen atmosphere, the transesterification reaction was carried out by gradually heating and stirring to 240° C. After removing the alcohol component produced by the transesterification reaction, dibutyl phosphate (12.6 mg (60 μmol)) was added as a heat stabilizer. ) was added thereto, and the temperature was gradually raised to 280° C. and the pressure was reduced to 130 Pa to carry out a polycondensation reaction while removing phenol.After completion of the reaction, the contents were taken out from the reactor to obtain a polyester carbonate resin.

Table 2 shows the polymer composition ratio (proportion (molar ratio) of structural units derived from each polymerization component used in preparation) and the evaluation results of each physical property value of each polyester resin obtained in Examples 4 to 6. The values in parentheses in the column of polymer composition ratio in Table 2 indicate the charged composition ratio (molar ratio) of the corresponding polymerization components.

In Examples 5 and 6, the peaks of the ¹ H-NMR spectra overlapped, making it difficult to calculate an accurate polymer composition ratio. m (molar ratio) = 15/65/25, BNEF/EG (molar ratio) = about 60/40; The ratio was estimated to be about the same as the composition ratio of the feed.

As is clear from the results in Table 2, Examples 4 to 6 all had an excellent balance of optical properties and heat resistance. In particular, Example 4 not only exhibits excellent optical properties such as a higher refractive index, a lower Abbe number, and a lower birefringence than Example 1, but also has relatively high heat resistance without excessively increasing Tg. In addition, it had a high molecular weight and relatively good moldability, and had an excellent balance between heat resistance and moldability. Example 5 similarly had all of the above characteristics in a well-balanced manner. In Example 5, although the birefringence is slightly larger than that of Example 4, despite containing a structural unit derived from SA-m which is an aliphatic dicarboxylic acid component, it has a surprisingly high refractive index and a low Abbe number. In particular, the refractive index was greatly improved to 1.7 or more. Moreover, from Example 6, even the polyester carbonate resin was excellent in the balance between the optical properties and the heat resistance. Therefore, it is particularly useful as an optical material such as an optical lens.

The thermoplastic resin of the present invention can be used in various applications, for example, coating agents or coating films, specifically, paints, inks, protective films such as electronic devices and liquid crystal members, etc.; adhesives, adhesives; resin filling Agent; electric/electronic materials or electric/electronic parts (electric/electronic devices), specifically, antistatic agents, carrier transport agents, light emitters, organic photoreceptors, heat-sensitive recording materials, photochromic materials, hologram recording materials, charging Trays, conductive sheets, optical discs, inkjet printers, digital paper, color filters, organic EL elements, organic semiconductor lasers, dye-sensitized solar cells, sensors, EMI shielding films, etc.; machine materials or machine parts (equipment), specifically may be used for automobile materials or parts, aerospace-related materials or parts, sliding members, and the like.

Thermoplastic resins can be effectively used as optical members because they can satisfy optical properties such as a high refractive index, a low Abbe number, and a low birefringence, and heat resistance and moldability (productivity) in a well-balanced manner.

Typical optical members include optical films (optical sheets) such as liquid crystal films and organic EL films; optical lenses such as spectacle lenses and camera lenses; prisms, holograms, and optical fibers.

Examples of optical films include polarizing films, polarizing elements and polarizing plate protective films constituting polarizing films, retardation films, oriented films (oriented films), viewing angle widening (compensation) films, diffusion plates (films), and prism sheets. , light guide plate, brightness enhancement film, near-infrared absorption film, reflective film, anti-reflection (AR) film, reflection reduction (LR) film, anti-glare (AG) film, transparent conductive (ITO) film, anisotropic conductive film ( ACF), electromagnetic shielding (EMI) films, films for electrode substrates, films for color filter substrates, barrier films, color filter layers, black matrix layers, adhesive layers or release layers between optical films, and the like. These optical films can be effectively used as optical films for displays such as liquid crystal displays (LCD), organic EL displays (OLED), plasma displays (PDP), field emission displays (FED), and electronic paper. Examples of equipment or devices include televisions; personal computers (PCs) such as desktop PCs, notebook PCs or tablet PCs; smartphones, mobile phones; car navigation systems; flat panel displays (FPDs) such as touch panels. A device or device equipped with the device may be mentioned.

Examples of optical lenses include spectacle lenses, contact lenses, camera lenses, VTR zoom lenses, pickup lenses, Fresnel lenses, solar condensing lenses, objective lenses, and rod lens arrays. Since thermoplastic resins can reduce the Abbe number, they may be suitably used for lenses that require a low Abbe number, such as camera lenses. Devices or devices equipped with such an optical lens typically include compact devices or mobile devices with a camera function such as smartphones, mobile phones, and digital cameras; cameras for Since thermoplastic resins have high heat resistance, they may be used in applications that are assumed to be used in high-temperature environments, such as optical lenses for vehicles.

Claims (19)

A thermoplastic resin containing a dicarboxylic acid unit (A), wherein the dicarboxylic acid unit (A) is represented by the following formula (1)

(Wherein, Z ¹ represents a monocyclic or condensed polycyclic arene ring,
Z ² represents an arene ring, R ¹ represents a substituent, k1 represents an integer of 0 or more, m represents an integer of 1 or more,
^R2 represents a substituent, and k2 represents an integer of 0 or more. )
A thermoplastic resin having at least the first dicarboxylic acid unit (A1) represented by In the above formula (1), Z ¹ is a monocyclic or condensed polycyclic arene ring having 6 to 14 carbon atoms,
The thermoplastic resin according to Claim 1, wherein Z2 is an arene ring having ⁶ to 14 carbon atoms and m is an integer of 1 to 3. In the formula (1), Z ¹ is a benzene ring or a naphthalene ring,
Z ² is at least one arene ring selected from a benzene ring, a naphthalene ring and a biphenyl ring, m is an integer of 1 to 2,
3. The thermoplastic resin according to claim 1, wherein the first dicarboxylic acid unit (A1) accounts for 1 to 50 mol % of the total dicarboxylic acid unit (A). The dicarboxylic acid unit (A) is represented by the following formula (2)

(Wherein, R ³ represents a substituent, k3 represents an integer of 0 to 8,
A ^1a and A ^1b independently represent a divalent hydrocarbon group optionally having a substituent. ), the thermoplastic resin according to any one of claims 1 to 3, comprising a second dicarboxylic acid unit (A2) represented by In the formula (2), R ³ is an aryl group, k3 is an integer of 0 to 4,
5. The thermoplastic resin according to claim 4, wherein A1a and ^A1b are linear or branched ^alkylene groups. The second dicarboxylic acid unit (A2) contains at least a dicarboxylic acid unit (A2-2) in which R3 is an aryl group and ^k3 is an integer of 1 or more in the formula (2),
6. The thermoplastic resin according to claim 4 or 5, wherein the ratio of said dicarboxylic acid units (A2-2) is 1 to 100 mol% of the total second dicarboxylic acid units (A2). Any one of claims 4 to 6, wherein the ratio of the first dicarboxylic acid unit (A1) and the second dicarboxylic acid unit (A2) is the former/latter (molar ratio) = 5/95 to 90/10. The thermoplastic resin according to claim 1. The thermoplastic resin according to any one of claims 1 to 7, wherein the dicarboxylic acid unit (A) contains an aliphatic dicarboxylic acid unit as a third dicarboxylic acid unit (A3). 9. The thermoplastic resin according to claim 8, wherein the third dicarboxylic acid unit (A3) contains a structural unit derived from a linear or branched alkanedicarboxylic acid having 2 to 20 carbon atoms. The ratio of the first dicarboxylic acid unit (A1) and the third dicarboxylic acid unit (A3) is the former/latter (molar ratio) = 5/95 to 90/10,
10. The ratio of the second dicarboxylic acid unit (A2) and the third dicarboxylic acid unit (A3) is the former/latter (molar ratio)=10/90 to 95/5 according to claim 8 or 9. Thermoplastic resin. The thermoplastic resin according to any one of claims 1 to 10, which is a polyester resin further containing a diol unit (B). The diol unit (B) is represented by the following formula (3)

(Wherein, R ⁴ represents a substituent, k4 represents an integer of 0 to 8,
Z ^3a and Z ^3b independently represent an arene ring,
R ^5a and R ^5b independently represent a substituent, k5a and k5b independently represent an integer of 0 or more,
A ^2a and A ^2b independently represent a linear or branched alkylene group, and n2a and n2b independently represent an integer of 0 or 1 or more. )
The first diol unit (B1) represented by and the following formula (4)

( ^In the formula, A3 represents a linear or branched alkylene group, and n3 represents an integer of 1 or more.)
12. The thermoplastic resin according to claim 11, comprising at least one diol unit selected from the second diol units (B2) represented by: In the formula (3), Z ^3a and Z ^3b are monocyclic or condensed polycyclic arene rings,
A ^2a and A ^2b have 2 to 6 carbon atoms, n2a and n2b are integers of 0 to 10,
13. The thermoplastic resin according to claim 12, wherein A ³ has 2 to 6 carbon atoms and n3 is an integer of 1 to 4 in the formula (4). The diol unit (B) includes both the first diol unit (B1) and the second diol unit (B2), and the first diol unit (B1) and the second diol unit ( The thermoplastic resin according to claim 12 or 13, wherein the ratio with B2) is the former/latter (molar ratio) = 1/99 to 99/1. The thermoplastic resin according to any one of claims 1 to 14, which has a weight average molecular weight Mw of 6,000 to 250,000. A method for producing the thermoplastic resin according to any one of claims 1 to 15 by polymerizing a polymerization component containing at least a first dicarboxylic acid component corresponding to the first dicarboxylic acid unit (A1). A molded article comprising the thermoplastic resin according to any one of claims 1 to 15. 18. The molded article according to claim 17, which is an optical member. 19. The molded article according to claim 17 or 18, which is an optical lens.

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