Resin composition and molded article thereof

Abstract

To provide a polyester resin composition and its molded article, and a fluidity improving method and a fluidity improver, wherein the polyester resin composition exhibits superior melt fluidity (moldability or processability) without unduly reducing mechanical properties or optical properties, even in the absence of an additive having a 9,9-bisarylfluorene skeleton.SOLUTION: A polyester resin composition is prepared which comprises at least a polyester resin and a fluorene compound represented by the following formula (1), (in which R2a, R2b, R2c, and R2d denote H or a substituent, R3a and R3b denote H or a substituent, and X1a and X1b denote a group represented by formula (X1)).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a resin composition (or polyester resin composition) containing a polyester resin and a fluorene compound (or fluorene derivative) having a specific chemical structure, a molded product thereof, a method for improving flowability, and a flowability improver. [Background technology]

[0002] Polyester resins are widely used in a variety of applications. However, many polyester resins have low melt flowability, making them difficult to mold into fine shapes. Therefore, methods for improving the flowability of polyester resins have been proposed.

[0003] Japanese Patent Application Laid-Open No. 2015-218265 (Patent Document 1) discloses a method for improving the melt fluidity of a thermoplastic resin by introducing a specific structural unit into the resin.

[0004] Japanese Patent Application Laid-Open Publication No. 2018-203975 (Patent Document 2) discloses a fiber-reinforced resin composition containing an ester bond-containing thermoplastic resin, a fibrous reinforcing material, and a compound having a 9,9-bisarylfluorene skeleton, and describes that this composition can achieve both high mechanical properties and high melt fluidity (moldability).

[0005] Japanese Patent Application Laid-Open Publication No. 2014-218655 (Patent Document 3) discloses a heat resistance improver composed of a compound having a 9,9-bisarylfluorene skeleton as an additive for improving the heat resistance of polyester resins having a number average molecular weight of 10,000 or less, and describes that this heat resistance improver can maintain the viscosity (melt viscosity) of the resin without increasing the viscosity, thereby achieving both low viscosity and improved heat resistance.

[0006] In addition, International Publication No. 2021 / 172300 (Patent Document 4) discloses a novel fluorene derivative and a resin composition containing this fluorene derivative and a resin, and states that the fluorene compound can be used as a strength improver (mechanical property improver) for resin, a flowability improver, etc.

[0007] Furthermore, U.S. Pat. No. 2,299,948 (Patent Document 5) describes that 9,9-di-(β-carbamoyl-ethyl)fluorene represented by the following formula is useful as an intermediate for preparing synthetic resins.

[0008] [ka] [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-218265 [Patent Document 2] Japanese Patent Application Publication No. 2018-203975 [Patent Document 3] Japanese Patent Application Laid-Open No. 2014-218655 [Patent Document 4] International Publication No. 2021 / 172300 [Patent Document 5] U.S. Patent No. 2,299,948 Summary of the Invention [Problem to be solved by the invention]

[0010] In the examples of Patent Document 1, it is described that a dicarboxylic acid component containing 9,9-bis[2-(methoxycarbonyl)ethyl]fluorene (FDPM) is polymerized with a diol component, and the resulting polyester resin has significantly improved melt fluidity while maintaining a high refractive index and heat resistance.

[0011] However, since it is necessary to introduce specific structural units into the polyester resin, there are cases where applications are limited.

[0012] In the examples of Patent Document 2, it is described that by kneading a compound having a 9,9-bisarylfluorene skeleton such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (hereinafter also referred to as BPEF) with polybutylene terephthalate (PBT) or bisphenol A polycarbonate and a fibrous reinforcing material such as glass fiber, it is possible to improve the MFR without significantly reducing the mechanical properties.

[0013] Although the addition of a compound having a 9,9-bisarylfluorene skeleton can improve MFR to some extent without significantly reducing mechanical properties, the fluidity and mechanical properties may not be sufficient for applications requiring fine molding.

[0014] In the examples of Patent Document 3, it is described that by adding a compound having a 9,9-bisarylfluorene skeleton such as BPEF to a polyester resin having a number average molecular weight Mn of approximately 3600 to 4300 (weight average molecular weight Mw of approximately 4600 to 5200), heat resistance can be improved without increasing viscosity, and it is described that in Examples 6 and 7, in which 10% or 20% BPEF was added, the melt viscosity was improved.

[0015] However, since the molecular weight of the polyester resin is limited, the applications may be limited, and in applications requiring fine molding, the fluidity and mechanical properties may be insufficient.

[0016] Furthermore, Patent Documents 2 and 3 state that a 9,9-bisarylfluorene skeleton is essential in the chemical structure of the additive, and make no mention of fluorene compounds that do not have aryl groups at the 9,9-positions.

[0017] Patent Document 4 describes polyester resin as a resin that forms a resin composition, but only lists it as an example along with many other resins, including thermosetting resins that are cured by heat (or do not exhibit melt fluidity), and does not specifically describe the preparation of a polyester resin composition. The examples only include examples in which a specific fluorene derivative is added to a polyolefin resin or a polyamide resin, and it is shown that the MFR is improved only when the fluorene derivative is added to a polyamide resin, but there is no description of the effect of adding the fluorene derivative to a polyester resin, which has completely different properties.

[0018] In the examples of Patent Document 5, 9,9-di-(β-carbamoyl-ethyl)fluorene is prepared by reacting 9,9-di-(β-cyanoethyl)fluorene with sulfuric acid under specific conditions.

[0019] However, there is no description or suggestion as to the use of 9,9-di-(β-carbamoyl-ethyl)fluorene as an additive for improving the melt flowability of polyester resins.

[0020] Therefore, an object of the present disclosure is to provide a polyester resin composition and a molded product thereof that have excellent melt fluidity (moldability or processability) without excessively reducing mechanical or optical properties, even without containing an additive having a 9,9-bisarylfluorene skeleton, as well as a method for improving fluidity and a flowability improver. [Means for solving the problem]

[0021] As a result of intensive research to achieve the above object, the present inventors have found that adding a fluorene compound having a specific chemical structure to a polyester resin can effectively improve the fluidity of the polyester resin, even though the fluorene compound does not have a 9,9-bisarylfluorene skeleton, and have completed the present invention (or the present disclosure). That is, the present disclosure may include the following aspects.

[0022] Aspect [1]: A polyester resin composition containing at least a polyester resin and a fluorene compound represented by the following formula (1):

[0023] [ka] [In the formula, R 1 represents a substituent, k represents an integer of 0 to 8, R 2a , R 2b , R 2c and R 2d each independently represents a hydrogen atom or a substituent, R 3a and R 3b each independently represents a hydrogen atom or a substituent, X 1a and X 1b are independently represented by the following formula (X1)

[0024] [ka] (In the formula, R 4 and R 5 each independently represents a hydrogen atom or a hydrocarbon group, or R 4 and R 5 and are bonded to each other to form a heterocycle together with the adjacent nitrogen atom. represents a group represented by the formula:

[0025] Aspect [2]: In the formula (1), R 1 represents a hydrocarbon group, k represents an integer of 0 to 4, R 2a , R 2b , R 2c and R 2d each independently represents a hydrogen atom or a hydrocarbon group; R 3a and R 3b each independently represents a hydrogen atom or a hydrocarbon group; In the formula (X1), R 4 and R 5 are independently a hydrogen atom or an alkyl group.

[0026] Aspect [3]: In the formula (X1), R 4 and R 5 The polyester resin composition according to embodiment [1] or [2], wherein is a hydrogen atom.

[0027] Aspect [4]: ​​The polyester resin composition according to any one of aspects [1] to [3], wherein the polyester resin contains a structural unit having a fluorene skeleton.

[0028] Aspect [5]: The polyester resin composition according to any one of aspects [1] to [4], wherein the polyester resin contains a diol unit represented by the following formula (2) as a structural unit having a fluorene skeleton:

[0029] [ka] (In the formula, R 6 represents a substituent, m represents an integer of 0 to 8, Z 1a and Z 1b each independently represents an arene ring, R 7a and R 7b each independently represents a substituent, n1 and n2 independently represent an integer of 0 or more, A 1a and A 1b each independently represents an alkylene group (a linear or branched alkylene group), and p1 and p2 each independently represents an integer of 0 or 1 or more).

[0030] Aspect [6]: The polyester resin composition according to any one of aspects [1] to [5], wherein the polyester resin contains at least one dicarboxylic acid unit selected from an aliphatic dicarboxylic acid unit, an alicyclic dicarboxylic acid unit, and an aromatic dicarboxylic acid unit.

[0031] Aspect [7]: The polyester resin composition according to any one of aspects [1] to [6], wherein the proportion of the fluorene compound is 0.01 to 30 parts by mass per 100 parts by mass of the total amount of the polyester resin and the fluorene compound.

[0032] Aspect [8]: The polyester resin composition according to any one of aspects [1] to [7], wherein the proportion of the polyester resin is 50 mass % or more based on the total resin components in the composition.

[0033] Aspect [9]: A molded article comprising the polyester resin composition according to any one of aspects [1] to [8].

[0034] Aspect

[10] : A method for improving the flowability of a polyester resin by adding the fluorene compound represented by formula (1) according to any one of aspects [1] to [8] to the polyester resin.

[0035] Aspect

[11] : A flowability improver for polyester resin, comprising a fluorene compound represented by formula (1) according to any one of aspects [1] to [8].

[0036] The present disclosure may also achieve the following secondary objectives (or solve secondary problems).

[0037] That is, another object of the present disclosure is to provide a polyester resin composition and a molded product thereof that have excellent melt fluidity even when a fluorene compound is used as an additive in a small amount, as well as a flowability improving method and a flowability improving agent.

[0038] Yet another object of the present disclosure is to provide a polyester resin composition having an excellent balance of melt fluidity, mechanical properties, optical properties, and handleability (or stability), a molded product thereof, a method for improving fluidity, and a flowability improver.

[0039] In this specification and claims, the number of carbon atoms in a substituent is defined as C1, C6, C 10For example, an alkyl group with 1 carbon atom is called a "C1 alkyl," and an aryl group with 6 to 10 carbon atoms is called a "C 6-10 It is indicated as "aryl" etc.

[0040] Furthermore, in this specification and claims, the terms "diol unit" and "structural unit derived from a diol component" refer to a unit (or a divalent group) obtained by removing a hydrogen atom from each of the two hydroxyl groups of the corresponding diol component, and the term "diol component" (including compounds exemplified as diol components) may be used synonymously with the corresponding "diol unit."

[0041] Similarly, a "dicarboxylic acid unit" and a "structural unit derived from a dicarboxylic acid component" refer to a unit (or a divalent group) obtained by removing OH (hydroxyl group) from each of the two carboxyl groups of the corresponding dicarboxylic acid, and a "dicarboxylic acid component" (including compounds exemplified as dicarboxylic acid components) is sometimes used synonymously with the corresponding "dicarboxylic acid unit."

[0042] In the present specification and claims, the term "dicarboxylic acid component" refers to a dicarboxylic acid and its ester-forming derivatives. Examples of the ester-forming derivatives include alkyl esters, acid halides such as acid chlorides, and acid anhydrides. Examples of the alkyl esters include lower alkyl esters, such as C alkyl esters, methyl esters, ethyl esters, and t-butyl esters. 1-4 Alkyl esters, etc. The ester-forming derivatives may be monoesters (half esters) or diesters.

[0043] In the present specification and claims, "independently" means that two components are independent components, and the group R 2a and group R 2b In the case of R 2a and R 2b and do not necessarily have to be the same hydrogen atom or substituent, and may be different from each other.

[0044] In this specification and claims, a numerical range indicated as "X to Y" may include the numerical values ​​X and Y. [Effects of the Invention]

[0045] According to the present disclosure, it is possible to provide a polyester resin composition and a molded product thereof that have excellent melt fluidity (moldability or processability) without excessively reducing mechanical properties or optical properties, even without containing an additive having a 9,9-bisarylfluorene skeleton, as well as a flowability improving method and a flowability improving agent. DETAILED DESCRIPTION OF THE INVENTION

[0046] The polyester resin composition of the present disclosure is a thermoplastic (or non-thermosetting) composition containing at least a polyester resin and a fluorene compound having a specific chemical structure represented by formula (1).

[0047] In this specification and claims, unless otherwise specified, the term "fluorene compound" refers to a compound (low molecular weight compound) represented by formula (1), rather than an aromatic polyester resin containing a structural unit having a fluorene skeleton, which will be described later.

[0048] The polyester resin composition of the present disclosure combines a polyester resin with a fluorene compound having a specific chemical structure, and thus can achieve excellent mechanical and optical properties as well as excellent melt flowability, even without the addition of an additive having a 9,9-bisarylfluorene skeleton. Therefore, the polyester resin composition may have a high level of balance between mechanical properties such as tensile strength, flexural strength, and impact resistance, optical properties such as refractive index, and melt flowability. Furthermore, the polyester resin composition has excellent melt flowability even with a small amount of the fluorene compound as an additive, and may effectively suppress bleed-out of the fluorene compound. Therefore, the polyester resin composition can also have a high level of balance between melt flowability, mechanical properties, optical properties, and handleability (or stability). The present disclosure also encompasses a method of adding a fluorene compound as an additive to a polyester resin to improve flowability (melt flowability) without impairing mechanical and / or optical properties.

[0049] [Fluorene compounds] In the present disclosure, the fluorene compound that functions as a flowability improver (melt flowability improver) is a compound represented by the following formula (1), and by combining it with a polyester resin, it is possible to improve the melt flowability without impairing (while maintaining or improving) the mechanical properties and optical properties.

[0050] [ka] [In the formula, R 1 represents a substituent, k represents an integer of 0 to 8, R 2a , R 2b , R 2c and R 2d each independently represents a hydrogen atom or a substituent, R 3a and R 3b each independently represents a hydrogen atom or a substituent, X 1a and X 1b each independently represents a group represented by the following formula (X1):

[0051] [ka] (In the formula, R 4 and R 5 each independently represents a hydrogen atom or a hydrocarbon group, or R 4 and R 5 and bond to each other to form a heterocycle together with the adjacent nitrogen atom).

[0052] In the formula (1), the group R 1 The substituent may be a non-reactive substituent inert to the reaction, and examples thereof include a cyano group; a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; and a hydrocarbon group such as an alkyl group or an aryl group. The aryl group may be a C 6-10 Aryl groups are preferred. 1 is a cyano group, a halogen atom, or an alkyl group, particularly an alkyl group.

[0053] Examples of the alkyl group include C methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl groups. 1-12 Alkyl groups, preferably C 1-8 C alkyl groups, especially methyl groups 1-4 Examples of suitable alkyl groups include:

[0054] In addition, the group R 1 When the number of substitutions k is plural (2 or more), two or more groups R 1 The types of groups may be the same or different, and two or more groups R 1 The types of groups R may be the same or different. 1 The bonding position (substitution position) of is not particularly limited as long as it is the 1st to 8th positions of the fluorene ring, and examples thereof include the 2nd, 7th, and 2,7th positions of the fluorene ring.

[0055] The number of substitutions k may be, for example, an integer of about 0 to 6, and preferred ranges are integers of 0 to 4, 0 to 3, and 0 to 2, stepwise, more preferably 0 or 1, and particularly preferably 0. In the two benzene rings constituting the fluorene ring, the group R 1 The number of substitutions in each of the above may be different from each other, but is preferably the same.

[0056] R 2a , R 2b , R 2c and R 2d The substituent represented by the formula (I) may be a non-reactive substituent that is inactive in the reaction, and examples thereof include hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups.

[0057] Examples of the alkyl group include linear or branched C alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, neopentyl, hexyl, octyl, and decyl groups. 1-12 alkyl groups, preferably straight-chain or branched-chain C 1-10 Alkyl groups, more preferably linear or branched C 1-6 It is an alkyl group.

[0058] Examples of the cycloalkyl group include C cyclopentyl and cyclohexyl groups. 5-10 Cycloalkyl groups are exemplified.

[0059] Examples of the aryl group include C phenyl, alkylphenyl, biphenylyl, and naphthyl groups. 6-12 Examples of the alkylphenyl group include mono- to tri-C alkylphenyl groups such as methylphenyl (or tolyl) and dimethylphenyl (or xylyl). 1-4 Examples include alkyl-phenyl groups.

[0060] Examples of the aralkyl group include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl-C1-4 Examples of suitable alkyl groups include:

[0061] R 2a , R 2b , R 2c and R 2d Preferred substituents represented by the formula: 1-6 Alkyl group, C 1-5 Alkyl group, C 1-4 Alkyl group, C 1-3 alkyl group, more preferably C 1-2 It is an alkyl group, in particular a methyl group.

[0062] Preferred R 2a , R 2b , R 2c , R 2d is a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom. 2c and R 2d is preferably a hydrogen atom, and in such an embodiment, the preferred R 2a and R 2b is a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom (i.e., R 2a , R 2b , R 2c and R 2d are preferably hydrogen atoms).

[0063] Also, R 2a , R 2b , R 2c , R 2d The types of R may be different from each other, 2a and R 2b are identical and R 2c and R 2d are preferably the same.

[0064] R 3a and R 3bThe substituent represented by may be a non-reactive substituent that is inert to the reaction, and examples thereof include hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. Examples of these hydrocarbon groups include the above-mentioned R 2a , R 2b , R 2c and R 2d Examples of the substituent represented by the formula (I) include the same groups as the hydrocarbon groups exemplified above.

[0065] R 3a and R 3b Among the substituents represented by the formula (I), preferred substituents are alkyl groups, and preferred alkyl groups are as follows, in the order of steps: 1-6 Alkyl group, C 1-5 Alkyl group, C 1-4 Alkyl group, C 1-3 alkyl group, more preferably C 1-2 It is an alkyl group, in particular a methyl group.

[0066] Also, the preferred R 3a and R 3b is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0067] X 1a and X 1b (or formula (X1)), R 4 and R 5 Examples of the hydrocarbon group in the formula include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and a group in which a plurality of these groups are combined. Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group, and a group in which a plurality of these groups are combined include, for example, the above-mentioned R 2a , R 2b , R 2c and R 2d Examples of the substituent represented by the formula (I) include the same groups as the hydrocarbon groups exemplified above.

[0068] R 4 and R 5Among the hydrocarbon groups in the formula (I), aliphatic hydrocarbon groups such as alkyl groups and cycloalkyl groups are preferred, and among these, alkyl groups (linear or branched alkyl groups) such as methyl groups, ethyl groups, and isopropyl groups are preferred. More preferred alkyl groups are those listed in the following order: 1-8 Alkyl group, C 1-6 Alkyl group, C 1-4 is an alkyl group, C 1-3 Alkyl group, C 1-2 R is an alkyl group or an ethyl group. 4 and R 5 When both of R 4 and R 5 The types may be different from each other, but are preferably the same.

[0069] Also, R 4 and R 5 and may be bonded to each other to form a heterocycle (N-containing heterocycle) together with the adjacent nitrogen atom, the heteroatom being the nitrogen atom [i.e., R 4 , R 5 and a nitrogen atom bonding with a carbonyl group to form an amide group (amide bond or carboxylic acid amide), and may further contain one or more heteroatoms in addition to the nitrogen atom, as necessary. Examples of the heteroatom that may further be contained include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocycle may contain at least one heteroatom selected from these, and preferably contains at least an oxygen atom. The number of heteroatoms constituting the heterocycle may be, for example, about 1 to 3, preferably 1 to 2, and more preferably 2. The heterocycle is often, for example, a 5- to 7-membered ring (5- to 7-membered heterocycle), preferably a 5- or 6-membered ring, and more preferably a 6-membered ring. The heterocycle may be aromatic, but is preferably non-aromatic.

[0070] Representative heterocycles include heterocycles containing one or more nitrogen atoms, such as a pyrrolidine ring, a piperidine ring, and a homopiperidine ring (an azepane ring, a hexahydroazepine ring, or a hexamethyleneimine ring), and heterocycles containing a nitrogen atom and a heteroatom of a different kind, such as a morpholine ring. Preferred are non-aromatic 5- to 7-membered heterocycles containing a nitrogen atom and a heteroatom of a different kind, particularly an oxygen atom, such as a morpholine ring.

[0071] R 4 ,R 5 is preferably a hydrogen atom or a hydrocarbon group such as an aliphatic hydrocarbon group, more preferably a hydrogen atom or an alkyl group (a linear or branched alkyl group), and even more preferably a hydrogen atom or a C 1-6 Alkyl group, hydrogen atom or C 1-5 Alkyl group, hydrogen atom or C 1-4 Alkyl group, hydrogen atom or C 1-3 Alkyl group, hydrogen atom or C 1-2 an alkyl group, a hydrogen atom or an ethyl group, in particular a hydrogen atom; R 4 and R 5 Most preferably, both are hydrogen atoms.

[0072] X 1a and X 1b The types may be different from each other, but are preferably the same.

[0073] In formula (X1), R adjacent to the nitrogen atom 4 and R 5 may both be hydrogen atoms; one may be a hydrogen atom and the other may be a hydrocarbon group such as an aliphatic hydrocarbon group; R 4 and R 5 may both be hydrocarbon groups such as aliphatic hydrocarbon groups, or may be linked together to form a heterocyclic ring. 1a ] and / or [-C(=O)-X 1b] may be an unsubstituted amide group (or a carbamoyl group [—C(═O)—NH]); a monosubstituted amide group (or an N-substituted amide group); or a disubstituted amide group (or an N,N-disubstituted amide group). When it is a disubstituted amide group, R 4 and R 5 Preferably, both of the groups are aliphatic hydrocarbon groups.

[0074] Preferred groups [—C(═O)—X 1a ] and / or [-C(=O)-X 1b ] is preferably an unsubstituted amide group or a monosubstituted amide group, and from the viewpoint of easily maintaining or improving mechanical properties such as flexural modulus, and particularly effectively improving fluidity (melt fluidity), an unsubstituted amide group is more preferred, and the group [—C(═O)—X 1a ] and [-C(=O)-X 1b It is particularly preferred that both of the groups 1 and 2 are unsubstituted amide groups.

[0075] Representative fluorene compounds include, for example, those represented by the formula (1) in which R 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, R 4 and R 5 and a compound in which both are hydrogen atoms (unsubstituted amide compound), specifically, for example, 9,9-bis[(2-carbamoyl)C such as 9,9-bis(2-carbamoylethyl)fluorene and 9,9-bis(2-carbamoylpropyl)fluorene. 2-3 alkyl]fluorene, etc.; in formula (1), R 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, R 4 and R 5and the other is an alkyl group (N-alkyl substituted compound), specifically, for example, 9,9-bis[2-(NC)-methylcarbamoylethyl]fluorene, 9,9-bis[2-(N-methylcarbamoyl)propyl]fluorene, 9,9-bis[2-(N-ethylcarbamoyl)ethyl]fluorene, 9,9-bis[2-(N-isopropylcarbamoyl)ethyl]fluorene, 9,9-bis[2-(N-isopropylcarbamoyl)propyl]fluorene, 9,9-bis[2-(N-butylcarbamoyl)ethyl]fluorene, etc. 1-6 Alkyl-carbamoyl)C 2-3 alkyl]fluorene, etc.; in formula (1), R 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, R 4 and R 5 is an alkyl group (N,N-dialkyl substituted compound), specifically, for example, 9,9-bis[2-(N,N-diC] such as 9,9-bis[2-(N,N-dimethylcarbamoyl)ethyl]fluorene, 9,9-bis[2-(N,N-dimethylcarbamoyl)propyl]fluorene, 9,9-bis[2-(N,N-diethylcarbamoyl)ethyl]fluorene, 9,9-bis[2-(N,N-diethylcarbamoyl)propyl]fluorene, 9,9-bis[2-(N,N-diisopropylcarbamoyl)ethyl]fluorene, and 9,9-bis[2-(N,N-dibutylcarbamoyl)ethyl]fluorene. 1-6 Alkyl-carbamoyl)C 2-3 alkyl]fluorene, etc.; in formula (1), R 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, R 4 and R 5and bond to each other to form a 5- to 7-membered heterocycle which may further contain at least one heteroatom selected from a nitrogen atom, an oxygen atom, and a sulfur atom in addition to the nitrogen atom constituting the amide group, specifically, for example, 9,9-bis[2-(N-containing heterocycle-N-yl-carbonyl)C such as 9,9-bis[2-(morpholin-4-yl-carbonyl)ethyl]fluorene, 9,9-bis[2-(morpholin-4-yl-carbonyl)propyl]fluorene, 9,9-bis[2-(pyrrolidin-1-yl-carbonyl)ethyl]fluorene, 9,9-bis[2-(piperidin-1-yl-carbonyl)ethyl]fluorene, and 9,9-bis[2-(homopiperidin-1-yl-carbonyl)ethyl]fluorene. 2-3 alkyl]fluorene and the like.

[0076] The molecular weight of the fluorene compound may be, for example, about 308 to 2000, and preferably in the following stepwise order: 308 to 1000, 308 to 800, 308 to 500, 308 to 450, 308 to 400, and 308 to 350. When the molecular weight is within an appropriate range that is not too large, fluidity tends to be easily improved.

[0077] The fluorene compound may be in crystalline or amorphous form, and the melting point in the crystalline form is determined by the group [—C(═O)—X 1a ] and [-C(=O)-X 1b When the group [—C(═O)—X 1a ] and [-C(=O)-X 1b When the group [—C(═O)—X 1a ] and [-C(=O)-X 1b When [Chemical Formula 1] is a disubstituted amide group, the temperature may be, for example, about 50 to 200°C, preferably 70 to 180°C, more preferably 80 to 160°C, even more preferably 80 to 100°C, and particularly preferably 85 to 90°C.

[0078] In this specification and claims, the melting point can be measured using a melting point meter or the like, specifically, by the method described in the examples of WO 2021 / 172300.

[0079] The 5% weight loss temperature of the fluorene compound may be, for example, about 200 to 400°C, and preferably the following stepwise temperatures: 230 to 380°C, 250 to 360°C, 280 to 350°C, 300 to 340°C, and 310 to 330°C. Thus, the fluorene compound has high heat resistance. Therefore, it can be effectively used as a flow improver or strength improver without decomposing even in a high-temperature environment.

[0080] In this specification and claims, the 5% weight loss temperature can be measured using thermogravimetry (TG), specifically, by the method described in the examples of WO 2021 / 172300.

[0081] These fluorene compounds can be used alone or in combination of two or more.Among these fluorene compounds, the unsubstituted amide compound, the N-alkyl-substituted compound or the N,N-dialkyl-substituted compound is preferred, and the unsubstituted amide compound or the N-alkyl-substituted compound is more preferred, and the unsubstituted amide compound is particularly preferred from the viewpoint that it is easy to maintain or improve mechanical properties such as flexural modulus, and in particular, it can effectively improve fluidity (melt fluidity).

[0082] The method for producing the fluorene compound represented by the formula (1) is not particularly limited, and for example, the method described in WO 2021 / 172300, specifically, 1 and k, and 9H-fluorenes corresponding to R 2a ~R 2d , R 3a ~R 3b and X 1a ~X 1b (or R 4 ~R 5) with a corresponding acryloyl group-containing compound (Michael addition reaction).

[0083] The proportion of the fluorene compound may be selected from a range of, for example, about 0.01 to 80 parts by mass relative to 100 parts by mass of the total amount of the polyester resin and the fluorene compound, preferably in the following stepwise manner: 0.01 to 50 parts by mass, 0.01 to 30 parts by mass, 0.03 to 20 parts by mass, 0.05 to 15 parts by mass, 0.08 to 10 parts by mass, 0.1 to 8 parts by mass, 0.15 to 5 parts by mass, 0.2 to 4 parts by mass, 0.25 to 3 parts by mass, 0.3 to 2.5 parts by mass, 1 to 2.5 parts by mass, 1.5 to 2.5 parts by mass, 2 to 2.5 parts by mass. When the proportion of the fluorene compound is in a moderate range that is not too high, it tends to be easier to maintain or improve mechanical properties and optical properties, to improve fluidity, and to suppress bleed-out of the fluorene compound. When the proportion of the fluorene compound is within a moderate range that is not too small, it tends to be easier to improve mechanical properties such as fluidity and bending properties. However, in the present disclosure, even if the proportion of the fluorene compound is relatively small, it may be possible to effectively improve fluidity and mechanical properties such as bending properties.

[0084] [Polyester resin] Polyester resins are resins having a main chain linked or formed by ester bonds (excluding carbonate ester bonds), and examples thereof include polymers of diol components and dicarboxylic acid components, polymers of lactone components and / or hydroxycarboxylic acid components, and copolymers thereof. Examples of the diol component, dicarboxylic acid component, lactone component, and hydroxycarboxylic acid component include diol components corresponding to the diol units described below, dicarboxylic acid components corresponding to the dicarboxylic acid units described below, lactone components described below, and hydroxycarboxylic acid components described below, respectively. The diol component, dicarboxylic acid component, lactone component, and hydroxycarboxylic acid component may each be used alone or in combination of two or more.

[0085] Representative polyester resins include aromatic polyester resins such as polyalkylene arylate resins, polyarylate resins, and liquid crystal polyesters (LCPs), and aliphatic polyester resins such as polycaprolactone, etc. Examples of polyalkylene arylate resins include polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), poly 1,4-cyclohexyldimethylene terephthalate (PCT), polyethylene naphthalate (PEN), and copolymers thereof.

[0086] These polyester resins may be used alone or in combination of two or more. Among these polyester resins, aromatic polyester resins such as polyalkylene arylate resins are preferred.

[0087] The polyester resin is preferably an aromatic polyester resin containing a structural unit having a fluorene skeleton. Such polyester resins often have excellent mechanical properties and optical properties. In the present disclosure, even if the fluorene compound represented by formula (1) is added, these excellent properties are not excessively reduced (maintained or improved), and the melt fluidity can be effectively improved.

[0088] Among the constituent units (units derived from polymerization components) of the polyester resin, the diol unit and / or the dicarboxylic acid unit may contain a constituent unit having a fluorene skeleton, and it is preferable that at least the diol unit contains a constituent unit having a fluorene skeleton.

[0089] (Diol unit (A)) The polyester resin often contains a diol unit (A) derived from a diol component.

[0090] Diol unit (A1) The diol unit (A) may not necessarily be contained, but it is preferable that the diol unit (A1) is contained as a structural unit having a fluorene skeleton, the structural unit being represented by the following formula (2) [hereinafter, also referred to as diol unit (A1)].

[0091] [ka] (In the formula, R 6 represents a substituent, m represents an integer of 0 to 8, Z 1a and Z 1b each independently represents an arene ring, R 7a and R 7b each independently represents a substituent, n1 and n2 independently represent an integer of 0 or more, A 1a and A 1b each independently represents an alkylene group (a linear or branched alkylene group), and p1 and p2 each independently represents an integer of 0 or 1 or more).

[0092] In the formula (2), Z 1a and Z 1b Examples of the arene ring (aromatic hydrocarbon ring) represented by the formula (I) include a monocyclic arene ring such as a benzene ring, and a polycyclic arene ring. The polycyclic arene ring includes a fused polycyclic arene ring (fused polycyclic aromatic hydrocarbon ring) and a ring-assembled arene ring (ring-assembled polycyclic aromatic hydrocarbon ring).

[0093] The fused polycyclic arene ring includes, for example, fused bicyclic arene rings, fused tricyclic arene rings, and other fused bicyclic to tetracyclic arene rings. The fused bicyclic arene ring includes, for example, fused bicyclic C rings such as naphthalene rings and indene rings. 10-16 Examples of the fused tricyclic arene ring include fused tricyclic C arene rings such as anthracene rings and phenanthrene rings. 14-20 Preferred fused polycyclic arene rings include fused polycyclic C arene rings such as naphthalene rings. 10-14 It is an arene ring.

[0094] Examples of the ring-assembled arene ring include biarene rings such as biphenyl ring, phenylnaphthalene ring, and binaphthyl ring; and terarene rings such as terphenyl ring. Preferred ring-assembled arene rings include C 12-18 It is a biarene ring.

[0095] In this specification and claims, the term "ring assembly arene ring" refers to two or more ring systems (arene ring systems) directly connected by single bonds or double bonds, and the number of bonds directly connecting the rings is one less than the number of ring systems. For example, as described above, phenylnaphthalene rings and binaphthyl rings are classified as ring assembly arene rings even though they have a fused polycyclic arene ring skeleton, and are clearly distinguished from "fused polycyclic arene rings" such as naphthalene rings (non-ring assembly arene rings).

[0096] Z 1a and Z 1b The types of Z may be the same or different from each other, and are preferably the same. 1a and Z 1b is a C ring such as a benzene ring, naphthalene ring, or biphenyl ring. 6-12 arene rings, and more preferably C rings such as benzene rings and naphthalene rings. 6-10 arene rings, particularly naphthalene rings.

[0097] In addition, Z bonded to the 9-position of the fluorene ring 1a and Z 1b The substitution position of is not particularly limited, and for example, Z 1a , Z 1b When Z is a benzene ring, it may be at any position. 1a , Z 1b When is a naphthalene ring, it is either the 1-position (1-naphthyl) or the 2-position (2-naphthyl), preferably the 2-position, and Z 1a , Z 1b When is a biphenyl ring, it is at the 2-, 3- or 4-position, preferably the 3-position.

[0098] R 6The substituent represented by is preferably a non-reactive group or a non-polymerizable group that is inert to the reaction, and examples thereof include a halogen atom, a hydrocarbon group, a group [—OR h ](where R h represents a hydrocarbon group), the group [-SR h ](where R h represents a hydrocarbon group), an acyl group, a nitro group, a cyano group, a substituted amino group (mono- or di-substituted amino group), and the like.

[0099] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0100] R 6 Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

[0101] The alkyl group may be a straight-chain or branched-chain alkyl group, for example, a C 1 group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, or a t-butyl group. 1-10 alkyl group, preferably C 1-6 alkyl group, more preferably C 1-4 It is an alkyl group.

[0102] Examples of the cycloalkyl group include C cyclopentyl and cyclohexyl groups. 5-10 Cycloalkyl groups are exemplified.

[0103] Examples of the aryl group include C phenyl, alkylphenyl, biphenylyl, and naphthyl groups. 6-12 Examples of the alkylphenyl group include mono- to tri-C alkylphenyl groups such as methylphenyl (or tolyl) and dimethylphenyl (or xylyl). 1-4 Examples include alkyl-phenyl groups.

[0104] Examples of the aralkyl group include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl-C1-4 Examples of suitable alkyl groups include:

[0105] The group [-OR h ], group [-SR h ] in R h Examples of the hydrocarbon group represented by the formula include the above-mentioned R 6 Examples of the hydrocarbon group include the same groups as those exemplified above.

[0106] The group [-OR h ] includes, for example, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, etc., and specifically, the hydrocarbon group R h Examples of the alkoxy group include linear or branched alkoxy groups, such as C alkoxy groups, including methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, and t-butoxy groups. 1-10 Examples of the cycloalkyloxy group include a C alkoxy group such as a cyclohexyloxy group. 5-10 Examples of the aryloxy group include a C aryloxy group such as a phenoxy group. 6-10 Examples of the aralkyloxy group include C aryloxy groups such as benzyloxy groups. 6-10 Aryl-C 1-4 Examples thereof include alkyloxy groups.

[0107] The group [—SR h ] includes, for example, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, etc., and specifically, the hydrocarbon group R h Examples of the alkylthio group include a C thio group, such as a methylthio group, an ethylthio group, a propylthio group, an n-butylthio group, and a t-butylthio group. 1-10 Examples of the cycloalkylthio group include a C alkylthio group such as a cyclohexylthio group. 5-10 Examples of the arylthio group include a C thiophenoxy group. 6-10Examples of the aralkylthio group include a C arylthio group such as a benzylthio group. 6-10 Aryl-C 1-4 Examples include alkylthio groups.

[0108] Acyl groups include C groups such as acetyl groups. 1-6 Examples include alkyl-carbonyl groups.

[0109] Examples of the mono- or di-substituted amino group include a dialkylamino group and a bis(alkylcarbonyl)amino group. Examples of the dialkylamino group include a di-C group such as a dimethylamino group. 1-4 Examples of the bis(alkylcarbonyl)amino group include bis(C acetylamino group, etc. 1-4 alkyl-carbonyl)amino groups.

[0110] Among these groups, representative R 6 Examples of R include a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, and a substituted amino group. 6 is a halogen atom, a hydrocarbon group, or a cyano group, and more preferably a hydrocarbon group such as an alkyl group. The alkyl group may be a linear or branched alkyl group, for example, a C alkyl group such as a methyl group, an ethyl group, or a t-butyl group. 1-6 alkyl groups, and C groups such as methyl groups. 1-4 Alkyl groups are preferred.

[0111] Also, R 6 The number of substitutions m is, for example, an integer of 0 to 6, preferably an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, an integer of 0 to 1, and particularly preferably 0. When the number of substitutions m is 2 or more, two or more groups R 6 The types of R may be the same or different, and are preferably the same. 6 The bonding positions (substitution positions) of are not particularly limited as long as they are positions 1 to 8 of the fluorene ring, and examples thereof include positions 2, 7, and 2,7 of the fluorene ring, with positions 2,7 being preferred.

[0112] R 7a and R 7b The substituent represented by R is preferably a non-reactive group or a non-polymerizable group that is inert to the reaction. 6 Representative substituents include halogen atoms, hydrocarbon groups, alkoxy groups, acyl groups, nitro groups, cyano groups, and substituted amino groups. 7a , R 7b Examples of the alkyl group include hydrocarbon groups such as alkyl groups, cycloalkyl groups, and aryl groups, and groups such as alkoxy groups [—OR h ], and more preferably a linear or branched C 1-6 C such as alkyl group and cyclohexyl group 5-8 C such as cycloalkyl group and phenyl group 6-14 Linear or branched C such as aryl group, methoxy group 1-4 Among these, alkyl groups and aryl groups are preferred, and in particular, straight-chain or branched C groups such as methyl groups are preferred. 1-4 C such as alkyl group and phenyl group 6-10 An aryl group is preferred. 7a , R 7b is an aryl group, R 7a , R 7b are rings Z 1a , Z 1b may form the ring assembly arene ring together with

[0113] R 7a , R 7b The numbers of substitutions n1 and n2 may each be an integer of 0 or greater, and the ring Z 1a , Z 1b n1 and n2 may be different from each other, but are preferably the same. When n1 is 2 or more, n2 is preferably 2 or more ... 7amay be the same or different from each other, and when n2 is 2 or more, two or more R 7b The types of R may be the same or different. 7a , R 7b The types of R may be the same or different from each other. 7a , R 7b The substitution position of Z is not particularly limited. 1a , Z 1b In the above, the substituent may be any substituent other than the ether bond (—O—) forming the main chain and the bonding position with the 9-position of the fluorene ring. For example, Z 1a , Z 1b may be substituted at the ortho position (carbon atom adjacent to the bonding position of the ether bond) relative to the ether bond (—O—).

[0114] A 1a , A 1b Examples of the alkylene group (linear or branched alkylene group) represented by the formula (I) include C alkylene groups such as an ethylene group, a propylene group (1,2-propanediyl group), a trimethylene group, a 1,2-butanediyl group, and a tetramethylene group. 2-6 alkylene groups, and preferably C 2-4 C alkylene group, more preferably ethylene group, propylene group, etc. 2-3 Alkylene groups, especially ethylene groups, are preferred.

[0115] Alkyleneoxy group [-(A 1a O)-], [-(A 1b The repeat numbers (number of moles added) p1 and p2 of the formula [O)-] may each be 0 or greater and can be selected, for example, from a range of about 0 to 15, preferably in the following stepwise order: 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, and 0 to 1. Furthermore, when the repeat numbers p1 and p2 are 1 or greater, polymerization reactivity is easily improved, and they can be selected, for example, from a range of about 1 to 15, preferably in the following stepwise order: 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, and 1 to 2, with 1 being particularly preferred.

[0116] In the present specification and claims, the "number of repetitions (number of moles added)" may be an average value (arithmetic mean value, additive mean value) or an average number of moles added, and preferred embodiments may be the same as the preferred ranges described above. When p1 and p2 are in an appropriate range that is not too large, there is a tendency that a decrease in heat resistance and refractive index tends to be easily suppressed. Furthermore, p1 and p2 may be the same or different from each other. When p1 is 2 or more, two or more alkyleneoxy groups [-(A 1a The types of alkyleneoxy groups [-(A 1b The types of A)- may be different from each other, but are preferably the same. 1a and A 1b The types may be different from each other, but are preferably the same.

[0117] The group [-O-(A 1a O) p1 -], [-O-(A 1b O) p2 -] (i.e., the ether bond forming the main chain) 1a , Z 1b The substitution position for Z is not particularly limited. 1a , Z 1b The group [-O-(A 1a O) p1 -], [-O-(A 1b O) p2 -] Ring Z 1a , Z 1b The substitution position for Z 1a , Z 1b When Z is a benzene ring, it is preferably substituted at the 2-, 3- or 4-position of the phenyl group bonded to the 9-position of the fluorene ring, among which the 3- or 4-position, and particularly the 4-position. 1a , Z 1bWhen Z is a naphthalene ring, it is often substituted at any one of the 5- to 8-positions of the naphthyl group bonded to the 9-position of the fluorene ring. For example, the 1- or 2-position of the naphthalene ring is substituted with the 9-position of the fluorene ring (substitution in a 1-naphthyl or 2-naphthyl relationship), and it is preferred that Z be substituted with the 1,5- or 2,6-position, particularly 2,6-position, relative to this substitution position. 1a , Z 1b is a ring-assembled arene ring, the group [-O-(A 1a O) p1 -], [-O-(A 1b O) p2 The substitution position of Z - is not particularly limited, and may be, for example, substituted on the arene ring bonded to the 9-position of the fluorene or on the arene ring adjacent to this arene ring. 1a , Z 1b is a biphenyl ring (or Z 1a , Z 1b is a benzene ring, n1 and n2 are 1, R 7a , R 7b is a phenyl group), the 3- or 4-position of the biphenyl ring, preferably the 3-position, may be bonded to the 9-position of the fluorene. When the 3-position of the biphenyl ring is bonded to the 9-position of the fluorene, the group [—O—(A 1a O) p1 -], [-O-(A 1b O) p2 The substitution position of -] may be, for example, any of the 2-, 4-, 5-, 6-, 2'-, 3'-, and 4'-positions of the biphenyl ring, preferably the 6- or 4'-position, and particularly preferably the 6-position.

[0118] Examples of the diol component (A1) corresponding to the diol unit (A1) include 9,9-bis(hydroxyaryl)fluorenes in which p1 and p2 are 0 in the formula (2); and 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes in which p1 and p2 are 1 or more, for example, about 1 to 10.

[0119] In this specification and claims, unless otherwise specified, the term "(poly)alkoxy" is used to mean both an alkoxy group and a polyalkoxy group.

[0120] Examples of 9,9-bis(hydroxyaryl)fluorenes include 9,9-bis(hydroxyphenyl)fluorene, 9,9-bis(alkyl-hydroxyphenyl)fluorene, 9,9-bis(aryl-hydroxyphenyl)fluorene, and 9,9-bis(hydroxynaphthyl)fluorene.

[0121] Examples of 9,9-bis(hydroxyphenyl)fluorene include 9,9-bis(4-hydroxyphenyl)fluorene.

[0122] Examples of the 9,9-bis(alkyl-hydroxyphenyl)fluorene include 9,9-bis[(mono- or di-)C]fluorene such as 9,9-bis(4-hydroxy-3-methylphenyl)fluorene and 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene. 1-4 alkyl-hydroxyphenyl]fluorene and the like.

[0123] Examples of 9,9-bis(aryl-hydroxyphenyl)fluorene include 9,9-bis(C 6-10 aryl-hydroxyphenyl)fluorene.

[0124] 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.

[0125] Examples of 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes include 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorene, 9,9-bis[alkyl-hydroxy(poly)alkoxyphenyl]fluorene, 9,9-bis[aryl-hydroxy(poly)alkoxyphenyl]fluorene, and 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorene.

[0126] Examples of the 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[hydroxy(mono- to deca)C such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene and 9,9-bis[4-(2-hydroxypropoxy)phenyl]fluorene. 2-4 alkoxy-phenyl]fluorene and the like.

[0127] Examples of the 9,9-bis[alkyl-hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[(mono- or di-)C such as 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene, and 9,9-bis[4-(2-hydroxypropoxy)-3-methylphenyl]fluorene. 1-4 Alkyl-hydroxy (mono or deca)C 2-4 alkoxy-phenyl]fluorene and the like.

[0128] Examples of the 9,9-bis[aryl-hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[C such as 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene and 9,9-bis(4-(2-hydroxypropoxy)-3-phenylphenyl)fluorene. 6-10 Aryl-hydroxy(mono or deca)C 2-4 alkoxy-phenyl]fluorene and the like.

[0129] Examples of the 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorene include 9,9-bis[hydroxy(mono- to deca)C such as 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, 9,9-bis[5-(2-hydroxyethoxy)-1-naphthyl]fluorene, and 9,9-bis[6-(2-hydroxypropoxy)-2-naphthyl]fluorene. 2-4 Alkoxy-naphthyl]fluorene and the like.

[0130] These diol units (A1) may be contained alone or in combination of two or more. Preferred diol units (A1) are 9,9-bis[hydroxy(mono- to penta)C 2-4 Alkoxy C 6-12 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes such as 9,9-bis[hydroxy(poly)alkoxyaryl]fluorene; more preferably 9,9-bis[hydroxyC 2-4 Alkoxy C 6-12 9,9-bis[hydroxyalkoxyaryl]fluorenes such as 9,9-bis[hydroxyalkoxyaryl]fluorene; more preferably 9,9-bis[hydroxyC 2-3 9,9-bis[hydroxy C]alkoxy-naphthyl]fluorene 2-3 Alkoxy C 6-10 It is a structural unit derived from arylfluorene, etc.

[0131] The proportion of the preferred diol units (A1) such as 9,9-bis[hydroxyalkoxyaryl]fluorene relative to the total diol units (A1) is, for example, about 10 to 100 mol %, preferably 50 mol % or more, 70 mol % or more, 90 mol % or more, and more preferably 100 mol %.

[0132] Diol unit (A2) The diol unit (A) may or may not contain a diol unit represented by the following formula (3) [hereinafter also referred to as a diol unit (A2)].

[0133] [ka] (In the formula, A 2 represents an alkylene group (a linear or branched alkylene group), and q represents an integer of 1 or more).

[0134] In the formula (3), A 2Examples of the alkylene group (linear or branched alkylene group) represented by the formula (I) include C alkylene groups such as ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, 1,3-butanediyl group, tetramethylene group, 1,5-pentanediyl group, 1,6-hexanediyl group, 1,8-octanediyl group, and 1,10-decanediyl group. 2-12 Preferred alkylene groups include the following in the order listed below: 2-10 Alkylene group, C 2-8 Alkylene group, C 2-6 Alkylene group, C 2-4 C alkylene groups, more preferably ethylene groups, propylene groups, etc. 2-3 An alkylene group is preferred, with an ethylene group being particularly preferred.

[0135] Alkyleneoxy group [-(A 2 The repeat number q of the alkyleneoxy group [(-A)-] may be selected, for example, from the range of about 1 to 10, preferably from 1 to 4, 1 to 3, 1 to 2, and particularly preferably 1. The repeat number q may be an average value (arithmetic mean value or additive mean value), and preferred embodiments are the same as the range of integers described above. When q is 2 or more, two or more alkyleneoxy groups [(-A 2 O-) may be different from each other, but are preferably the same.

[0136] Examples of the diol component (A2) corresponding to the diol unit (A2) include alkanediols (or alkylene glycols), polyalkanediols (or polyalkylene glycols), and the like.

[0137] Examples of alkylene glycols include those represented by the formula (3) where q is 1 and A 2corresponding to the alkylene group exemplified above, specifically, C 10 alkylene glycols such as ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, tetramethylene glycol (or 1,4-butanediol), 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, and 1,10-decanediol. 2-12 alkylene glycol, etc., and a preferred embodiment is 2 The same applies to

[0138] The polyalkylene glycol may be, for example, a polyalkylene glycol represented by the formula (3) where q is 2 or more, preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 to 4; 2 Polylinear or branched alkylene glycols corresponding to the alkylene groups exemplified above, specifically di- or deca-C alkylene glycols such as diethylene glycol, dipropylene glycol, and triethylene glycol. 2-12 alkylene glycols, and preferably di- to hexa-C 2-6 Alkylene glycol, more preferably di- or tetra-C 2-4 Alkylene glycols are included.

[0139] These diol units (A2) may be contained alone or in combination of two or more. Preferred diol units (A2) are 2-6 alkylene glycols, such as linear or branched alkylene glycols, preferably C 2-4 C alkylene glycol, more preferably ethylene glycol, propylene glycol, etc. 2-3 It is preferred that the alkylene glycol contains units derived from alkylene glycol, particularly ethylene glycol.

[0140] The proportion of the diol units (A2) in a preferred embodiment, such as linear or branched alkylene glycol, relative to the total diol units (A2) is, for example, about 10 to 100 mol %, preferably 50 mol % or more, 70 mol % or more, 90 mol % or more, and more preferably 100 mol %.

[0141] Diol unit (A3) The diol unit (A) may or may not contain a diol unit (hereinafter also referred to as diol unit (A3)) different from the diol unit (A1) and the diol unit (A2), as necessary.

[0142] Examples of the diol unit (A3) include structural units derived from alicyclic diol components, aromatic diol components (excluding the diol component (A1)), and alkylene oxide (alkylene carbonate or haloalkanol) adducts of these diol components.

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

[0144] Examples of aromatic diol components include dihydroxyarenes such as hydroquinone and resorcinol; aromatic aliphatic diols such as benzenedimethanol; bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol C, bisphenol G, and bisphenol S; and biphenols such as p,p'-biphenol.

[0145] Examples of alkylene oxide (corresponding alkylene carbonate or haloalkanol) adducts of these diol components include C 2-4 C alkylene oxide adducts, preferably ethylene oxide adducts, propylene oxide adducts, etc. 2-3Examples thereof include alkylene oxide adducts, and the number of moles added is not particularly limited.Specific examples include adducts in which about 2 to 10 moles of ethylene oxide are added to 1 mole of bisphenol A.

[0146] These diol units (A3) may be contained alone or in combination of two or more kinds.

[0147] The proportion of the diol units (A3) is, for example, less than 50 mol%, preferably 30 mol% or less, and more preferably 10 mol% or less, based on the total diol units (A). It is preferable that the diol units (A3) are substantially free of the diol units (A3). When the diol units (A3) are contained, the proportion may be, for example, about 0.1 to 5 mol%.

[0148] The proportion of the total amount of the diol units (A1) and the diol units (A2) relative to the total amount of the diol units (A) may be, for example, 1 mol% or more, specifically about 10 to 100 mol%, and is preferably 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, and particularly 100 mol% in the following stepwise manner.

[0149] The proportion of the diol units (A1) may be, for example, about 1 to 100 mol%, specifically about 30 to 98 mol%, and preferably 50 to 95 mol%, 60 to 90 mol%, and 70 to 85 mol%, based on the total diol units (A). When the proportion of the diol units (A1) is in an appropriate range that is not too low, there is a tendency to easily suppress deterioration in mechanical properties and optical properties, and when it is in an appropriate range that is not too high, there is a tendency to easily improve the molecular weight.

[0150] The ratio of diol units (A1) to diol units (A2) (molar ratio) can be selected from the range of 0 / 100 to 100 / 0, for example, about 1 / 99 to 100 / 0, and preferably the following stepwise ratios: 30 / 70 to 98 / 2, 50 / 50 to 95 / 5, 60 / 40 to 90 / 10, and 70 / 30 to 85 / 15. If the ratio of diol units (A1) is within an appropriate range, not too low, the mechanical and optical properties may be reduced, whereas if it is within an appropriate range, not too high, the molecular weight tends to be improved more easily.

[0151] The proportion of the diol units (A) [total amount of diol units (A1) to (A3)] relative to all of the constituent units (units derived from the polymerization components) of the polyester resin may be, for example, 1 mol % or more, specifically about 10 to 50 mol %, and preferably 20 to 50 mol %, 30 to 50 mol %, and 40 to 50 mol % in the following stepwise manner.

[0152] (Dicarboxylic acid unit (B)) The polyester resin may contain, in addition to the diol units (A), dicarboxylic acid units (B) derived from a dicarboxylic acid component, as needed.

[0153] Examples of the dicarboxylic acid unit (B) include an aliphatic dicarboxylic acid unit derived from an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid unit derived from an alicyclic dicarboxylic acid (hereinafter also referred to as a dicarboxylic acid unit (B1)), and an aromatic dicarboxylic acid unit derived from an aromatic dicarboxylic acid (hereinafter also referred to as a dicarboxylic acid unit (B2)). These dicarboxylic acid units may be contained alone or in combination of two or more. Among these dicarboxylic acid units, an alicyclic dicarboxylic acid unit and an aromatic dicarboxylic acid unit are preferred.

[0154] Dicarboxylic acid unit (B1) The dicarboxylic acid unit (B) may or may not contain an alicyclic dicarboxylic acid unit (B1). The alicyclic dicarboxylic acid unit (B1) may contain at least one aliphatic hydrocarbon ring (alicyclic) skeleton in its chemical structure, but may not contain an aromatic ring skeleton. The aliphatic hydrocarbon ring may be a non-aromatic ring structure formed by an aliphatic chain, and may be monocyclic or polycyclic, such as a cross-linked ring or spirocyclic ring, and may or may not contain an unsaturated bond such as a double bond. Examples of such aliphatic hydrocarbon rings include monocyclic aliphatic hydrocarbon rings and cross-linked aliphatic hydrocarbon rings.

[0155] Examples of the monocyclic aliphatic hydrocarbon ring include a cycloalkane ring and a cycloalkene ring. Examples of the cycloalkane ring include a C cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, and the like. 3-20 Examples of the cycloalkene ring include a C cyclopentene ring and a cyclohexene ring. 3-20 Examples include a cycloalkene ring.

[0156] Examples of the bridged cyclic aliphatic hydrocarbon ring include a bridged cyclic cycloalkane ring and a bridged cyclic cycloalkene ring. Examples of the bridged cyclic cycloalkane ring include C cycloalkane rings such as a decalin ring, a norbornane ring, an adamantane ring, a tricyclodecane ring, and a tetracyclododecane ring. 7-20 Examples of the tricyclodecane ring include tricyclo[5.2.1.0] and tetracycloalkane rings. 2,6 ]decane ring, etc. Examples of the tetracyclododecane ring include tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodecane ring, etc. Examples of the bridged cyclic cycloalkene ring include a C cycloalkene ring such as a norbornene ring, a tricyclodecene ring, and a tetracyclododecene ring. 7-20 Examples include bicycloalkene rings and tetracycloalkene rings.

[0157] The alicyclic dicarboxylic acid unit (B1) may contain these aliphatic hydrocarbon rings alone or in combination of two or more. Among these aliphatic hydrocarbon rings, cycloalkane rings such as cyclohexane rings, and bicycloalkane rings or tetracycloalkane rings such as decalin rings and tricyclodecane rings are preferred.

[0158] The alicyclic dicarboxylic acid unit (B1) may also contain an alkylene group in its chemical structure, such as an alkylene group that bonds (or connects) the aliphatic hydrocarbon ring with a carbonyl group [—C(═O)—] derived from a polymerizable group such as a carboxyl group, or an alkylene group that bonds two or more of the aliphatic hydrocarbon rings together. Examples of such alkylene groups (linear or branched alkylene groups) include C alkylene groups such as methylene, ethylene, trimethylene, propylene, 1,2-butanediyl, and 2-methylpropane-1,3-diyl. 1-8 Preferred alkylene groups include C alkylene groups such as methylene, ethylene, trimethylene, propylene, and 2-methylpropane-1,3-diyl groups. 1-6 Alkylene groups, more preferably C 1-4 C such as an alkylene group, more preferably a methylene group 1-3 It is an alkylene group.

[0159] A preferred alicyclic dicarboxylic acid unit (B1) is represented by the following formula (4).

[0160] [ka] (In the formula, Z 2 represents an aliphatic hydrocarbon ring, R 8 represents a substituent, r represents an integer of 0 or more, A 3a and A 3b each independently represents a direct bond (or a single bond) or an alkylene group (a linear or branched alkylene group).

[0161] In the formula (4), Z 2Examples of the aliphatic hydrocarbon ring represented by the formula (I) include the monocyclic aliphatic hydrocarbon ring and the bridged cyclic aliphatic hydrocarbon ring, and are preferably bicycloalkane rings or tricycloalkane rings such as a cycloalkane ring, a decalin ring, or a tricyclodecane ring, and more preferably C rings such as a cyclohexane ring. 5-10 It is a cycloalkane ring.

[0162] R 8 Examples of the substituent represented by the formula (I) include R 6 and the like (non-reactive substituents or non-polymerizable substituents) exemplified as above, and preferably a halogen atom, a hydrocarbon group (excluding groups containing an aromatic ring skeleton such as an aryl group or an aralkyl group), a group [—OR h ](where R h represents a hydrocarbon group), more preferably an aliphatic hydrocarbon group such as a linear or branched alkyl group or a cycloalkyl group, and particularly preferably a C 1-4 C such as alkyl group and cyclohexyl group 5-10 It is a cycloalkyl group.

[0163] R 8 The number of permutations r of Z 2 Depending on the type of r, it is, for example, an integer of 0 to 10, preferably an integer of 0 to 6, an integer of 0 to 4, an integer of 0 to 2, an integer of 0 to 1, and particularly 0. When r is 2 or more, 2 or more R 8 The types may be the same or different from each other.

[0164] A 3a , A 3b may be an alkylene group (a linear or branched alkylene group), and examples thereof include the same groups as those exemplified as the alkylene group that may be contained in the chemical structure of the above-mentioned alicyclic dicarboxylic acid unit (B1). Preferred alkylene groups are listed in the following order: 1-6 Alkylene group, C 1-4 Alkylene group, C 1-3 C is an alkylene group, and more preferably a methylene group. 1-2 It is an alkylene group.

[0165] A 3a , A 3b may be an alkylene group, but may be a direct bond (or a single bond), i.e., Z 2 and the carbonyl group [—C(═O)—] are preferably directly bonded to each other. 3a and A 3b The types may be the same or different from each other.

[0166] Z 2 And, A 3a and A 3b (or carbonyl group [—C(═O)—]) is not particularly limited, and Z 2 The furthest position in the 2 is a cyclohexane ring, the 1- and 4-positions are 2 When it is a decalin ring, the 2- and 6-positions are 2 When is a tricyclodecane ring, the positions may be 4, 8, etc.

[0167] Representative alicyclic dicarboxylic acid components that form the structural unit represented by the formula (4) include, for example, cycloalkanedicarboxylic acids, specifically, C 1,4-cyclohexanedicarboxylic acid and the like. 5-10 Cycloalkane dicarboxylic acids, etc.; bridged cyclic cycloalkane dicarboxylic acids, specifically, bi- or tricycloalkane dicarboxylic acids such as decalin dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid, tricyclodecane dicarboxylic acid, etc.; cycloalkene dicarboxylic acids, specifically, C such as cyclohexene dicarboxylic acid, etc. 5-10 Examples thereof include cycloalkene-dicarboxylic acids; bridged cyclic cycloalkene dicarboxylic acids, specifically bi- or tricycloalkene dicarboxylic acids such as norbornene dicarboxylic acid; and ester-forming derivatives thereof.

[0168] The alicyclic dicarboxylic acid unit (B1) can be used alone or in combination of two or more. Among these, preferred are crosslinked cyclic cycloalkanedicarboxylic acids such as cycloalkanedicarboxylic acids, bicycloalkanedicarboxylic acids, or tricycloalkanedicarboxylic acids, and more preferred are C cyclohexanedicarboxylic acids. 5-10 Cycloalkane-dicarboxylic acids, bicycloalkane-dicarboxylic acids such as 2,6-decalindicarboxylic acid, and in particular C 5-8 Constitutional units derived from cycloalkane-dicarboxylic acids are preferred.

[0169] The proportion of the alicyclic dicarboxylic acid units represented by the formula (4) can be selected, for example, from 1 mol% or more, specifically from a range of about 10 to 100 mol%, based on the total amount of the alicyclic dicarboxylic acid units (B1), and is preferably 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, and more preferably 100 mol%.

[0170] The dicarboxylic acid component derived from the alicyclic dicarboxylic acid unit (B1), such as the structural unit represented by the formula (4), may be a mixture of isomers.

[0171] Dicarboxylic acid unit (B2) The dicarboxylic acid unit (B) may or may not contain an aromatic dicarboxylic acid unit (B2). The dicarboxylic acid unit (B) preferably contains at least one selected from an alicyclic dicarboxylic acid unit (B1) and an aromatic dicarboxylic acid unit (B2), and more preferably contains at least an aromatic dicarboxylic acid unit (B2).

[0172] The aromatic dicarboxylic acid unit (B2) may contain at least one aromatic hydrocarbon ring (arene ring) skeleton in its chemical structure. The aromatic dicarboxylic acid unit (B2) preferably contains a dicarboxylic acid unit represented by the following formula (5) as a structural unit having a fluorene skeleton:

[0173] [ka] (In the formula, R 9a and R 9b each independently represents a substituent, s1 and s2 independently represent an integer of 0 to 4, A 4a and A 4b each independently represents a straight-chain or branched-chain alkylene group).

[0174] In the formula (5), the group A 4a and A 4b Examples of the alkylene group (linear or branched alkylene group) represented by the formula (I) include C 1, C 2, C 3, C 4, C 5, C 6, C 7, C 8, C 9, C 10, C 11, C 12, C 13, C 14, C 15, C 16, C 17, C 18, C 19, C 20, C 21, C 22, C 23, C 24, C 25, C 26, C 27, C 28, C 29, C 30, C 31, C 32, C 33, C 28, C 34, C 29, C 35, C 26, C 27, C 28, C 29, C 36, C 29, C 37, C 29, C 38, C 29, C 39, C 1-8 Preferred alkylene groups include C alkylene groups such as methylene, ethylene, trimethylene, propylene, and 2-methylpropane-1,3-diyl. 1-6 alkylene groups, and preferably, 1-4 Alkylene group, C 2-4 Alkylene groups, especially C groups such as ethylene and propylene groups 2-3 An alkylene group, particularly an ethylene group, is preferred. 4a and A 4b The types may be different from each other, but are preferably the same.

[0175] R 9a and R 9b The substituent represented by is preferably a non-reactive group or a non-polymerizable group that is inactive to the polymerization reaction. For example, in the diol unit (A1), R 6 Examples of the substituents (non-reactive groups or non-polymerizable groups) exemplified as R 9a and R 9b Examples of the alkyl group include a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, and a substituted amino group.

[0176] Preferred R 9a and R 9bis a hydrocarbon group, a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom, or a cyano group, and more preferably an alkyl group or an aryl group. Examples of the alkyl group (linear or branched alkyl group) include C groups such as a methyl group, an ethyl group, and a t-butyl group. 1-6 alkyl groups, and C groups such as methyl groups. 1-4 The alkyl group is preferred. The aryl group is C 6-12 aryl groups, and C groups such as phenyl, 1-naphthyl, and 2-naphthyl groups. 6-10 Aryl groups are preferred.

[0177] R 9a , R 9b The numbers of substitutions s1 and s2 may each be an integer of 0 to 4, for example, an integer of about 1 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly 0. s1 and s2 may be different from each other, but are preferably the same.

[0178] In addition, when s1 or s2 is 2 or more, R 9a or R 9b The types of R may be the same or different. 9a and R 9b The types of R may be the same or different, and are preferably the same. 9a and R 9b The substitution positions of these may be any of the 1st to 4th positions and the 5th to 8th positions of the fluorene skeleton, but are, for example, the 2nd, 3rd and / or 7th positions, preferably the 2nd and / or 7th positions. When s1 and s2 are both 1, preferred substitution positions (or bonding positions) are the 1st and 8th positions, the 2nd and 7th positions, the 3rd and 6th positions, and the 4th and 5th positions, with the 2nd and 7th positions being particularly preferred.

[0179] Examples of the dicarboxylic acid unit represented by the formula (5) include 9,9-bis(carboxyalkyl)fluorenes, specifically 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)fluorene and 9,9-bis(2-carboxypropyl)fluorene. 2-6alkyl)fluorene; 9,9-bis(carboxyalkyl)-diarylfluorenes, specifically 9,9-bis(carboxyalkyl)-di(C alkyl)fluorenes such as 9,9-bis(carboxyalkyl)-diphenylfluorene and 9,9-bis(carboxyalkyl)-dinaphthylfluorene; 6-12 Examples of structural units include those derived from aryl)fluorene.

[0180] Examples of 9,9-bis(carboxyalkyl)-diphenylfluorene include 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)-1,8-diphenylfluorene, 9,9-bis(2-carboxyethyl)-2,7-diphenylfluorene, 9,9-bis(2-carboxyethyl)-3,6-diphenylfluorene, 9,9-bis(2-carboxyethyl)-4,5-diphenylfluorene, and 9,9-bis(2-carboxypropyl)-2,7-diphenylfluorene. 2-6 alkyl)-diphenylfluorene.

[0181] Examples of 9,9-bis(carboxyalkyl)-dinaphthylfluorene include 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)-1,8-di(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-2,7-di(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-3,6-di(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-4,5-di(2-naphthyl)fluorene, 9,9-bis(2-carboxypropyl)-2,7-di(2-naphthyl)fluorene, and 9,9-bis(2-carboxyethyl)-2,7-di(1-naphthyl)fluorene. 2-6 alkyl)-dinaphthylfluorene and the like.

[0182] The dicarboxylic acid unit represented by the formula (5) may be contained alone or in combination of two or more kinds. Among these dicarboxylic acid units represented by the formula (5), 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)fluorene is preferred. 2-4A structural unit derived from alkyl)fluorene is preferred.

[0183] The aromatic dicarboxylic acid unit (B2) may or may not contain an aromatic dicarboxylic acid unit other than that of the formula (5).

[0184] Examples of the aromatic dicarboxylic acid component corresponding to the other aromatic dicarboxylic acid unit include monocyclic aromatic dicarboxylic acids, polycyclic aromatic dicarboxylic acids, and ester-forming derivatives thereof. Examples of the monocyclic aromatic dicarboxylic acids include benzene dicarboxylic acids such as phthalic acid, terephthalic acid, and isophthalic acid; alkyl benzene dicarboxylic acids, specifically, C alkyl benzene dicarboxylic acids such as 4-methylisophthalic acid; 1-4 alkyl-benzenedicarboxylic acids and the like.

[0185] Examples of polycyclic aromatic dicarboxylic acids include condensed polycyclic aromatic dicarboxylic acids, specifically condensed polycyclic C dicarboxylic acids such as naphthalenedicarboxylic acid, anthracenedicarboxylic acid, and phenanthrenedicarboxylic acid. 10-24 Arene-dicarboxylic acids, preferably fused polycyclic C 10-14 arene-dicarboxylic acids, etc.; biaryldicarboxylic acids, specifically, 2,2'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, etc.; bis(carboxyalkoxy)biC 6-10 Aryl, specifically bis(carboxy C such as 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl 1-4 Alkoxy)BiC 6-10 Aryl, etc.; Bis[(carboxyalkoxy)-C 6-10 aryl]alkanes, specifically bis[(carboxy C 1-4 Alkoxy)-C 6-10 Aryl)C 1-6 Alkanes, etc.; diarylalkanedicarboxylic acids, specifically, di-C such as 4,4'-diphenylmethanedicarboxylic acid 6-10 Aryl C 1-6Alkane-dicarboxylic acids, etc.; diaryl ketone dicarboxylic acids, specifically, di(C) such as 4,4'-diphenyl ketone dicarboxylic acid 6-10 aryl) ketone-dicarboxylic acids; diaryl ether dicarboxylic acids, specifically, di(C) such as 4,4'-diphenyl ether dicarboxylic acid 6-10 aryl) ether-dicarboxylic acids; diarylsulfonedicarboxylic acids, specifically, di(C) such as 4,4'-diphenylsulfonedicarboxylic acid; 6-10 aryl) sulfone-dicarboxylic acids and the like.

[0186] 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, and 2,6-naphthalenedicarboxylic acid.

[0187] The proportion of the dicarboxylic acid units represented by the formula (5) can be selected, for example, from 1 mol% or more, specifically from a range of about 10 to 100 mol%, based on the total aromatic dicarboxylic acid units (B2), and is preferably 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, and more preferably 100 mol%.

[0188] Dicarboxylic acid unit (B3) The dicarboxylic acid unit (B) may or may not contain a dicarboxylic acid unit (hereinafter also referred to as dicarboxylic acid unit (B3)) different from the dicarboxylic acid unit (B1) and the dicarboxylic acid unit (B2), as necessary.

[0189] Examples of the dicarboxylic acid unit (B3) include structural units derived from an aliphatic dicarboxylic acid component.

[0190] Examples of the aliphatic dicarboxylic acid component include linear or branched alkanedicarboxylic acids, specifically, C carboxylic acids such as succinic acid, adipic acid, suberic acid, sebacic acid, and decanedicarboxylic acid. 2-12Alkane-dicarboxylic acids, etc.; linear or branched unsaturated aliphatic dicarboxylic acids, specifically C such as maleic acid, fumaric acid, and itaconic acid 2-10 Alkene-dicarboxylic acids; and ester-forming derivatives thereof.

[0191] The dicarboxylic acid units (B3) may be contained alone or in combination of two or more kinds.

[0192] The proportion of the dicarboxylic acid units (B3) is, for example, less than 50 mol%, preferably 30 mol% or less, and more preferably 10 mol% or less, based on the total dicarboxylic acid units (B). It is preferable that the dicarboxylic acid units (B3) are substantially free of the dicarboxylic acid units (B3). When the dicarboxylic acid units (B3) are contained, the proportion may be, for example, about 0.1 to 5 mol%.

[0193] The total proportion of the alicyclic dicarboxylic acid units (B1) and the aromatic dicarboxylic acid units (B2) relative to the total dicarboxylic acid units (B) may be, for example, 1 mol% or more, specifically about 10 to 100 mol%, and is preferably 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, stepwise, with substantially 100 mol% being particularly preferred.

[0194] The proportion of the alicyclic dicarboxylic acid units (B1) may be, for example, 1 mol% or more, specifically about 10 to 100 mol%, based on the total dicarboxylic acid units (B), and is preferably 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, stepwise, with substantially 100 mol% being particularly preferred.

[0195] The proportion of the aromatic dicarboxylic acid units (B2) relative to the total dicarboxylic acid units (B) may be, for example, 1 mol% or more, specifically about 10 to 100 mol%, and is preferably 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, stepwise, with substantially 100 mol% being particularly preferred.

[0196] The proportion of the dicarboxylic acid units (B) [total amount of dicarboxylic acid units (B1) to (B3)] relative to all of the constituent units (units derived from the polymerization components) of the polyester resin may be, for example, 1 mol % or more, specifically about 10 to 50 mol %, and preferably 20 to 50 mol %, 30 to 50 mol %, and 40 to 50 mol % in the following stepwise manner.

[0197] The ratio of the diol unit (A) to the dicarboxylic acid unit (B) in the polyester resin is the former / latter (molar ratio) = 1 / 0.8 to 1 / 1.2, preferably 1 / 0.9 to 1 / 1.1, and is preferably approximately equimolar.

[0198] The proportion of the total amount of structural units having a fluorene skeleton, for example, the proportion of the total amount of diol units (A1) and structural units represented by the formula (5), relative to all structural units (units derived from polymerization components) of the polyester resin, may be, for example, about 10 to 100 mol %, and preferably is 30 to 100 mol %, 40 to 99 mol %, 50 to 98 mol %, 60 to 95 mol %, 70 to 93 mol %, and 80 to 90 mol %, in the following stepwise manner.

[0199] (Other structural units (C)) Furthermore, the polyester resin may or may not contain other structural units (C) different from the diol units (A) and the dicarboxylic acid units (B) as needed, within a range that does not impair the effects of the present disclosure.

[0200] Examples of other structural units (C) include structural units derived from hydroxycarboxylic acid components, corresponding lactone components, and polyfunctional polymerizable components having three or more polymerizable groups (carboxyl groups and / or hydroxyl groups).

[0201] Examples of the hydroxycarboxylic acid component include aromatic hydroxycarboxylic acids such as hydroxybenzoic acid, aliphatic hydroxycarboxylic acids (hydroxyalkanoic acids) such as lactic acid, 3-hydroxybutyric acid, and 6-hydroxyhexanoic acid, and ester-forming derivatives thereof. Examples of the corresponding lactone component include lactones corresponding to hydroxyalkanoic acids such as ε-caprolactone.

[0202] Examples of polyfunctional polymerization components having a total of three or more polymerizable groups (carboxyl groups and / or hydroxyl groups) include trivalent or higher polycarboxylic acids such as trimellitic acid and pyromellitic acid; trivalent or higher polyhydric alcohols such as glycerin and pentaerythritol; and the like.

[0203] The proportion of such other structural units (C) relative to all structural units (total amount of diol units (A), dicarboxylic acid units (B) and other structural units (C)) is, for example, 50 mol % or less, preferably in the following stepwise manner: 0 to 30 mol %, 0 to 10 mol %, 0.01 to 5 mol %, and it is preferable that other structural units (C) are not substantially contained.

[0204] (Production method and properties of polyester resin) The polyester resin may be a commercially available product, or may be prepared by polymerizing the polymerization components using a conventional method such as a melt polymerization method such as transesterification or direct polymerization, a solution polymerization method, or an interfacial polymerization method. For example, the polyester resin may be prepared by a method similar to the manufacturing methods described in JP-A Nos. 2016-69643 and 2013-64119, specifically by polymerizing the polymerization components such as a diol component (A) and a dicarboxylic acid component (B) at an elevated temperature and reduced pressure in the presence of a catalyst such as manganese acetate tetrahydrate, calcium acetate monohydrate, germanium dioxide, or titanium (IV) tetrabutoxide.

[0205] The weight-average molecular weight Mw of the polyester resin can be measured by gel permeation chromatography (GPC) or the like, and may be, for example, about 10,000 to 300,000 in terms of polystyrene, and preferably ranges in the following stepwise directions: 20,000 to 200,000, 30,000 to 100,000, and 40,000 to 80,000. When the weight-average molecular weight Mw is in an appropriate range that is not too low, it tends to be easy to suppress a decrease in moldability (productivity) and there tends to be less restriction on applications.

[0206] The glass transition temperature Tg of the polyester resin may be, for example, about 90 to 200° C., and preferably in the following stepwise order: 100 to 180° C., 120 to 170° C., 130 to 160° C., and 140 to 150° C. If the Tg is within a moderate range that is not too low, it tends to be easier to prevent discoloration (or coloring) during production and / or use due to a decrease in heat resistance, and it tends to be less likely to deform in a high-temperature environment after being molded into a predetermined shape, making it easier to use in applications that require high thermal stability.

[0207] In this specification and claims, the glass transition temperature Tg can be measured using a differential scanning calorimeter (DSC) under conditions of a nitrogen atmosphere and a temperature rise rate of 10° C. / min.

[0208] The polyester resin may be crystalline (crystalline polymer) or amorphous (amorphous polymer).

[0209] The tensile strength of the polyester resin may be, for example, 10 to 1000 MPa, preferably 50 to 150 MPa, and more preferably 80 to 100 MPa.

[0210] The flexural strength of the polyester resin may be, for example, 10 to 1000 MPa, preferably 100 to 200 MPa, and more preferably 120 to 140 MPa.

[0211] The flexural modulus of the polyester resin may be, for example, 1000 to 10000 MPa, preferably 2000 to 5000 MPa, and more preferably 2500 to 3500 MPa.

[0212] The Charpy impact strength (notched) of polyester resin is, for example, 0.1 to 10 kJ / m 2 and preferably 0.5 to 2 kJ / m 2 , more preferably 1 to 1.5 kJ / m 2 is.

[0213] The refractive index nD of the polyester resin may be, for example, about 1.5 to 1.8, and preferably 1.6 to 1.7, at a temperature of 20° C. and a wavelength of 589 nm.

[0214] The MFR of the polyester resin may be, for example, 0.1 to 30 g / 10 min, preferably 0.5 to 15 g / 10 min, and more preferably 1 to 3 g / 10 min, at a temperature of 230° C. and a load of 2.16 kg.

[0215] In this specification and claims, the tensile strength, flexural strength, flexural modulus, Charpy impact strength, refractive index and MFR can be measured by the methods described in the examples below.

[0216] (Typical polyester resin) These polyester resins can be used alone or in combination of two or more. Typical polyester resins include aromatic polyester resins, for example, polyalkylene arylate resins such as PET, PBT, and PEN, and polyester resins containing structural units having a fluorene skeleton, and preferably polyester resins containing structural units having a fluorene skeleton, such as the diol unit (A1) represented by the formula (2) or the dicarboxylic acid unit represented by the formula (5).

[0217] Among the polyester resins containing a structural unit having a fluorene skeleton, a polyester resin (P1) containing, as the diol unit (A), the diol unit (A1) represented by the formula (2) is preferred; Among the polyester resins (P1), polyester resins (P2) containing the alicyclic dicarboxylic acid units (B1) and / or aromatic dicarboxylic acid units (B2) as the dicarboxylic acid units (B) are more preferred; More preferably, among the polyester resins (P2), the polyester resin (P3) further contains the diol unit (A2) as the diol unit (A); Among these, among the polyester resins (P2) and (P3), a polyester resin (P4) containing the aromatic dicarboxylic acid unit (B2) as the dicarboxylic acid unit (B) is particularly preferred; Among the polyester resins (P4), polyester resins (P5) containing a dicarboxylic acid unit represented by the formula (5) as the dicarboxylic acid unit (B) (the aromatic dicarboxylic acid unit (B2)) are particularly preferred.

[0218] The proportion of a typical polyester resin (e.g., the proportion of an aromatic polyester resin, particularly a polyalkylene arylate resin, and the proportion of the total amount of a polyester resin containing a structural unit having a fluorene skeleton) may be, for example, 50% by mass or more, specifically about 60 to 100% by mass, based on the total amount of polyester resins. Preferably, the proportion is 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, and preferably substantially 100% by mass. The proportion may be the proportion of the total amount of polyester resins containing a structural unit having a fluorene skeleton; the proportion of the total amount of the polyester resin (P1); the proportion of the total amount of the polyester resin (P2); the proportion of the total amount of the polyester resin (P3); the proportion of the total amount of the polyester resin (P4); or the proportion of the total amount of the polyester resin (P5).

[0219] The proportion of the polyester resin may be selected from the range of, for example, about 10% by mass or more, for example, 30% by mass or more, specifically about 50 to 99.99% by mass, based on the entire polyester resin composition, and is preferably 70 to 99.9% by mass, 80 to 99.8% by mass, 90 to 99.7% by mass, 95 to 99.5% by mass, and 97 to 99% by mass in the following stepwise manner.

[0220] [Other ingredients] The polyester resin composition may or may not further contain other components different from the polyester resin and the fluorene compound, as necessary, such as other flow improvers, thermoplastic resins, fibrous reinforcing materials, and conventional additives.

[0221] (Other flow improvers) The polyester resin composition may or may not contain a fluidity improver (second fluidity improver) different from the fluorene compound (first fluidity improver) represented by the formula (1). Examples of the second fluidity improver include compounds having a 9,9-bisarylfluorene skeleton such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF), specifically, the compounds described in JP 2018-203975 A.

[0222] These second flow improvers can be used alone or in combination of two or more. The proportion of the second flow improver is, for example, about 0 to 100 parts by mass, preferably 50 parts by mass or less, 30 parts by mass or less, 10 parts by mass or less, 5 parts by mass or less, and 1 part by mass or less, relative to 100 parts by mass of the fluorene compound (B) (first flow improver).

[0223] The flowability improver for polyester resins of the present disclosure may contain at least the fluorene compound (first flowability improver) represented by formula (1), and may also contain the second flowability improver, if necessary. In the flowability improver of the present disclosure, the fluorene compound (first flowability improver) represented by formula (1) may be used alone or in combination of two or more, and the second flowability improver may be used alone or in combination of two or more. In the flowability improver of the present disclosure, the ratio of the second flowability improver to 100 parts by mass of the fluorene compound (first flowability improver) represented by formula (1) may be the same as described above, including preferred embodiments. In the flowability improver of the present disclosure, the ratio of the fluorene compound represented by formula (1) to the total amount of the flowability improver may be, for example, about 10% by mass or more, preferably 30% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, and substantially 100% by mass is even more preferred. If the proportion of the fluorene compound represented by the formula (1) is too low, it tends to be easier to achieve a good balance between fluidity and mechanical properties.

[0224] (thermoplastic resin) Examples of thermoplastic resins other than polyester resins include polyolefin resins, specifically, linear olefin resins such as polyethylene resins and polypropylene resins, and cyclic polyolefin resins; styrene resins, specifically, polystyrene (PS) such as general-purpose polystyrene (GPPS) and syndiotactic polystyrene (SPS), and styrene copolymers, such as MS resin, AS resin, and rubber-containing resins such as high-impact polystyrene (HIPS), ABS resin, AAS resin, ACS resin, AES resin, and MBS resin. Styrene-based resins (or rubber-grafted styrene-based copolymers), etc.; (meth)acrylic resins, specifically, homopolymers or copolymers of (meth)acrylic monomers such as polymethyl methacrylate (PMMA); vinyl acetate-based resins, specifically, polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), polyvinyl formal (PVF), polyvinyl butyral (PVB), and other polyvinyl acetals; vinyl chloride-based resins, specifically, polyvinyl chloride (PVC), vinyl chloride-vinyl acetate copolymers, vinylidene chloride-vinyl chloride copolymers, etc. vinyl chloride and / or vinylidene chloride homo- or copolymers such as vinylidene chloride-acrylonitrile copolymers, vinylidene chloride-acrylonitrile copolymers; fluororesins, specifically, polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene ethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), etc.; polycarbonate resins (PC), specifically bisphenol-type polycarbonate resins such as bisphenol A; polyamide resins (PA), specifically aliphatic polyamide resins such as polyamide 6 and polyamide 66, aromatic polyamide resins (aramid resins) such as polyphenylene isophthalamide; polyacetal resins (POM); polyphenylene ether resins (PPE); polyphenylene sulfide resins (PPS);Polysulfone resins, specifically, polysulfone resin (PSF), polyethersulfone (PES), etc.; polyetherketone resins, specifically, polyetherketone resin (PEK), polyetheretherketone resin (PEEK), polyetherketoneetherketoneketone (PEKEKK), etc.; phenoxy resins; polyketone resins such as aliphatic polyketone resins; cellulose derivatives, specifically, cellulose esters such as nitrocellulose, cellulose acetate, and cellulose acetate propionate, and cellulose ethers such as ethyl cellulose; thermoplastic polyimide resins, specifically, polyetherimide (PEI), polyamideimide, etc.; polyethernitrile resins; thermoplastic elastomers (TPEs), specifically, polystyrene-based TPEs, polyolefin-based TPEs (TPOs), polydiene-based TPEs, chlorine-based TPEs, fluorine-based TPEs, polyurethane-based TPEs (TPUs), polyester-based TPEs (TPEEs), polyamide-based TPEs (TPAs), etc.;

[0225] These other thermoplastic resins may be contained alone or in combination of two or more. The polyester resin composition may be substantially free of polyolefin resins such as polypropylene resins, polycarbonate resins and / or polyamide resins (PA), or may be completely free of such resins.

[0226] If necessary, the polyester resin may form a polymer alloy with another thermoplastic resin, and the polymer alloy may contain a compatibilizer.

[0227] The proportion of the polyester resin may be, for example, about 10% by mass or more relative to the total resin components in the polyester resin composition (total amount of polyester resin and other thermoplastic resins), and is preferably 30% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, and 100% by mass in the following stepwise manner. When the proportion of the polyester resin is in an appropriate range that is not too small, it tends to be easier to effectively improve the fluidity and / or mechanical properties.

[0228] (fibrous reinforcing material) The polyester resin composition may or may not contain a fibrous reinforcing material (fibrous reinforcing material or fibrous filler) as needed. Generally, fibrous reinforcing materials can significantly improve the mechanical properties of a composition, but they also significantly increase viscosity, making it difficult to achieve both mechanical properties and fluidity (moldability or processability). In particular, in applications where mechanical properties are important, a high proportion of fibrous reinforcing material must be added, and the significant increase in viscosity associated with an increase in the amount of fibrous reinforcing material may require the sacrifice of fluidity (moldability or processability). However, in the present disclosure, fluidity can be effectively improved even when a fibrous reinforcing material is included, making it easy to achieve both mechanical properties and fluidity.

[0229] Examples of fibrous reinforcing materials include organic fibers and inorganic fibers. Examples of organic fibers include modified or unmodified cellulose fibers (fibers of cellulose or its derivatives), such as cellulose fibers and cellulose acetate fibers; polyester fibers, such as polyalkylene arylate fibers; and polyamide fibers, such as aliphatic polyamide fibers and aramid fibers. Examples of inorganic fibers include glass fibers, carbon fibers, boron fibers, and wollastonite, as well as metal fibers, such as whiskers. Examples of carbon fibers include polyacrylonitrile (PAN)-based carbon fibers, pitch-based carbon fibers, such as isotropic pitch-based carbon fibers and mesophase pitch-based carbon fibers, and vapor-grown carbon fibers.

[0230] These fibrous reinforcing materials can be used alone or in combination. Preferred fibrous reinforcing materials are inorganic fibers such as modified or unmodified cellulose fibers, glass fibers, and carbon fibers.

[0231] Examples of glass components that form glass fibers include E-glass (alkali-free electrical insulating glass), S-glass (high-strength glass), C-glass (chemical glass), A-glass (general-use alkali-containing glass), and YM-31-A-glass (high-elasticity glass). Among these, E-glass, C-glass, and S-glass are preferred from the standpoint of mechanical properties, and E-glass is particularly preferred. Glass fibers formed from these glass components can be used alone or in combination of two or more.

[0232] The form of the fibrous reinforcing material may be short fiber or long fiber, or may be fabric such as woven fabric, knitted fabric, or nonwoven fabric, depending on the application. These fibrous reinforcing materials may be used alone or in combination of two or more. Short fiber is preferred because it is easy to improve flowability.

[0233] The average fiber length of the fibrous reinforcing material (when in the form of a fabric, the average fiber length of the fibers constituting the fabric) may be selected, for example, from a range of about 0.1 to 10 mm, preferably in the following stepwise order: 0.2 to 8 mm, 0.5 to 6 mm, and 1 to 4 mm. The average fiber length of the fibrous reinforcing material in the composition or molded article may be shorter than that before mixing due to the influence of mixing (kneading) when preparing the composition or shear force during molding, and is, for example, 0.05 to 5 mm, preferably 0.1 to 3 mm, and more preferably 0.2 to 1 mm.

[0234] The average fiber diameter (filament diameter) of the fibrous reinforcing material may be on the order of nanometers, and examples of such fibrous reinforcing materials include modified or unmodified cellulose nanofibers, carbon nanotubes, carbon nanocoils, carbon nanofibers, etc. From the standpoint of mechanical strength, the average fiber diameter (filament diameter) may be on the order of microns, for example, selected from the range of about 1 to 200 μm, preferably 3 to 100 μm, more preferably 4 to 30 μm, and particularly 5 to 15 μm.

[0235] The cross-sectional shape of the fibrous reinforcing material may be, for example, circular, elliptical, polygonal, etc. The fibrous reinforcing material may be subjected to a conventional surface treatment, for example, may be treated with a surface treatment agent such as a bundling agent or a silane coupling agent.

[0236] The proportion of the fibrous reinforcing material may be, for example, 50% by mass or less, 0 to 30% by mass, or 1 to 10% by mass, based on the total amount of the polyester resin, the fluorene compound, and the fibrous reinforcing material.

[0237] (Conventional additives) The polyester resin composition may optionally contain various additives, such as fillers or reinforcing agents (excluding the fibrous reinforcing materials), colorants such as dyes and pigments, conductive agents, flame retardants, flame retardant assistants, plasticizers, lubricants, stabilizers, release agents, antistatic agents, dispersants, compatibilizers, flow control agents, leveling agents, antifoaming agents, surface modifiers, stress reducing agents, and carbon materials (excluding the fibrous reinforcing materials). Examples of the stabilizers include antioxidants, ultraviolet absorbers, and heat stabilizers. These additives may be used alone or in combination.

[0238] The proportion of the additive may be, for example, 50% by mass or less, 0 to 30% by mass, or 1 to 10% by mass, relative to the entire polyester resin composition.

[0239] The polyester resin composition can be prepared by mixing a polyester resin, a fluorene compound (flow improver), and, if necessary, other components, by a conventional method such as dry mixing or melt kneading, and the polyester resin composition may be in the form of pellets or the like.

[0240] [Properties of polyester resin composition and molded product] The polyester resin composition of the present disclosure has high melt fluidity, although its properties vary depending on the type and proportion of the polyester resin and fluorene compound. Therefore, the measured melt flow rate (MFR) [or melt flow index (MFI)] of the polyester resin composition may be, for example, about 110 to 3000, preferably 120 to 1000, 130 to 500, 140 to 300, and 150 to 200, where MFR is defined as 100 for a composition that does not contain a fluorene compound (a composition that contains the same mass of polyester resin instead of the fluorene compound in the composition; hereinafter simply referred to as blank).

[0241] The MFR of the blank varies depending on the type and proportion of polyester resin, but may be, for example, 0.1 to 30 g / 10 min, preferably 0.5 to 15 g / 10 min, and more preferably 1 to 3 g / 10 min, under measurement conditions of a temperature of 230°C and a test load of 2.16 kgf.

[0242] In this specification and claims, MFR can be measured in accordance with JIS K 7210-1 Method B, and specifically, can be measured by the method described in the examples below.

[0243] Furthermore, despite containing a fluorene compound, which is a low molecular weight compound, the polyester resin composition of the present disclosure may be able to improve mechanical properties such as bending properties and tensile properties without excessively deteriorating them.

[0244] The tensile strength (maximum tensile strength) of the polyester resin composition may be, for example, about 70 to 120, and preferably 80 to 115, 90 to 110, 95 to 105, and 98 to 103, where the tensile strength of a blank is 100.

[0245] The tensile strength of the blank varies depending on the type and proportion of polyester resin, but may be, for example, 10 to 1000 MPa, preferably 50 to 150 MPa, and more preferably 80 to 100 MPa.

[0246] In this specification and claims, the tensile properties can be measured in accordance with JIS K 7161-1, -2, and specifically, can be measured by the method described in the examples below.

[0247] The flexural strength of the polyester resin composition may be, for example, about 70 to 120, and preferably 80 to 115, 90 to 110, 95 to 105, and 98 to 103, where the flexural strength of the blank is taken as 100.

[0248] The flexural strength of the blank varies depending on the type and proportion of polyester resin, but may be, for example, 10 to 1000 MPa, preferably 100 to 200 MPa, and more preferably 120 to 140 MPa.

[0249] The flexural modulus of the polyester resin composition may be, for example, about 80 to 130, and preferably 85 to 120, 90 to 110, and 95 to 105, where the flexural modulus of the blank is 100.

[0250] The flexural modulus of the blank varies depending on the type and proportion of polyester resin, but may be, for example, 1000 to 10000 MPa, preferably 2000 to 5000 MPa, and more preferably 2500 to 3500 MPa.

[0251] In this specification and claims, the bending properties can be measured in accordance with JIS K 7171, and specifically, can be measured by the method described in the examples below.

[0252] The Charpy impact strength (notched) of the polyester resin composition may be, for example, about 30 to 150, and preferably in the following stepwise manner, 60 to 140, 75 to 130, 80 to 120, 85 to 115, and 90 to 110, where the tensile strength of the blank is 100.

[0253] The Charpy impact strength (notched) of the blank varies depending on the type and proportion of polyester resin, but is typically 0.1 to 10 kJ / m 2 and preferably 0.5 to 2 kJ / m 2 , more preferably 1 to 1.5 kJ / m 2 is.

[0254] In this specification and claims, the Charpy impact strength (notched) can be measured in accordance with JIS K 7111, and specifically, can be measured by the method described in the examples below.

[0255] The refractive index nD of the polyester resin composition at a temperature of 20° C. and a wavelength of 589 nm may be, for example, about 80 to 120, preferably 90 to 110 and 95 to 105, stepwise, when the tensile strength of the blank is 100.

[0256] The refractive index nD of the blank varies depending on the type and proportion of polyester resin, but may be, for example, about 1.5 to 1.8, and preferably 1.6 to 1.7, at a temperature of 20° C. and a wavelength of 589 nm.

[0257] In this specification and claims, the refractive index can be measured by the method described in the examples below.

[0258] (Molded body) The present disclosure also encompasses a molded article formed from the polyester resin composition. The shape of the molded article is not particularly limited and can be selected depending on the application, and may be, for example, a pellet-like shape, a linear (or filamentous) one-dimensional structure, a film-like, sheet-like, or plate-like two-dimensional structure, a block-like, rod-like, or hollow (tubular or tubular) three-dimensional structure, or a composite or complex shape that combines these shapes.

[0259] The molded article can be produced by utilizing a conventional molding method such as compression molding, injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, pressure molding, casting molding, calendering, or foam molding.

[0260] The molded article may be a composite molded article including a polyester resin composition part formed from the polyester resin composition and other constituent members. The proportion of the polyester resin composition (polyester resin composition part) in the molded article is not particularly limited, and may be, for example, about 10 to 100 mass %, or about 20 to 80 mass %. [Example]

[0261] The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples. Various evaluation methods and raw materials used are also shown below.

[0262] [Evaluation method] (Tensile properties) The tensile strength (maximum tensile strength) was measured at a test speed of 5 mm / min in accordance with JIS K 7161-1, -2.

[0263] (bending properties) The bending strength and bending modulus were measured at a support distance of 64 mm and a test speed of 2 mm / min in accordance with JIS K 7171. The bending modulus was calculated by the tangent method.

[0264] (shock resistance) The Charpy impact strength (notched) was measured in accordance with JIS K 7111.

[0265] (refractive index) The sample was heat-pressed at 200-240°C to form a film with a thickness of 200-300 μm. This film was cut into strips measuring 20-30 mm in length and 10 mm in width to obtain test pieces. The refractive index nD of the obtained test pieces at 589 nm (D line) was measured using a multi-wavelength Abbe refractometer (Atago Co., Ltd., "DR-M4 (circulating constant temperature water bath 60-C3)") at a measurement temperature of 20°C and diiodomethane as the contact liquid.

[0266] (MFR) Measurement was performed in accordance with JIS K 7210-1 Method B. Specifically, in Examples 1 to 12 and Comparative Examples 1 to 12, which used polyester resin A or B as the base resin, measurement was performed under conditions of a holding time of 5 minutes, a temperature of 230°C, and a test load of 2.16 kgf, while in Reference Examples 1 to 7, which used PP as the base resin, measurement was performed under conditions of a holding time of 5 minutes, a temperature of 190°C, and a test load of 2.16 kgf.

[0267] [Raw materials] (Additive (fluorene compound)) AAD-FL: 9,9-bis(2-carbamoylethyl)fluorene represented by the following formula (1-1), prepared in accordance with Comparative Example 1 of WO 2021 / 172300, melting point 254 to 259°C, 5% weight loss temperature 320°C

[0268] [ka]

[0269] DEAA-FL: 9,9-bis[2-(N,N-diethylcarbamoyl)ethyl]fluorene represented by the following formula (1-2), prepared in accordance with Example 1 of WO 2021 / 172300, melting point 87 to 89°C, 5% weight loss temperature 294°C

[0270] [ka]

[0271] BPEF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, "BPEF" manufactured by Osaka Gas Chemicals Co., Ltd. BNEF: 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, "BNEF" manufactured by Osaka Gas Chemicals Co., Ltd.

[0272] (resin) Polyester resin A: A polyester resin prepared according to Example 18 of JP 2016-69643 A. Ratio (molar ratio) of structural units derived from monomer components in the resin: BNEF / EG / FDP-m = 75 / 25 / 100, weight average molecular weight Mw: 48,000 Polyester resin B: A polyester resin prepared according to Reference Example 8 of JP 2013-64119 A. Ratio (molar ratio) of structural units derived from monomer components in the resin: BPEF / EG / CHDA = 80 / 20 / 100, weight average molecular weight Mw: 51,000 As monomer components, "EG" represents ethylene glycol, "FDP-m" represents 9,9-bis[2-(methoxycarbonyl)ethyl]fluorene, and "CHDA" represents 1,4-cyclohexanedicarboxylic acid, and BNEF and BPEF are the same as above. PP: Polypropylene resin, Prime Polypro (registered trademark) J105G manufactured by Prime Polymer Co., Ltd.

[0273] (Examples 1 to 8, Comparative Examples 2 to 7) Polyester resin A and an additive (fluorene compound) were dry-blended in the proportions shown in Table 1 below. The resulting mixture was melt-kneaded using a twin-screw extruder (Warner & Pfleiderer "ZSK40", L / D = 41.75, screw diameter: 44 mm) at a temperature of 250 ± 10°C, a screw rotation speed of 180 rpm, and a discharge rate of 60 kg / hour to prepare a pellet-shaped resin composition, and its tensile properties, flexural properties, impact resistance, refractive index, and MFR were measured. Test pieces for the tensile properties, flexural properties, and impact resistance were prepared by injection molding the resulting resin composition.

[0274] (Comparative Example 1) Each evaluation was carried out in the same manner as in Examples 1 to 8 and Comparative Examples 2 to 7, except that no additive (fluorene compound) was added.

[0275] The evaluation results of Comparative Examples 1 to 7 and Examples 1 to 8 are shown in Table 1 below, along with the blending ratios.

[0276] [Table 1]

[0277] As is clear from Table 1, in the Examples, compared to Comparative Example 1 (without additives), the MFR was significantly improved without significantly decreasing (maintaining or improving) the mechanical properties such as tensile properties, bending properties, and impact resistance, and the optical properties, and high mechanical properties, optical properties, and high melt fluidity were achieved.

[0278] For example, in Example 1, in which AAD-FL was added, and Example 6, in which DEAA-FL was added, even with the addition of only 0.3 parts by mass, the MFR was improved by about 1.2 times while maintaining or improving the mechanical and optical properties compared to Comparative Example 1. Furthermore, even when the amount of additive was increased compared to Examples 1 and 6, the MFR was further improved while maintaining or improving the mechanical and optical properties.

[0279] On the other hand, in Comparative Examples 2 to 7, in which the type of additive was changed to BNEF or BPEF, it was difficult to maintain mechanical properties such as tensile strength, flexural strength, and impact resistance, and the degree of improvement in MFR was also low compared to Examples 1 to 3 and 6 to 8, in which the additive ratio was the same.

[0280] Furthermore, when comparing Examples 1 to 3 (AAD-FL) and Examples 6 to 8 (DEAA-FL) with the same addition ratio, it was found that Examples 1 to 3 (AAD-FL) were easier to improve the MFR, while Examples 6 to 8 (DEAA-FL) were easier to maintain or improve mechanical properties such as tensile properties and impact resistance.

[0281] Furthermore, in Example 5, which contained a larger amount of additive than the other examples, the surface of the test piece felt sticky and the refractive index was slightly lower than that of Comparative Example 1, possibly due to the tendency for bleed-out to occur.

[0282] (Examples 9 to 12, Comparative Examples 9 to 12) Polyester resin B and an additive (fluorene compound) were dry-blended in the proportions shown in Table 2 below. The resulting mixture was melt-kneaded using a twin-screw extruder (Warner & Pfleiderer "ZSK40", L / D = 41.75, screw diameter: 44 mm) at a temperature of 250 ± 10°C, a screw rotation speed of 180 rpm, and a discharge rate of 60 kg / hour to prepare a pellet-shaped resin composition, and its tensile properties, flexural properties, impact resistance, refractive index, and MFR were measured. Test pieces for the tensile properties, flexural properties, and impact resistance were prepared by injection molding the resulting resin composition.

[0283] (Comparative Example 8) Each evaluation was carried out in the same manner as in Examples 9 to 12 and Comparative Examples 9 to 12, except that no additive (fluorene compound) was added.

[0284] The evaluation results of Comparative Examples 8 to 12 and Examples 9 to 12 are shown in Table 2 below, along with the blending ratios.

[0285] [Table 2]

[0286] As is clear from Table 2, Examples 9 to 12 are examples in which polyester resin B was used instead of polyester resin A used in Examples 1 to 8, but generally similar trends were observed as in Examples 1 to 8. Compared to Comparative Example 8 (no additives), the MFR was significantly improved without significantly decreasing (maintaining or improving) the mechanical properties and optical properties such as tensile properties, flexural properties, and impact resistance, and the mechanical properties, optical properties, and melt fluidity were satisfied.

[0287] On the other hand, in Comparative Examples 9 to 12, in which the type of additive added to polyester resin B was changed to BNEF or BPEF, it was difficult to maintain mechanical properties such as tensile strength, flexural strength, and impact resistance, and the degree of improvement in MFR was also low compared to Examples 9 to 12, in which the additive ratio was the same.

[0288] Furthermore, when comparing Examples 9-10 (AAD-FL) and Examples 11-12 (DEAA-FL), it was found that Examples 9-10 (AAD-FL) were easier to improve MFR while maintaining or improving mechanical properties such as tensile properties and bending properties.

[0289] (Reference examples 2~7) PP and an additive (fluorene compound) were dry-blended in the ratios shown in Table 3. The resulting mixture was melt-kneaded using a twin-screw extruder (Thermo Fisher Scientific's "Process 11 Twin Screw Extruder", L / D = 40) at a temperature of 190 to 230°C, a screw rotation speed of 200 rpm, and a discharge rate of 1 kg / hour to prepare a pellet-shaped resin composition, and the MFR was measured.

[0290] (Reference example 1) Evaluation was carried out in the same manner as in Reference Examples 2 to 7, except that no additive (fluorene compound) was added.

[0291] The evaluation results of Reference Examples 1 to 7 are shown in Table 3 below, along with the blending ratios.

[0292] [Table 3]

[0293] As is clear from Table 3, in Reference Examples 2 to 4, in which AAD-FL was added to PP as the base resin, no improvement in MFR was observed, and rather, a decrease in MFR was observed as the addition ratio increased. On the other hand, in Reference Examples 5 and 6, in which DEAA-FL was added, an improvement in MFR was observed. Furthermore, in Reference Example 7, in which BPEF was added, the MFR was improved compared to Reference Examples 3 and 6, in which the additive was added at the same ratio. Therefore, the trends in Reference Examples 1 to 7, in which PP was used as the base resin, were completely different from those in Examples 1 to 12 and Comparative Examples 1 to 12, in which polyester resins were used. [Industrial Applicability]

[0294] The polyester resin composition of the present disclosure has good melt fluidity and excellent moldability without impairing mechanical properties or optical properties, and can therefore be effectively used in molded products that require higher mechanical strength while taking advantage of the polyester resin's properties such as toughness or impact resistance, transparency, electrical insulation, dimensional stability, and heat resistance, and can be used in a wide range of fields, such as electrical and electronic equipment, machinery, daily necessities, medical supplies, safety products, and leisure products.

[0295] Typical applications in the field of electrical and electronic equipment include, for example, antenna insulating materials, cases for semiconductors and circuit components, video camera components, AC adapter cases, stereo components, terminal boards, sockets, connectors, switches, optical disks, optical fibers, and lighting components. Examples of video camera components include chassis and bodies. Examples of optical disks include CDs and DVDs. Examples of lighting components include lighting globes, lampshades, and signal lights.

[0296] Typical applications in the machinery field include, for example, automobile components, precision equipment components, casings or housings, agricultural machinery, etc. Automotive components include, for example, automobile exteriors such as bumpers, wheel covers, lamp components such as lamp lenses, instrument panels, heater fans, power distributors such as caps, and meters. Precision equipment components include, for example, gears, cams, watch components, camera and strobe components, office equipment components, sewing machine components, microscope components, and projector components. Casings or housings include, for example, pumps, motors, and power tools.

[0297] Representative applications in the field of daily necessities include beverage containers, food containers, detergent containers, body care product containers, sunglasses, etc. Examples of beverage containers include soft drink bottles, alcohol bottles, and baby bottles. Examples of food containers include prepared food containers, cooking oil bottles, and seasoning bottles. Examples of detergent containers include bottles for laundry detergent and kitchen detergent. Examples of body care product containers include bottles for hair care products such as shampoo, conditioner, treatment, and hair growth agent, and cosmetic products such as lotion, emulsion, and facial cleanser.

[0298] Typical applications in the medical supplies field include syringes, medicine containers such as eye drop containers, dentures, X-ray parts, and blood transfusion joints.

[0299] Representative applications in the field of safety products include helmets, protective eyewear such as dust-proof glasses, fire alarm covers, and fire extinguisher parts.

[0300] Typical applications in the field of leisure goods include ski equipment and fishing reel parts.

[0301] The polyester resin composition of the present disclosure can also be formed into textile products that can be used in the above fields, etc. Examples of textile products include fibers, threads, ropes, nets, and fabrics (woven fabrics, knitted fabrics, nonwoven fabrics, etc.).

Claims

1. A polyester resin and a compound represented by the following formula (1) 【Chemical 1】 [In the formula, R １ represents a substituent, k represents an integer of 0 to 8, R ２ａ , R ２ｂ , R ２ｃ and R ２ｄ each independently represents a hydrogen atom or a substituent, R ３ａ and R ３ｂ each independently represents a hydrogen atom or a substituent, X １ａ and X １ｂ are independently represented by the following formula (X1): 【Chemistry 2】 (In the formula, R ４ and R ５ each independently represents a hydrogen atom or a hydrocarbon group, or R ４ and R ５ and are bonded to each other to form a heterocycle together with the adjacent nitrogen atom. represents a group represented by the following formula: and a fluorene compound represented by the formula (I):

2. In the formula (1), R １ represents a hydrocarbon group, k represents an integer of 0 to 4, R ２ａ , R ２ｂ , R ２ｃ and R ２ｄ each independently represents a hydrogen atom or a hydrocarbon group; R ３ａ and R ３ｂ each independently represents a hydrogen atom or a hydrocarbon group; In the formula (X1), R ４ and R ５ 2. The polyester resin composition according to claim 1, wherein each of is independently a hydrogen atom or an alkyl group.

3. In the formula (X1), R ４ and R ５ 3. The polyester resin composition according to claim 1, wherein R is a hydrogen atom.

4. 3. The polyester resin composition according to claim 1, wherein the polyester resin contains a structural unit having a fluorene skeleton.

5. The polyester resin contains, as a structural unit having a fluorene skeleton, a compound represented by the following formula (2): 【Chemistry 3】 (In the formula, R ６ represents a substituent, m represents an integer of 0 to 8, Z １ａ and Z １ｂ each independently represents an arene ring, R ７ａ and R ７ｂ each independently represents a substituent; n1 and n2 each independently represents an integer of 0 or more; A １ａ and A １ｂ each independently represents an alkylene group, and p1 and p2 each independently represent an integer of 0 or 1 or more. The polyester resin composition according to claim 4, which contains a diol unit represented by the formula:

6. 6. The polyester resin composition according to claim 5, wherein the polyester resin contains at least one dicarboxylic acid unit selected from the group consisting of an aliphatic dicarboxylic acid unit, an alicyclic dicarboxylic acid unit, and an aromatic dicarboxylic acid unit.

7. 3. The polyester resin composition according to claim 1, wherein the proportion of the fluorene compound is 0.01 to 30 parts by mass per 100 parts by mass of the total amount of the polyester resin and the fluorene compound.

8. 3. The polyester resin composition according to claim 1, wherein the polyester resin accounts for 50% by mass or more of the total resin components in the composition.

9. A molded article comprising the polyester resin composition according to claim 1 or 2.

10. A method for improving the flowability of a polyester resin by adding the fluorene compound represented by formula (1) according to claim 1 to the polyester resin.

11. A flowability improver for polyester resins, comprising the fluorene compound represented by formula (1) according to claim 1.

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