Aromatic thermoplastic resin, its production method and use

Abstract

To provide an aromatic thermoplastic resin having low melt viscosity and improved moldability regardless of high optical characteristics and high heat resistance and a method for producing the same, and a use of the same.SOLUTION: Into an aromatic thermoplastic resin including a unit of at least one aromatic component selected from an aromatic dicarboxylic acid component and an aromatic diol component, a constitutional unit derived from a branched aliphatic component that are selected from an aliphatic dicarboxylic acid component, an aliphatic diol component and an aliphatic hydroxycarboxylic acid component, includes one or a plurality of branched chains, in which at least the one branched chain having a linear or branched chain alkyl group having 3 to 30 carbon atoms or a linear or branched chain alkenyl group having 3 to 30 carbon atoms is introduced. The aromatic dicarboxylic acid component contains 9,9-bis(carboxy C6-10 aryl)fluorene, and the aromatic diol component contains 9,9-bis[hydroxy(polyalkoxy)phenyl]fluorene.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an aromatic thermoplastic resin, a method for producing the same, and uses of the aromatic thermoplastic resin. [Background technology]

[0002] Examples of resin materials suitable for optical plastics include polyester resins, polycarbonate resins, and polyester carbonate resins. Among these, a polyester resin, as described in JP 2016-69643 A (Patent Document 1), is known, which comprises a diol component containing a diol having hydroxy(poly)alkoxy fused polycyclic aromatic groups at the 9,9-positions of a fluorene skeleton and a dicarboxylic acid component containing a dicarboxylic acid having a fluorene skeleton as polymerization components. Specifically, an example of Patent Document 1 describes a polyester resin obtained by reacting a dicarboxylic acid component containing 9,9-di(2-methoxycarbonyl)fluorene (FDPM) with a diol component containing 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF).

[0003] Known examples of polycarbonate resins and polyester carbonate resins include thermoplastic resins that use a diol component in which each of the two benzene rings of a fluorene ring is substituted with an aryl group, as described in International Publication No. 2019 / 044214 (Patent Document 2). Specifically, the examples in Patent Document 2 describe polycarbonate resins and polyester carbonate resins that use 9,9-bis[4-(2-hydroxyethoxy)phenyl]-2,7-diphenylfluorene or 9,9-bis[4-(2-hydroxyethoxy)phenyl]-2,7-di(2-naphthyl)fluorene as the diol component (polymerization component).

[0004] Furthermore, International Publication No. 2020 / 213470 (Patent Document 3) describes a thermoplastic resin using a dicarboxylic acid component in which each of the two benzene rings of a fluorene ring is substituted with an aryl group, specifically a polyester resin and a polyester carbonate resin whose polymerization components are a dicarboxylic acid component containing 9,9-bis(2-methoxycarbonylethyl)-2,7-di(2-naphthyl)fluorene (2-DNFDP-m) and a diol component containing BNEF and ethylene glycol.

[0005] Furthermore, Japanese Patent Application Laid-Open No. 2018-178026 (Patent Document 4) describes a method for producing a bisphenol A type aromatic polycarbonate resin (I) containing a carbonate structural unit (A) having a bisphenol A skeleton and 1,1-bisphenol C 8-24 Patent Document 4 describes an aromatic polycarbonate resin composition containing 4 to 40 parts by mass of a polycarbonate copolymer (II) containing carbonate structural units (B) having an alkane skeleton, wherein the proportion of carbonate structural units (B) in the copolymer (II) is greater than 10 mol % and not more than 36.5 mol % relative to 100 mol % of the total of the structural units (A) and (B). Patent Document 4 describes that the fluidity of the resin composition is improved by incorporating the copolymer (II) having carbonate structural units (B) having an aliphatic hydrocarbon chain into the aromatic polycarbonate resin (I), and in the examples, describes copolymerization of bisphenol A with 1,1-bis(4-hydroxyphenyl)decane or 1,1-bis(4-hydroxyphenyl)dodecane in a molar ratio of approximately 61 / 39 to 85 / 15. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-69643 [Patent Document 2] International Publication No. 2019 / 044214 [Patent Document 3] International Publication No. 2020 / 213470 [Patent Document 4] Japanese Patent Application Publication No. 2018-178026 Summary of the Invention [Problem to be solved by the invention]

[0007] The resins described in Patent Documents 1 to 3 are suitable as optical materials because they can achieve both a high refractive index and low birefringence and have a high glass transition temperature. However, because they have high heat resistance, they require molding at high temperatures, and there is room for improvement in terms of ease of molding. In particular, it is difficult to efficiently mold thin members at low temperatures. The aromatic polycarbonate resin composition of Patent Document 4 has improved fluidity and transparency and reduced coloration, but has a low refractive index and large birefringence, so there is still room for improvement as an optical material.

[0008] SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide an aromatic thermoplastic resin having excellent optical properties, heat resistance and moldability, a method for producing the same, and uses thereof. [Means for solving the problem]

[0009] As a result of intensive research to achieve the above object, the present inventors have found that, in an aromatic thermoplastic resin containing at least one aromatic component selected from an aromatic dicarboxylic acid component and an aromatic diol component as a polymerization component, copolymerizing an aliphatic component having a branched structure with a relatively long branched chain as an aliphatic dicarboxylic acid component, an aliphatic diol component and / or an aliphatic hydroxycarboxylic acid component makes it possible to obtain a thermoplastic resin that has both a high refractive index and low birefringence, and that has high molding flowability while maintaining high heat resistance, thereby completing the present invention.

[0010] Generally, optical properties and moldability are in a trade-off relationship, where improving optical properties reduces moldability, and improving moldability reduces optical properties. Therefore, as optical devices such as cameras and image display devices become more sophisticated, the high level of properties required for optical components may not be satisfied. However, according to the present invention, it is possible to provide an optical component that achieves both optical properties and moldability, and is therefore compatible with high-performance optical devices such as cameras and image display devices.

[0011] That is, the aromatic thermoplastic resin of the present invention is an aromatic thermoplastic resin containing, as polymerization components, at least one aromatic component selected from an aromatic dicarboxylic acid component and an aromatic diol component, and at least one aliphatic component selected from an aliphatic dicarboxylic acid component, an aliphatic diol component, and an aliphatic hydroxycarboxylic acid component, wherein the aliphatic component-derived structural unit contains one or more branched chains, and at least one of the branched chains contains a branched aliphatic component-derived structural unit having a linear or branched alkyl group having 3 to 30 carbon atoms or a linear or branched alkenyl group having 3 to 30 carbon atoms. Note that the term "structural unit derived from" refers to a chemical structure remaining in the polymer after the corresponding component (aliphatic component, branched aliphatic component, etc.) has undergone a polymerization reaction (the same applies hereinafter).

[0012] The aromatic dicarboxylic acid component may contain a compound (first aromatic dicarboxylic acid) represented by the following formula (1).

[0013] [ka]

[0014] (In the formula, Z 1a and Z 1b independently represent an arene ring, and R 1a and R 1b each independently represents a substituent, k1 and k2 independently represent an integer of 0 to 4, and R 2a and R 2beach independently represents a substituent; m1 and m2 each independently represents an integer of 0 or more; n1 and n2 each independently represents an integer of 0 to 4; A 1a and A 1b each independently represents a linear or branched alkylene group; X 1a and X 1b each independently represents a hydroxyl group, an alkoxy group, or a halogen atom.

[0015] The aromatic dicarboxylic acid component may contain a compound (first aromatic dicarboxylic acid) represented by the following formula (1-1a), (1-2a), or (1-2b).

[0016] [ka]

[0017] (In the formula, R 1a and R 1b each independently represents a halogen atom, a cyano group, or a linear or branched alkyl group having 1 to 6 carbon atoms; k1 and k2 each independently represent an integer of 0 to 2; A 1a and A 1b each independently represents a linear or branched alkylene group having 1 to 8 carbon atoms; X 1a and X 1b are the same as in the above formula (1))

[0018] The aromatic diol component may contain a compound (first aromatic diol) represented by the following formula (3).

[0019] [ka]

[0020] (In the formula, R 4 represents a substituent, r represents an integer of 0 to 8, and Z 3a and Z 3b independently represent an arene ring, and R 5a and R 5b independently represent a substituent, s1 and s2 independently represent an integer of 0 or more, and A 3a and A3b each independently represents a linear or branched alkylene group, and t1 and t2 each independently represent an integer of 0 or greater.

[0021] The aromatic diol component may contain a compound (first aromatic diol) represented by the following formula (3-1) or (3-2).

[0022] [ka]

[0023] (In the formula, R 4 represents a linear or branched alkyl group having 1 to 4 carbon atoms, r represents 0 or 1, and R 5a and R 5b each independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms; s1 and s2 each independently represent an integer of 0 to 2; A 3a and A 3b each independently represents a linear or branched alkylene group having 1 to 4 carbon atoms, and t1 and t2 each independently represent an integer of 0 to 10.

[0024] The structural unit derived from the aromatic component may contain at least one structural unit derived from an aromatic component selected from the structural units derived from the aromatic dicarboxylic acid component and the structural units derived from the aromatic diol component, and may contain structural units derived from both aromatic components.

[0025] The structural unit derived from the branched aliphatic component may have a linear or branched alkyl group having 3 to 22 carbon atoms, or a linear or branched alkenyl group having 3 to 22 carbon atoms as a branched chain. Specifically, the structural unit derived from the branched aliphatic component may be a branched alkanediol having 6 to 20 carbon atoms, a branched alkylene dicarboxylic acid having 12 to 22 carbon atoms (or a branched alkylene dicarboxylic acid having 10 to 20 carbon atoms), and a branched hydroxyalkanecarboxylic acid having 7 to 25 carbon atoms (or a branched hydroxyalkane dicarboxylic acid having 7 to 25 carbon atoms). 6-24The branched aliphatic component may be a structural unit derived from at least one selected from the group consisting of 1,2-alkanediols (1,2-C alkylene-carboxylic acids) and may have, as at least one branched chain, a linear or branched alkyl group having 3 to 18 carbon atoms; or a linear or branched alkenyl group having 3 to 18 carbon atoms. The branched aliphatic component may be a 1,2-alkanediol (1,2-C alkanediol) having 6 to 16 carbon atoms. 6-16 Alkanediol) or 1,2-alkenediol having 6 to 16 carbon atoms (1,2-C 6-16 alkenediol).

[0026] The branched aliphatic component comprises at least one selected from a branched aliphatic dicarboxylic acid component, a branched aliphatic diol component, and a branched aliphatic hydroxycarboxylic acid component, and the proportion of all structural units derived from the branched aliphatic component relative to all structural units derived from the dicarboxylic acid component, the diol component, and the hydroxycarboxylic acid component (or all structural units derived from the above-mentioned polymerization components) may be 1 to 35 mol %.Furthermore, the proportion of all structural units derived from the branched aliphatic component relative to all structural units derived from the dicarboxylic acid component, the diol component, and the hydroxycarboxylic acid component may be 2 to 30 mol %. For example, the branched aliphatic component may include a 1,2-alkanediol having 6 to 16 carbon atoms, particularly a linear or branched alkyl group having 3 to 10 carbon atoms; or a 1,2-alkanediol having 6 to 16 carbon atoms and having a linear or branched alkenyl group having 3 to 10 carbon atoms; a 1,3-alkanediol having 6 to 16 carbon atoms, particularly a linear or branched alkyl group having 3 to 10 carbon atoms; or a 1,3-alkanediol having 6 to 16 carbon atoms and having a linear or branched alkenyl group having 3 to 10 carbon atoms; and the proportion of the structural units derived from a 1,2-alkanediol having 6 to 16 carbon atoms and / or the structural units derived from a 1,3-alkanediol having 6 to 16 carbon atoms relative to the total structural units derived from the dicarboxylic acid component, diol component, and hydroxycarboxylic acid component may be 3 to 25 mol %.

[0027] When a carboxyl group and a hydroxyl group are referred to as reactive groups, the branched aliphatic component may contain multiple branched chains, and the multiple branched chains may each be branched from the same or different carbon atoms on the chain (main chain) connecting the two reactive groups; the two reactive groups may each be bonded to a primary carbon atom, or to a primary carbon atom and a secondary carbon atom, respectively. In a preferred embodiment, when multiple branched chains are contained, the multiple branched chains may each be branched from different carbon atoms on the chain (main chain) connecting the two reactive groups; and the two reactive groups may each be bonded to a primary carbon atom and a secondary carbon atom, respectively.

[0028] The aromatic thermoplastic resin may be a polyester resin or a polyester carbonate resin.

[0029] An aromatic thermoplastic resin can be produced by reacting an aromatic dicarboxylic acid component and an aromatic diol component with at least one aliphatic component selected from an aliphatic dicarboxylic acid component, an aliphatic diol component, and an aliphatic hydroxycarboxylic acid component. In the present invention, in this method, the aromatic thermoplastic resin is prepared (produced) by reacting (or copolymerizing) the aliphatic component with a branched aliphatic component containing one or more branched chains, at least one of which has a linear or branched alkyl group having 3 to 30 carbon atoms or a linear or branched alkenyl group having 3 to 30 carbon atoms.

[0030] The present invention also encompasses a molded article containing the aromatic thermoplastic resin. Such a molded article may be an optical component. Specifically, the molded article may be an optical film or an optical lens.

[0031] The present invention may also solve the following problems as a secondary object.

[0032] That is, another object of the present invention is to provide an aromatic thermoplastic resin that can reduce water absorption or hygroscopicity, a method for producing the same, and uses thereof.

[0033] In this specification and claims, the terms "dicarboxylic acid component," "dicarboxylic acid," and "hydroxycarboxylic acid component" are not limited to compounds having a free carboxyl group, but also include their reactive derivatives or ester-forming derivatives, specifically, halocarboxylic acids such as acyl chloride, alkyl esters such as methyl esters, and acid anhydrides. Unless otherwise specified, "dicarboxylic acid component" and "dicarboxylic acid" are used synonymously with "unit of dicarboxylic acid component" and "structural unit derived from dicarboxylic acid component," "diol component" and "diol" are used synonymously with "unit of diol component" and "structural unit derived from diol component," and "hydroxycarboxylic acid component" and "hydroxycarboxylic acid" are used synonymously with "unit of hydroxycarboxylic acid component" and "structural unit derived from hydroxycarboxylic acid component." Therefore, in thermoplastic resins, "dicarboxylic acid component," "dicarboxylic acid," "diol component," "diol," "hydroxycarboxylic acid component," and "hydroxycarboxylic acid" are included as structural units.

[0034] In this specification and claims, an aliphatic dicarboxylic acid component, an aliphatic diol component, and an aliphatic hydroxycarboxylic acid component may be simply referred to as an "aliphatic component," and a branched aliphatic dicarboxylic acid component, a branched aliphatic diol component, and a branched aliphatic hydroxycarboxylic acid component may be simply referred to as a "branched aliphatic component."

[0035] In this specification and claims, a carboxyl group (or a reactive derivative group) and a hydroxyl group may be collectively referred to as a "reactive group," and "two reactive groups" is used synonymously with "two carboxyl groups (or reactive derivative groups)," "two hydroxyl groups," and "a carboxyl group (or reactive derivative group) and a hydroxyl group."

[0036] In this specification and claims, the chain (alkyl chain or alkenyl chain) connecting the carbon atoms to which the two reactive groups of a branched aliphatic component are bonded is referred to as the "linear portion" or "main chain," and the chain branched (or forked) from the linear portion is referred to as the "side chain portion" or "branched chain."

[0037] The carbon atom to which the two reactive groups of a branched aliphatic component are bonded corresponds to the "linear portion" or "main chain," and the "side chain portion" or "branched chain" may branch from the carbon atom to which the two reactive groups are bonded, or may branch from a carbon atom in the linear portion other than the carbon atom to which the two reactive groups are bonded. Furthermore, the number of carbon atoms in the alkyl or alkenyl group in the side chain portion (or branched chain) does not include the carbon atom in the linear portion (or main chain) to which the side chain portion (or branched chain) is bonded.

[0038] For example, in 12-hydroxystearic acid represented by the following formula (A), the chain connecting the carbon atoms at positions 1 and 12 in the following formula (A) corresponds to the "straight chain portion" or "main chain," and the chain connecting the carbon atoms at positions 13 and 18, which branches off from the carbon atom at position 12 and bonds to it, corresponds to the "side chain portion" or "branched chain." The number of carbon atoms in the "straight chain portion" is 12, and the number of carbon atoms in the "side chain portion" is 6.

[0039] For example, in 2-propyl-1,3-pentanediol represented by the following formula (B), the chain connecting the carbon atoms at positions 1 and 3 in the following formula (B) corresponds to the "straight chain portion" or "main chain," and the chain connecting the carbon atoms at positions 4 and 6, which branches off from and bonds to the carbon atom at position 2, corresponds to the "side chain portion" or "branched chain." The number of carbon atoms in the "straight chain portion" is 3, and the number of carbon atoms in the "side chain portion" is 3. [ka]

[0040] Also, the number of carbon atoms in the substituent is C1, C6, C 10 For example, an alkyl group with 1 carbon atom is represented as a "C1 alkyl group," and an aryl group with 6 to 10 carbon atoms is represented as a "C 6-10 In other words, "a linear or branched alkyl group having 1 to 8 carbon atoms" is expressed as "a linear or branched C 1-8 Similarly, "a linear or branched alkylene group having 1 to 8 carbon atoms" is sometimes referred to as "a linear or branched C 1-8In this case, the branched C alkylene group is 1-2 The meaning does not include alkylene groups, i.e., linear C 1-8 Alkylene group or branched chain C 3-8 It is used to mean an alkylene group.

[0041] Furthermore, for example, the carbon number of 3 to 8 in "(branched) alkylene dicarboxylic acid having 3 to 8 carbon atoms" includes two carbon atoms contained in the dicarboxylic acid, and "(branched) C 1-6 For example, the carbon number of 3 to 8 in "(branched) hydroxyalkanecarboxylic acid having 3 to 8 carbon atoms" includes one carbon atom contained in the carboxylic acid, and is used synonymously with "(branched) hydroxyalkanecarboxylic acid having 3 to 8 carbon atoms." 2-7 The term "alkane-carboxylic acid" is used synonymously with "alkane-carboxylic acid of the formula (I)."

[0042] The term "ring assembly arene ring" refers to a ring system in which two or more ring systems (arene ring systems) are 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 below, phenylnaphthalene rings and binaphthyl rings are classified as ring assembly arene rings even though they contain a fused polycyclic arene ring, and are clearly distinguished from "fused polycyclic arene rings" such as naphthalene rings (non-ring assembly arene rings).

[0043] Unless otherwise specified, the term "(poly)alkoxy" is used to mean both an alkoxy group and a polyalkoxy group. [Effects of the Invention]

[0044] In the present invention, aromatic dicarboxylic acid components and / or aromatic diol components are used as reaction components, resulting in aromatic thermoplastic resins with excellent optical properties and heat resistance. Furthermore, because branched aliphatic components having branched chains are used as the aliphatic dicarboxylic acid component, aliphatic diol component, and / or aliphatic hydroxycarboxylic acid component, moldability and melt fluidity can be significantly improved while maintaining high optical properties and heat resistance. Furthermore, by using a specific aromatic dicarboxylic acid component and aromatic diol component, the absolute value of birefringence can be reduced while maintaining a high refractive index and heat resistance, and moldability or fluidity can be improved. Furthermore, despite the inclusion of an aliphatic component, the water absorption of the resulting aromatic thermoplastic resin can be reduced, likely due to the use of the specific branched aliphatic component. [Brief explanation of the drawings]

[0045] [Figure 1] FIG. 1 shows the chemical formulas and abbreviations of the materials used in the examples and comparative examples. [Figure 2] FIG. 2 shows the chemical formulas and abbreviations of the materials used in the examples and comparative examples. DETAILED DESCRIPTION OF THE INVENTION

[0046] The aromatic thermoplastic resin of the present invention contains, as a repeating unit, at least one aromatic component selected from an aromatic dicarboxylic acid component and an aromatic diol component. That is, it contains, as a repeating unit, a dicarboxylic acid component containing at least an aromatic dicarboxylic acid component and / or a diol component containing at least an aromatic diol component. In a preferred embodiment, in order to improve the refractive index and heat resistance, aromatic components of both the aromatic dicarboxylic acid component and the aromatic diol component are contained as repeating units. Furthermore, the aromatic thermoplastic resin contains units of at least one aliphatic component selected from an aliphatic dicarboxylic acid component, an aliphatic diol component, and an aliphatic hydroxycarboxylic acid component.

[0047] [Dicarboxylic acid component] Examples of the dicarboxylic acid component include an aromatic dicarboxylic acid component, an alicyclic dicarboxylic acid component, and an aliphatic dicarboxylic acid component. The dicarboxylic acid component preferably contains at least an aromatic dicarboxylic acid component in order to improve the refractive index and heat resistance. The aliphatic dicarboxylic acid component may contain a first aliphatic dicarboxylic acid component (branched aliphatic component) having a predetermined branched structure, or may contain a second aliphatic dicarboxylic acid component not having the branched structure. The alicyclic dicarboxylic acid component, particularly at least the first aliphatic dicarboxylic acid component, is preferably a copolymerization component.

[0048] [Aromatic dicarboxylic acid component] The aromatic dicarboxylic acid component may be a compound having one or more arene rings, such as a compound having a monocyclic arene ring, a fused polycyclic arene ring, or a ring-assembly polycyclic arene ring. The aromatic dicarboxylic acid component may be a dicarboxylic acid component having a 9,9-bisarylfluorene skeleton or a 9,9-bisalkylfluorene skeleton (first aromatic dicarboxylic acid component), a dicarboxylic acid component having a monocyclic arene ring, a fused polycyclic arene ring, or a ring-assembly polycyclic arene ring with a carboxyl group bonded to the arene ring (second aromatic dicarboxylic acid component), or a bisphenol-type dicarboxylic acid component having a monocyclic arene ring bonded via an alkylene group or the like (third aromatic dicarboxylic acid component). A preferred aromatic dicarboxylic acid component contains at least a first aromatic dicarboxylic acid component and / or a second aromatic dicarboxylic acid component, particularly at least a first aromatic dicarboxylic acid component.

[0049] First Aromatic Dicarboxylic Acid Component The first aromatic dicarboxylic acid component is a 9,9-bis(carboxy C), such as 9,9-bis(4-carboxyphenyl)fluorene. 6-10 The first aromatic dicarboxylic acid component may be a (aryl)fluorene, and a preferred first aromatic dicarboxylic acid component may include a compound represented by the following formula (1):

[0050] [ka]

[0051] (In the formula, Z 1a and Z 1b independently represent an arene ring, and R 1a and R 1b each independently represents a substituent, k1 and k2 independently represent an integer of 0 to 4, and R 2a and R 2b each independently represents a substituent; m1 and m2 each independently represents an integer of 0 or more; n1 and n2 each independently represents an integer of 0 to 4; A 1a and A 1b each independently represents a linear or branched alkylene group; X 1a and X 1b each independently represents a hydroxyl group, an alkoxy group, or a halogen atom.

[0052] R 1a and R 1b Examples of the substituent represented by the formula (I) include an alkyl group, a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom, and a cyano group; examples of the alkyl group include a linear or branched C 1-6 alkyl groups. 1a and R 1b is a linear or branched C such as a methyl group 1-4 It is an alkyl group.

[0053] R 1a and R 1b The substitution positions of R may be the 1-position, 2-position, 7-position, 3,6-position, 4,5-position, or 2,7-position of the fluorene ring. 1a and R 1b The numbers of substitutions k1 and k2 in R can be selected from integers of 0 to 4, and are integers of 0 to 3, preferably integers of 0 to 2, more preferably 0 or 1, and particularly preferably 0. When k1 and k2 are integers of 2 or more, R 1a and R 1b The types of the substituents may be the same or different.

[0054] Ring Z 1a and ring Z 1bExamples of the arene ring (aromatic hydrocarbon ring) represented by the formula (I) include monocyclic arene rings such as a benzene ring, and polycyclic arene rings; examples of the polycyclic arene rings include fused polycyclic arene rings (fused polycyclic aromatic hydrocarbon rings) and ring-assembled arene rings (ring-assembled polycyclic aromatic hydrocarbon rings).

[0055] The fused polycyclic arene rings include fused bicyclic arene rings, specifically, fused bicyclic C rings such as naphthalene rings and indene rings. 10-16 fused tricyclic arene rings, and fused bicyclic to tetracyclic arene rings such as fused tricyclic arene rings. The fused tricyclic arene rings include fused tricyclic C 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 The ring-assembled arene ring includes 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.

[0056] Preferred Ring Z 1a and Z 1b is C 6-14 C arene ring, preferably benzene ring, naphthalene ring, biphenyl ring, etc. 6-12 C such as an arene ring, more preferably a benzene ring or a naphthalene ring 6-10 arene rings, particularly benzene rings and naphthalene rings.

[0057] Ring Z 1a and Z 1b The types may be different from each other, but are usually the same.

[0058] Also, ring Z 1a and Z 1bmay be substituted at any of the 1-4 positions and the 5-8 positions of the fluorene ring, and are usually the 2-, 3- and / or 7- and 8-positions. Preferred substitution positions (or bonding positions) are symmetrical positions on the paper in the formula (1), such as the 1,8-, 2,7-, 3,6- and 4,5-positions of the fluorene ring, particularly the 2,7-position. 1a , Z 1b When is a naphthalene ring, it may be at either the 1st or 2nd position of the naphthalene ring, and from the viewpoint of improving heat resistance, it is preferably the 1st position of the naphthalene ring, and from the viewpoint of preparing a resin that satisfies a good balance of a high refractive index, a low Abbe number, and a low birefringence (or a large negative birefringence), it is particularly preferably the 2nd position of the naphthalene ring.

[0059] R 2a and R 2b Examples of the substituent represented by the formula (I) include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an acyl group, a nitro group, a cyano group, and a di-substituted amino group.

[0060] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0061] The alkyl group includes a linear or branched alkyl group, and C groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. 1-10 Alkyl groups, preferably C 1-6 alkyl group, more preferably C 1-4 Examples of the aryl group include C alkyl groups such as phenyl groups, alkylphenyl groups, biphenylyl groups, and naphthyl groups. 6-12 Aryl group; mono- to tri-C such as methylphenyl group (or tolyl group), dimethylphenyl group (or xylyl group) 1-4 Examples include alkyl-phenyl groups.

[0062] The alkoxy group includes a linear or branched alkoxy group, and C alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, and a t-butoxy group. 1-10Examples of acyl groups include C groups such as acetyl groups. 1-6 Examples include alkyl-carbonyl groups.

[0063] The mono- or di-substituted amino group includes di-C such as dimethylamino group. 1-4 Alkylamino group; bis(C) such as diacetylamino group 1-4 alkyl-carbonyl)amino groups.

[0064] Typical group R 2a and R 2b Examples of the group R include alkyl groups, aryl groups, alkoxy groups, acyl groups, nitro groups, and cyano groups. 2a and R 2b is an alkyl group, specifically a linear or branched C 1-6 Alkyl groups; alkoxy groups, specifically, linear or branched C groups such as methoxy groups 1-4 Alkoxy groups are particularly preferred; linear or branched C groups such as methyl groups are particularly preferred. 1-4 It is an alkyl group. 2a and R 2b is an aryl group, the group R 2a and R 2b are rings Z 1a or Z 1b may form the ring assembly arene ring together with

[0065] The numbers of substitutions m1 and m2 are integers of 0 to 4, preferably integers of 0 to 2, more preferably 0 or 1, and particularly preferably 0. When m1 and m2 are integers of 2 or more, the group R 2a and R 2b The types may be the same or different.

[0066] The substitution numbers n1 and n2 can be selected, for example, from the range of integers from 0 to 4, and are integers from 0 to 3, preferably integers from 0 to 2, more preferably 0 or 1, and particularly preferably 1. Use of a compound in which n1 and n2 are 1 or more is useful for increasing the refractive index and glass transition temperature of an aromatic thermoplastic resin and reducing the Abbe number and absolute value of birefringence.

[0067] Base A 1a and A 1b Examples of the linear or branched alkylene group represented by the formula (I) include linear or branched C alkylene groups such as methylene, ethylene, trimethylene, propylene, 1,4-butanediyl, and 2-methylpropane-1,3-diyl. 1-8 Preferred alkylene groups include linear or branched C 1-6 Alkylene groups, more preferably linear or branched C 2-4 Alkylene groups, particularly linear or branched C groups such as ethylene and propylene groups 2-3 An alkylene group is preferred, and an ethylene group is particularly preferred.

[0068] X 1a and X 1b The alkoxy group represented by the formula (I) is a straight-chain or branched C alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, or a t-butoxy group. 1-4 Examples include alkoxy groups, and C 1-2 An alkoxy group is preferred. Examples of halogen atoms include a chlorine atom and a bromine atom. Preferred X 1a and X 1b is a hydroxyl group, a methoxy group, or an ethoxy group, and for low-temperature reaction, a halogen atom such as a chlorine atom is also preferred.

[0069] Representative dicarboxylic acid components represented by the formula (1) include dicarboxylic acid components in which n1 and n2 are 0, i.e., 9,9-bis(carboxyalkyl)fluorenes; and dicarboxylic acids in which n1 and n2 are 1, i.e., 9,9-bis(carboxyalkyl)-diarylfluorenes.

[0070] That is, a preferred first aromatic dicarboxylic acid component may contain a compound (aromatic dicarboxylic acid component) represented by the following formula (1-1a), (1-2a) or (1-2b).

[0071] [ka]

[0072] (In the formula, R 1a and R 1b are independently a halogen atom, a cyano group, a linear or branched C 1-6 represents an alkyl group, k1 and k2 independently represent an integer of 0 to 2, and A 1a and A 1b are independently linear or branched chain C 1-8 represents an alkylene group, and X 1a and X 1b are the same as in the above formula (1))

[0073] Compounds in which n1 and n2 are 0 in formula (1) [9,9-bis(carboxyalkyl)fluorenes corresponding to the formula (1-1a)] include 9,9-bis(carboxyC) compounds such as 9,9-bis(2-carboxyethyl)fluorene and 9,9-bis(2-carboxypropyl)fluorene. 2-6 alkyl)fluorene, and preferably 9,9-bis(carboxy C 2-4 alkyl)fluorene, more preferably 9,9-bis(carboxy C 2-3 alkyl)fluorenes, particularly 9,9-bis(2-carboxyethyl)fluorene and 9,9-bis(2-carboxypropyl)fluorene, among which 9,9-bis(2-carboxyethyl)fluorene is preferred.

[0074] Examples of compounds in which n1 and n2 are 1 in formula (1) (9,9-bis(carboxyalkyl)-diarylfluorenes) include 9,9-bis(carboxyalkyl)-diphenylfluorenes corresponding to the formula (1-2a), specifically, 9,9-bis(carboxyC) compounds 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. 2-69,9-bis(carboxyalkyl)-dinaphthylfluorenes corresponding to the formula (1-2b), specifically, 9,9-bis(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, 9,9-bis(2-carboxyethyl)-2,7-di(1-naphthyl)fluorene, etc. 2-6 alkyl)-dinaphthylfluorene and the like.

[0075] These first aromatic dicarboxylic acid components may be used alone or in combination of two or more. Among the dicarboxylic acids represented by the formula (1), 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)fluorene and 9,9-bis(2-carboxypropyl)fluorene are preferred. 2-4 alkyl)fluorene; 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)-2,7-diphenylfluorene and 9,9-bis(2-carboxypropyl)-2,7-diphenylfluorene 2-4 alkyl)-2,7-diphenylfluorene; 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)-2,7-dinaphthylfluorene and 9,9-bis(2-carboxypropyl)-2,7-dinaphthylfluorene 2-4 alkyl)-2,7-dinaphthylfluorene is preferred. 2-4 In the alkyl)-2,7-dinaphthylfluorene, the naphthyl group is a 1-naphthyl group (i.e., 9,9-bis(carboxy C 2-3 The fluorene may be a 2-naphthyl group (i.e., a 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)-2,7-di(2-naphthyl)fluorene), but is preferably a 2-naphthyl group (i.e., a 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)-2,7-di(2-naphthyl)fluorene). 2-3It is 2,7-di(2-naphthyl)fluorene).

[0076] The aromatic dicarboxylic acid component represented by the formula (1) and its production method are known. A compound in which n1 and n2 are 0 can be prepared by reacting 9H-fluorenes with a group -A according to the method described in JP-A-2005-89422. 1a -CO-X 1a and -A 1b -CO-X 1b The compound in which n1 and n2 are 1 or more can be prepared by reacting a compound having a group -A at the 9,9-position according to the method described in Patent Document 3. 1a -CO-X 1a and -A 1b -CO-X 1b and a compound having a fluorene skeleton having ring Z 1a and Z 1b a method of coupling a compound having an arene ring corresponding to the above; 1a and Z 1b and then coupling the resulting compound (a compound having a 9H-fluorene skeleton) with a compound having an arene ring corresponding to the group -A by using the method described in JP-A-2005-89422. 1a -CO-X 1a and -A 1b -CO-X 1b With a component corresponding to the above, for example, (meth)acrylic acid or an ester thereof, etc.

[0077] Second Aromatic Dicarboxylic Acid Component The aromatic dicarboxylic acid component may contain a second aromatic dicarboxylic acid component in addition to the first aromatic dicarboxylic acid component. Such a second aromatic dicarboxylic acid component can be represented by the following formula (2). The second aromatic dicarboxylic acid component is useful for adjusting the birefringence to the plus (+) side (or positive side) while maintaining a high refractive index and glass transition temperature.

[0078] [ka]

[0079] (In the formula, Z 2 indicates an arene ring, and R 3 represents a substituent, p represents an integer of 0 or more, and X 1a and X 1b (same as above)

[0080] Ring Z 2 The arene ring represented by the formula (1) includes ring Z 1a and Z 1b Examples of the ring Z include the same arene rings as those shown in the above. 2 is a C ring such as a benzene ring, naphthalene ring, or biphenyl ring. 6-14 arene rings, and more preferably C 6-12 arene rings; among them, C 6-10 In order to improve the refractive index and heat resistance, a C ring such as a naphthalene ring or a biphenyl ring may be used. 10-12 Polycyclic arene rings, particularly fused polycyclic arene rings such as naphthalene rings, are preferred.

[0081] R 3 Examples of the substituent represented by the formula (1), including preferred embodiments thereof, include the group R 2a and R 2b The preferred groups R 3 Examples of the alkyl group include linear or branched C alkyl groups, specifically methyl groups. 1-6 alkyl groups; aryl groups, specifically, C groups such as phenyl groups 6-14 aryl groups; alkoxy groups, specifically linear or branched C groups such as methoxy groups; 1-4 Alkoxy groups are preferred, and alkyl and aryl groups are particularly preferred. 1-4 C such as alkyl group and phenyl group 6-10 An aryl group is preferred. 3 is an aryl group, the group R 3 is the ring Z 2 may form a ring assembly arene ring together with

[0082] base R 3 The number of substitutions p is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0. When p is an integer of 2 or more, a plurality of groups R 3 The types may be the same or different from each other.

[0083] Ring Z 2 The positions of the two carbonyl groups [—C(═O)—] on the ring Z are not particularly limited. 2 is a benzene ring, it is preferably substituted at any of the o-, m-, or p-positions, preferably at the m- or p-positions, particularly preferably at the p-positions; 2 When is a naphthalene ring, it is preferably substituted at the 1,5 or 2,6 positions, particularly at the 2,6 positions; 2 is a biphenyl ring, it is preferred that both benzene rings are substituted at the 2,2', 3,3' or 4,4' positions, preferably at the 2,2' or 4,4' positions, particularly at the 2,2' positions.

[0084] The second aromatic dicarboxylic acid component may, for example, be a ring Z 2 Benzenedicarboxylic acid in which ring Z is a benzene ring; 2 is a polycyclic arene ring, and the like.

[0085] Examples of the benzenedicarboxylic acid component include benzenedicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; C 5-methylisophthalic acid; 1-4 alkyl-benzenedicarboxylic acids and the like.

[0086] Examples of the polycyclic arene dicarboxylic acid component include condensed polycyclic arene dicarboxylic acids, ring-assembled arene dicarboxylic acids, etc. Examples of the condensed polycyclic arene dicarboxylic acids include naphthalenedicarboxylic acids such as 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; anthracene dicarboxylic acid; and condensed polycyclic C such as phenanthrene dicarboxylic acid. 10-24 arene-dicarboxylic acids, fluorenedicarboxylic acids such as 2,7-dicarboxyfluorene, etc., and preferably fused polycyclic C 10-14 The ring-assembled arene dicarboxylic acids include, for example, bi-C such as 2,2'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, and 4,4'-biphenyldicarboxylic acid. 6-10 arene-dicarboxylic acids, and biphenyldicarboxylic acid is preferred.

[0087] These second aromatic dicarboxylic acid components may be used alone or in combination of two or more. Among these second aromatic dicarboxylic acid components, benzene dicarboxylic acids such as isophthalic acid and terephthalic acid; condensed polycyclic C dicarboxylic acids such as naphthalenedicarboxylic acid; 10-14 Arene-dicarboxylic acids; Bi-C such as biphenyldicarboxylic acid 6-10 Arene-dicarboxylic acids are preferred, and in order to improve the refractive index and heat resistance, ring Z 2 is a polycyclic arene ring, such as 2,2'-biphenyldicarboxylic acid, and especially 2,6-naphthalenedicarboxylic acid.

[0088] The molar ratio of the first aromatic dicarboxylic acid component to the second aromatic dicarboxylic acid component (former / latter) can be selected from the range of 50 / 50 to 100 / 0, and is preferably in the following stepwise manner: 55 / 45 to 100 / 0, 60 / 40 to 100 / 0, 65 / 35 to 100 / 0, 70 / 30 to 100 / 0, preferably 75 / 25 to 100 / 0, particularly 80 / 20 to 100 / 0.

[0089] A third aromatic dicarboxylic acid component The aromatic dicarboxylic acid component may further contain a third aromatic dicarboxylic acid component, if necessary. Examples of such aromatic dicarboxylic acid components include diarylalkane dicarboxylic acids, specifically, di-C such as 4,4'-diphenylmethane dicarboxylic acid. 6-10 Aryl C 1-6 Alkane-dicarboxylic acids, etc.; diaryl ketone dicarboxylic acids, specifically, di(C) such as 4,4'-diphenyl ketone dicarboxylic acid 6-10 aryl) ketone-dicarboxylic acids; diarylsulfonedicarboxylic acids, specifically di(C aryl) ketone-dicarboxylic acids such as 4,4'-diphenylsulfonedicarboxylic acid; 6-10 aryl) sulfone-dicarboxylic acids and the like.

[0090] The molar ratio of the third aromatic dicarboxylic acid component to the first aromatic dicarboxylic acid component (former / latter) can be selected within a range of 70 / 30 to 100 / 0, preferably 80 / 20 to 100 / 0, more preferably 85 / 15 to 100 / 0, and particularly preferably 90 / 10 to 100 / 0.

[0091] The first aromatic dicarboxylic acid component may be contained as the main component relative to the total aromatic dicarboxylic acid components, and the proportion of the first aromatic dicarboxylic acid component relative to the total aromatic dicarboxylic acid components can be selected from the range of 50 to 100 mol%, preferably in the following stepwise manner: 55 to 100 mol%, 60 to 100 mol%, 65 to 100 mol%, 70 to 100 mol%, more preferably 75 to 100 mol%, and particularly preferably 80 to 100 mol%.

[0092] [Alicyclic dicarboxylic acid component] Examples of the alicyclic dicarboxylic acid component include cycloalkane dicarboxylic acids, specifically, C 1,4-cyclohexane dicarboxylic acids. 5-10Cycloalkane dicarboxylic acids, etc.; bridged cyclic cycloalkane dicarboxylic acids, specifically, di- or tricycloalkane dicarboxylic acids such as decalin dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid, tricyclodecane dicarboxylic acid, etc.; cycloalkene dicarboxylic acids, specifically, C such as cyclohexene dicarboxylic acid, etc. 5-10 Cycloalkene-dicarboxylic acids and the like; bridged cyclic cycloalkene dicarboxylic acids, specifically, di- or tricycloalkene dicarboxylic acids such as norbornene dicarboxylic acid and the like.

[0093] These alicyclic dicarboxylic acid components may be used alone or in combination of two or more. The proportion of the alicyclic dicarboxylic acid component may be selected from the range of 0 to 40 mol % relative to the total dicarboxylic acid components, and is preferably 30 mol % or less, 20 mol % or less, 10 mol % or less, and 5 mol % or less in the following stepwise manner, and the alicyclic dicarboxylic acid component may not be contained.

[0094] [Diol component] The diol component may contain an aromatic diol component, an alicyclic diol component, and / or an aliphatic diol component. The diol component preferably contains at least an aromatic diol component to improve refractive index and heat resistance. The aliphatic diol component may contain a branched aliphatic diol component (first aliphatic diol component) having a specific branched structure, or may contain a second aliphatic diol component not having the branched structure. The alicyclic diol component, particularly at least the first aliphatic diol component, is preferably a copolymer component.

[0095] [Aromatic diol component] The aromatic diol component may be a compound having one or more arene rings, such as a compound having a monocyclic arene ring, a fused polycyclic arene ring, or a ring-assembly polycyclic arene ring. The aromatic diol component may be a diol component having a 9,9-bisarylfluorene skeleton (first aromatic diol component), a diol component having a fused polycyclic arene ring (including a ring-assembly arene ring to which a polycyclic arene ring is single-bonded) (second aromatic diol component), or a diol component having a monocyclic arene ring (including a ring-assembly arene ring to which a monocyclic arene ring is single-bonded, or a bisphenol-type arene ring to which a monocyclic arene ring is bonded via an alkylene chain or the like) (third aromatic diol component). A preferred aromatic diol component contains at least the first aromatic diol component and / or the second aromatic diol component, particularly at least the first aromatic diol component.

[0096] First Aromatic Diol Component The first aromatic diol component may contain a compound represented by the following formula (3).

[0097] [ka]

[0098] (In the formula, R 4 represents a substituent, r represents an integer of 0 to 4, and Z 3a and Z 3b independently represent an arene ring, and R 5a and R 5b independently represent a substituent, s1 and s2 independently represent an integer of 0 or more, and A 3a and A 3b each independently represents a linear or branched alkylene group, and t1 and t2 each independently represent an integer of 0 or greater.

[0099] In the formula (3), Z 3a and Z 3b Examples of the arene ring represented by the formula (1) include ring Z 1a and Z 1b The ring Z is an arene ring similar to the ring Z.3a and Z 3b The types of rings Z may be the same or different, and are usually the same. 3a and Z 3b Among them, C rings such as benzene ring, naphthalene ring, and biphenyl ring 6-12 An arene ring is preferred, and a C ring such as a benzene ring or a naphthalene ring is preferred. 6-10 In order to achieve both high optical properties (optical properties such as a high refractive index and a low absolute value of birefringence) and high heat resistance, a preferred arene ring is a polycyclic arene ring such as a fused polycyclic arene ring, and more preferably a fused polycyclic C 10-14 arene rings, particularly naphthalene rings.

[0100] In addition, the ring Z relative to the 9-position of the fluorene ring 3a and Z 3b The bonding position of is not particularly limited, and for example, 3a and Z 3b is a naphthalene ring, it is at either the 1-position or the 2-position, preferably the 2-position, and 3a and Z 3b When is a biphenyl ring, it is at the 2-, 3- or 4-position, preferably the 3-position.

[0101] Substituent R 4 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. 4 The alkyl group is, for example, a C methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, or the like. 1-12 Alkyl groups, preferably C 1-8 alkyl group, more preferably C 1-6 C alkyl groups, especially methyl groups 1-4 Examples of suitable alkyl groups include:

[0102] In addition, the group R 4 When the number of substitutions k is plural (2 or more), two or more groups R 4 The types of groups may be the same or different, and two or more groups R substituted on different benzene rings may be 4 The types of groups R may be the same or different. 4 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.

[0103] The number of substitutions r may be, for example, an integer of 0 to 6, and preferred ranges are integers of 0 to 4, 0 to 3, and 0 to 2, stepwise, as follows, and more preferably 0 or 1, particularly 0. In addition, in the two benzene rings constituting the fluorene ring, the group R 4 The number of substitutions in each of the above may be different from each other, but is preferably the same.

[0104] R 5a and R 5b Examples of the substituent represented by the formula (1) include R 2a and R 2b Examples of the substituents include the same groups as those exemplified as the substituents (such as a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, a nitro group, a cyano group, and a substituted amino group).

[0105] Preferred groups R 5a and R 5b is an alkyl group, an aryl group, an alkoxy group, and more preferably a linear or branched C group such as a methyl group. 1-6 C such as alkyl group and phenyl group 6-14 Linear or branched C such as aryl group, methoxy group 1-4 Among these substituents, alkyl groups and aryl groups are preferred, and in particular, linear or branched C groups such as methyl groups are preferred. 1-4 C such as alkyl group and phenyl group 6-10An aryl group is preferred. 5a or R 5b is an aryl group, the group R 5a or R 5b is the ring Z 3a or Z 3b may form the ring assembly arene ring together with

[0106] The numbers of substitutions s1 and s2 may each be an integer of 0 or more, and the number of substitutions s1 and s2 may each be an integer of 0 or more. 3a or Z 3b The number of substitutions s1 and s2 can be selected depending on the type of group R, and may be, for example, an integer of 0 to 8, preferably an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, and more preferably 0 or 1, particularly 0. When the number of substitutions s1 and s2 is an integer of 2 or more, the number of substitutions s1 and s2 can be selected depending on the type of group R 5a and R 5b The types may be the same or different.

[0107] When s1 and s2 are 1, the ring Z 3a and Z 3b is a benzene ring, a naphthalene ring or a biphenyl ring, a group R 5a and R 5b may be a methyl group, and when s1 and s2 are 2, the ring Z 3a and Z 3b is a benzene ring, and the group R 5a and R 5b may be a methyl group. 5a and R 5b The substitution position of is not particularly limited, and usually, 3a and Z 3b In this case, the substituent is often at least ortho to the ether bond (-O-) (the carbon atom adjacent to the bonding position of the ether bond).

[0108] Alkylene Group A 3a and A 3b Examples of the alkyl group include linear or branched C alkyl groups such as ethylene, propylene (1,2-propanediyl), trimethylene, 1,2-butanediyl, and tetramethylene groups. 2-6 alkylene groups, and the like, preferably linear or branched C 2-4A linear or branched alkylene group, more preferably an ethylene group or a propylene group 2-3 An alkylene group is preferred, with an ethylene group being particularly preferred.

[0109] The repeat numbers t1 and t2 may each be 0 or more, and may be selected from the range of integers from 0 to 15. To improve the esterification reaction, the repeat numbers t1 and t2 are 1 or more, preferably 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, and 1 to 2 in the following stepwise order, and particularly preferably 1. The repeat numbers t1 and t2 may be the same or different; when t1 and t2 are integers of 2 or more, the alkylene group A 3a and A 3b The types of may be the same or different. In this 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 are the same as the above-mentioned preferred ranges (range of integers). If the numbers of repetitions t1 and t2 are too large, the refractive index and heat resistance may decrease.

[0110] Ring Z 3a and Z 3b The group [-O-(A 3a O) t1 -] and [-O-(A 3b O) t2 The substitution position of the ether-containing group is not particularly limited, and may be any of the ring Z 3a and Z 3b When the ring Z is a benzene ring, it is often substituted at the 2-, 3- or 4-position, preferably the 3- or 4-position, particularly the 4-position, of the phenyl group bonded to the 9-position of the fluorene ring; 3a and Z 3b When the ring Z is a naphthalene ring, the 1st or 2nd position of the naphthalene ring is bonded to the 9th position of the fluorene ring (bonded in a 1-naphthyl or 2-naphthyl relationship), and the substituted ring is often substituted in a 1,5-position, 2,6-position, or particularly in a 2,6-position relationship relative to this bonding position. 3a and Z 3b is a biphenyl ring (or ring Z 3a and Z 3bis a benzene ring, s1 and s2 are 1, R 5a and R 5b is a phenyl group), the 3- or 4-position of the biphenyl ring may be bonded to the 9-position of the fluorene, and when the 3-position of the biphenyl ring is bonded to the 9-position of the fluorene, the substitution position of the ether-containing group may be the 6- or 4'-position of the biphenyl ring, particularly the 6-position.

[0111] Examples of the first aromatic diol component include 9,9-bis(hydroxyaryl)fluorenes in which t1 and t2 are 0 in the formula (3); and 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes in which t1 and t2 are 1 or more, for example, 1 to 10.

[0112] The first aromatic diol component may preferably contain a compound (aromatic diol component) represented by the following formula (3-1) or (3-2).

[0113] [ka]

[0114] (In the formula, R 4 is linear or branched chain C 1-4 Alkyl group, C 6-10 represents an aryl group, r represents 0 or 1, and R 5a and R 5b is independently C 1-4 Alkyl group, C 1-4 Alkoxy group, C 6-10 represents an aryl group, s1 and s2 independently represent an integer of 0 to 2, and A 3a and A 3b are independently linear or branched chain C 1-4 represents an alkylene group, and t1 and t2 independently represent an integer of 0 to 10.

[0115] Examples of the 9,9-bis(hydroxyphenyl)fluorenes corresponding to the formula (3-1) include 9,9-bis(hydroxyphenyl)fluorenes such as (3-1a) 9,9-bis(4-hydroxyphenyl)fluorene; (3-1b) 9,9-bis(alkyl-hydroxyphenyl)fluorenes, specifically, 9,9-bis[(mono- or di-)C] such as 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-isopropylphenyl)fluorene, and 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene. 1-4 alkyl-hydroxyphenyl]fluorene, etc.; (3-1c) 9,9-bis(aryl-hydroxyphenyl)fluorene, specifically, 9,9-bis(C 6-10 aryl-hydroxyphenyl)fluorene.

[0116] Furthermore, examples of the 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorenes corresponding to formula (3-1) include alkylene oxide adducts of the 9,9-bis(hydroxyaryl)fluorenes, for example, (3-1d) 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorene, specifically, 9,9-bis[hydroxy(mono- to deca)C such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-(2-hydroxyethoxy)ethoxy)phenyl]fluorene, and 9,9-bis[4-(2-hydroxypropoxy)phenyl]fluorene. 2-4 alkoxy-phenyl]fluorene, etc.; (3-1e) 9,9-bis[alkyl-hydroxy(poly)alkoxyphenyl]fluorenes, specifically, 9,9-bis[(mono- or di-)C such as 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-(2-hydroxyethoxy)ethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene, and 9,9-bis[4-(2-hydroxypropoxy)-3-methylphenyl]fluorene. 1-4 Alkyl-hydroxy (mono or deca)C 2-4 alkoxy-phenyl]fluorene, etc.; (3-1f) 9,9-bis[aryl-hydroxy(poly)alkoxyphenyl]fluorenes, specifically, 9,9-bis[C such as 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-bis[4-(2-(2-hydroxyethoxy)ethoxy)-3-phenylphenyl]fluorene, and 9,9-bis(4-(2-hydroxypropoxy)-3-phenylphenyl)fluorene. 6-10 Aryl-hydroxy(mono or deca)C 2-4 Examples include alkoxy-phenyl]fluorene.

[0117] Examples of the 9,9-bis(hydroxynaphthyl)fluorenes corresponding to the formula (3-2) include (3-2a) 9,9-bis(hydroxynaphthyl)fluorenes such as 9,9-bis(6-hydroxy-2-naphthyl)fluorene and 9,9-bis(5-hydroxy-1-naphthyl)fluorene; (3-2b) 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorenes 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, 9,9-bis[6-(2-(2-hydroxyethoxy)ethoxy)-2-naphthyl]fluorene, and 9,9-bis[6-(2-hydroxypropoxy)-2-naphthyl]fluorene. 2-4 Alkoxy-naphthyl]fluorene and the like.

[0118] The first aromatic diol component can be used alone or in combination of two or more. A preferred first aromatic diol component is 9,9-bis[hydroxy(mono- to hexa)C 2-4 Alkoxy C 6-12 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes such as 9,9-bis[hydroxy(mono or di)aryl]fluorene; more preferably 9,9-bis[hydroxy(mono or di)aryl]fluorene; 2-4 Alkoxy-C 6-12aryl]fluorene; more preferably 9,9-bis[hydroxy C such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, and 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene. 2-3 Alkoxy-C 6-12 Among them, 9,9-bis[hydroxy C aryl]fluorene such as 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene is preferred because it can provide high heat resistance while maintaining a high refractive index and can reduce the absolute value of birefringence. 2-3 Alkoxynaphthyl]fluorene is preferred.

[0119] Second Aromatic Diol Component The aromatic diol component may contain, in addition to the first aromatic diol component, a second aromatic diol component having a fused polycyclic arene ring.

[0120] The second aromatic diol component may be 2,6-naphthalenediol, 1,5-bis(2-hydroxyethoxy)naphthalene, 2,6-bis(2-hydroxyethoxy)naphthalene, etc., but may also contain a compound represented by the following formula (4): A thermoplastic resin containing units of such a second aromatic diol component appears to be able to impart a high refractive index and a low Abbe number while suppressing an excessive increase in glass transition temperature and an increase in birefringence.

[0121] [ka]

[0122] (In the formula, A 4 is a direct bond (single bond) or a linear or branched alkylene group, A 5a and A 5bare independently a linear or branched alkylene group, u1 and u2 are independently an integer of 0 or more, R 6a and R 6b are independently a substituent, and v1 and v2 are independently an integer of 0 to 6).

[0123] A 4 Examples of the alkylene group represented by the formula (I) include a straight-chain or branched C alkylene group such as a methylene group, an ethylene group, a propylene group, a trimethylene group, a 2,2-propanediyl group, and a tetramethylene group. 1-4 In terms of optical properties such as high refractive index, low Abbe number, and low birefringence, A 4 is a direct bond or C 1-2 An alkylene group is preferred, and a direct bond is particularly preferred.

[0124] Base A 5a and A 5b The alkylene group represented by the formula (3) includes the alkylene group A exemplified in the formula (3), including preferred embodiments. 3a and A 3b The repeating numbers u1 and u2, including preferred embodiments, are the same as the repeating numbers t1 and t2 exemplified in the formula (3). u1 and u2 may be the same or different, and when u1 or u2 is 2 or more, the alkylene group A 5a or A 5b The types of may be the same or different. 5a O) u1 -] and [-O(A 5b O) u2 -] is substituted at the 1,1'-position of the naphthalene ring. 4 The position may be any of the 2- to 4-positions and the 2'- to 4'-positions relative to the alkyl group, but the 2,2'-positions are preferred in terms of reducing birefringence.

[0125] R 6a and R 6b Examples of the substituent represented by the formula (1) include R 2a and R 2b Preferred groups R 6a and R 6bis a halogen atom such as a bromine atom. 6a and R 6b The substitution positions of A are not particularly limited, and A bonded to the 1,1' positions of the two naphthalene rings 4 In contrast, the positions are often 3 to 8 and / or 3' to 8'.

[0126] The substitution numbers v1 and v2 are each an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, particularly preferably 0. When v1 and v2 are an integer of 2 or more, the substituent R 6a and R 6b The types may be the same or different.

[0127] Representative second aromatic diol components represented by formula (4) include: A 4 is a direct bond. Examples of dihydroxy-1,1'-binaphthalenes include dihydroxy-1,1'-binaphthalenes such as 2,2'-dihydroxy-1,1'-binaphthalene; and bis[hydroxy(poly)alkoxy]-1,1'-binaphthalene. Examples of bis[hydroxy(poly)alkoxy]-1,1'-binaphthalenes include 2,2'-bis[hydroxy(mono- to deca)C such as 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene, 2,2'-bis(2-hydroxypropoxy)-1,1'-binaphthalene, and 2,2'-bis[2-(2-hydroxyethoxy)ethoxy]-1,1'-binaphthalene. 2-4 Alkoxy]-1,1'-binaphthalene and the like.

[0128] These second aromatic diol components can be used alone or in combination of two or more. Among the second aromatic diol components, 2,2'-bis[hydroxy(mono- to hexa)C 2-4 Alkoxy]-1,1'-binaphthalene, preferably 2,2'-bis[hydroxy(mono or di)C 2-42,2'-bis[hydroxy C alkoxy]-1,1'-binaphthalene, in particular 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene 2-3 Alkoxy]-1,1'-binaphthalene is preferred.

[0129] The molar ratio of the first aromatic diol component to the second aromatic diol component (former / latter) can be selected from the range of 50 / 50 to 100 / 0, and is preferably in the following stepwise manner: 55 / 45 to 100 / 0, 60 / 40 to 100 / 0, 65 / 35 to 100 / 0, 70 / 30 to 100 / 0, preferably 75 / 25 to 100 / 0, particularly 80 / 20 to 100 / 0.

[0130] Third Aromatic Diol Component The aromatic diol component may contain a third aromatic diol component containing a monocyclic arene ring. Examples of such a third aromatic diol component include dihydroxyarenes such as hydroquinone and resorcinol; aromatic aliphatic diols such as xylylenediol (benzenedimethanol); bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol C, bisphenol G, and bisphenol S; and biphenols such as p,p'-biphenol. The C of these diol components may be 2-4 Also included are alkylene oxide (corresponding alkylene carbonate or haloalkanol) adducts. Preferred alkylene oxide adducts include C alkylene oxide adducts such as ethylene oxide adducts and propylene oxide adducts. 2-3 Examples include alkylene oxide adducts, and the number of moles of addition may be 2 to 10 moles per mole of the diol component.

[0131] The molar ratio of the third aromatic diol component to the first aromatic diol component (former / latter) can be selected within the range of 70 / 30 to 100 / 0, preferably 80 / 20 to 100 / 0, more preferably 85 / 15 to 100 / 0, and particularly preferably 90 / 10 to 100 / 0.

[0132] The proportion of the first aromatic diol component relative to the total aromatic diol components may be selected from the range of 50 to 100 mol%, as long as it is contained as the main component, and the proportion of the first aromatic diol component relative to the total aromatic diol components may be selected in the following stepwise manner, preferably 55 to 100 mol%, 60 to 100 mol%, 65 to 100 mol%, 70 to 100 mol%, more preferably 75 to 100 mol%, and particularly preferably 80 to 100 mol%.

[0133] [Alicyclic diol component] Alicyclic diol components include cycloalkanediols such as cyclohexanediol; bis(hydroxyalkyl)cycloalkanes such as cyclohexanedimethanol; hydrogenated products of the above-mentioned aromatic diols such as hydrogenated bisphenol A; and alkylene oxide (alkylene carbonate or haloalkanol) adducts of these diol components.

[0134] The alicyclic diol component may be used alone or in combination of two or more. The proportion of the alicyclic diol component may be selected from the range of 0 to 40 mol % relative to the total diol components, and is preferably 30 mol % or less, 20 mol % or less, 10 mol % or less, and 5 mol % or less in the following stepwise manner, and the alicyclic diol component may not be contained.

[0135] [Hydroxycarboxylic acid component] The hydroxycarboxylic acid component may contain an aromatic hydroxycarboxylic acid component, an alicyclic hydroxycarboxylic acid component, and / or an aliphatic hydroxycarboxylic acid component, as necessary. The hydroxycarboxylic acid component preferably contains an aromatic hydroxycarboxylic acid component in order to improve the refractive index and heat resistance. The aliphatic hydroxycarboxylic acid component may contain a branched aliphatic hydroxycarboxylic acid component (first aliphatic hydroxycarboxylic acid component) having a specific branched structure, or may contain a second aliphatic hydroxycarboxylic acid component not having the branched structure.

[0136] [Aromatic hydroxycarboxylic acid component] Aromatic hydroxycarboxylic acid components include hydroxy C such as p-hydroxybenzoic acid, 1,5-hydroxynaphthoic acid, and 2,6-hydroxynaphthoic acid. 6-10 Examples include arene-carboxylic acids.

[0137] The aromatic hydroxycarboxylic acid component may be used alone or in combination of two or more. When an aromatic hydroxycarboxylic acid component is contained, the proportion of the aromatic hydroxycarboxylic acid component may be selected from the range of 0 to 40 mol % based on the total hydroxycarboxylic acid component, and preferably is 30 mol % or less, 20 mol % or less, 10 mol % or less, and 5 mol % or less in the following stepwise manner. The aromatic hydroxycarboxylic acid component may not be contained.

[0138] [Alicyclic hydroxycarboxylic acid component] Alicyclic hydroxycarboxylic acid components include hydroxy C such as 4-hydroxycyclohexanecarboxylic acid. 3-10 Examples include cycloalkane-carboxylic acids.

[0139] The alicyclic hydroxycarboxylic acid component may be used alone or in combination of two or more. When an alicyclic hydroxycarboxylic acid component is contained, the proportion of the alicyclic hydroxycarboxylic acid component may be selected from the range of 0 to 40 mol % based on the total hydroxycarboxylic acid components, and preferably is 30 mol % or less, 20 mol % or less, 10 mol % or less, and 5 mol % or less in the following stepwise manner, and the alicyclic hydroxycarboxylic acid component may not be contained.

[0140] [Aliphatic components] Generally, as the density of aromatic component units in the structural units of a thermoplastic resin increases, the refractive index and heat resistance tend to increase. Furthermore, as the refractive index and heat resistance increase, birefringence tends to increase, melt viscosity increases, and melt fluidity tends to decrease. That is, in aromatic thermoplastic resins into which aromatic component units have been introduced, a high refractive index and a low birefringence are usually in a trade-off relationship, and the relationship between heat resistance and moldability is also in a trade-off relationship. Therefore, it is difficult to increase the refractive index to reduce birefringence and improve melt viscosity or melt fluidity while maintaining high heat resistance. However, by introducing branched aliphatic component units having a branched alkyl or alkenyl group of a predetermined length into the structural units of a thermoplastic resin, birefringence can be reduced or adjusted while maintaining a high refractive index, and moldability can be improved while maintaining high heat resistance.

[0141] Therefore, in the present invention, in an aromatic thermoplastic resin into which at least units of the aromatic components (aromatic dicarboxylic acid components and aromatic diol components) and units of an aliphatic component (at least one selected from an aliphatic dicarboxylic acid component, an aliphatic diol component, and an aliphatic hydroxycarboxylic acid component) have been introduced, the units of the aliphatic components contain one or more branched chains, and at least one of the branched chains contains units of a branched aliphatic component (branched aliphatic dicarboxylic acid, branched aliphatic diol, and / or aliphatic hydroxycarboxylic acid component) having a predetermined linear or branched alkyl chain or an alkenyl group, preferably a predetermined linear or branched alkyl chain.

[0142] In this specification and claims, a branched aliphatic component is a component containing at least a branched alkane chain (alkyl chain) or alkene chain (alkenyl chain) unit (a component having a branched alkane chain or alkene chain), and preferably does not contain a unit such as a cyclic aliphatic ring, a saturated hydrocarbon ring (cycloalkane ring), or an unsaturated hydrocarbon ring (cycloalkene ring).

[0143] The branched aliphatic component (a component having a branched alkane chain or alkene chain) may have an alkyl group or alkenyl group having 1 or 2 carbon atoms as a branched chain, but preferably has an alkyl group having 3 or more carbon atoms (a linear or branched C 3-30 Alkyl group) or alkenyl group (linear or branched C 3-30 alkenyl group), and the branched alkyl group (or alkyl chain) is C 3-24 Alkyl groups, preferably C 3-22 alkyl group, more preferably C 4-22 Alkyl groups, more preferably C 5-20 Alkyl groups, particularly preferably C 8-18 It may be an alkyl group.

[0144] In addition, in the branched aliphatic dicarboxylic acid component, branched aliphatic diol component, and branched aliphatic hydroxycarboxylic acid component containing multiple branched chains, the alkyl group (or alkyl chain) of the branched chain is an alkyl group having an upper limit of the carbon number smaller than that of the branched chain, for example, C 3-20 Alkyl groups, preferably C 3-18 alkyl group, more preferably C 3-15 Alkyl groups, more preferably C 3-10 Alkyl groups, most preferably C 3-8 The use of a branched aliphatic component having an alkyl chain with an upper limit of the number of carbon atoms smaller than that of the branched chain is effective in maintaining a high refractive index and glass transition temperature.

[0145] Examples of branched alkyl groups include linear or branched C alkyl groups such as n-propyl, butyl, i-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, and icosyl groups. 3-24 Examples include alkyl groups, and straight or branched C 3-20 Alkyl groups are preferred, especially C 4-20The branched alkenyl group is preferably an alkenyl group containing one or two unsaturated double bonds, particularly one unsaturated double bond, such as a linear or branched C 1 group, such as a hexenyl group, an octenyl group, a decenyl group, or a dodecenyl group. 6-24 Alkenyl groups and the like can be exemplified, and linear or branched C 8-20 Alkenyl groups, especially linear or branched C such as dodecenyl groups 10-18 Alkenyl groups are preferred.

[0146] The branched chain is preferably a linear or branched alkyl group or an alkenyl group. The branched linear or branched alkyl group is preferably a C 3-24 Alkyl groups, preferably C 4-24 alkyl group, more preferably C 6-22 Alkyl groups, more preferably C 8-20 It may be an alkyl group, particularly C 8-22 Alkyl groups, especially C 10-20 In the branched aliphatic diol component (branched alkanediol or branched alkenediol component), C 3-18 Alkyl groups, preferably C 4-18 Alkyl group, C 3-16 Alkyl group, C 6-16 Alkyl group, C 3-12 Alkyl group, C 8-12 Alkyl groups, especially C 3-10 In the branched aliphatic hydroxycarboxylic acid component (branched hydroxyalkanecarboxylic acid or branched hydroxyalkenecarboxylic acid component), C 3-18 Alkyl groups are preferred, and the following stepwise 4-18 Alkyl group, C 3-16 Alkyl group, C 6-16 Alkyl group, C 3-12 Alkyl group, C 8-12 Alkyl group, C 3-10The branched alkyl group or alkenyl group may be an alkyl group; or an alkenyl group corresponding to such an alkyl group. It is expected that a decrease in the number of carbon atoms in the branched alkyl group or alkenyl group will increase the birefringence of the aromatic thermoplastic resin and reduce its moldability. However, in a branched aliphatic component, particularly a branched aliphatic diol component (branched alkanediol component), even if the number of carbon atoms in the branched linear or branched alkyl group is 3 (propyl group, particularly trimethylene group), particularly 4 (butyl group), this is effective in improving the optical and thermal properties of the thermoplastic resin and reducing the melt viscosity and moldability. Therefore, in a branched aliphatic component, particularly a branched aliphatic diol component, the lower limit of the number of carbon atoms in the branched linear or branched alkyl group may be 3, particularly 4, and such an alkyl group is preferably C 3-22 Alkyl groups, preferably C 4-18 alkyl group, more preferably C 4-16 Alkyl groups, more preferably C 4-12 In particular, compared with the branched aliphatic dicarboxylic acid component, the branched aliphatic diol component is useful for preparing a thermoplastic resin having a small absolute value of birefringence without significantly decreasing the refractive index and glass transition temperature.

[0147] In the branched aliphatic dicarboxylic acid component, the branched aliphatic diol component, and the branched aliphatic hydroxycarboxylic acid component, the two reactive groups (carboxyl group and / or hydroxyl group) may be bonded to a primary, secondary, or tertiary carbon atom, respectively. However, the two reactive groups may be bonded to a primary carbon atom, a secondary carbon atom, or a tertiary carbon atom, preferably a primary carbon atom and a secondary carbon atom, respectively. That is, the carboxyl group (in the acid anhydride, the ring-opened carboxyl group) or the hydroxyl group may be located on an alkylene chain that may contain a heteroatom such as a nitrogen atom (substituted on a secondary carbon atom) or at the terminal (substituted on a primary carbon atom). Between the substitution position of the carboxyl group or the hydroxyl group and the substitution position of the alkyl group as a branched chain, an alkylene group having 1 to 10 atoms that may contain a heteroatom, or a monocyclic or polycyclic hydrocarbon ring may be interposed. The monocyclic or polycyclic hydrocarbon ring may be a cyclohexene ring, a benzene ring, an octahydronaphthalene ring, or the like. Between the substitution position of the carboxyl group or hydroxyl group and the substitution position of the alkyl group as a branched chain, an alkylene group having 1 to 12 carbon atoms, preferably 1 to 10, more preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 to 3 carbon atoms, and especially preferably 1 or 2 alkylene groups (methylene or ethylene groups) is present. That is, in the branched aliphatic dicarboxylic acid component, branched aliphatic diol component, and branched aliphatic hydroxycarboxylic acid component, the alkyl or alkenyl group as a branched chain may be substituted at the 1:10, 1:8, or 1:6 positions, preferably at the 1:5, more preferably at the 1:4, particularly at the 1:3 or 1:2 positions, especially at the 1:2 position, based on the substitution position of the carboxyl or hydroxyl group. When the length (distance) of the alkylene chain or carbon chain between the carboxyl or hydroxyl group and the alkyl or alkenyl group as a branched chain increases, the refractive index and glass transition temperature of the thermoplastic resin tend to decrease.

[0148] The branched aliphatic component may have at least one branched alkyl group (branched linear or branched alkyl chain) or alkenyl group in one molecule, and may have a plurality of branched alkyl groups (branched linear or branched alkyl chain) or alkenyl groups in one molecule. The number of branched alkyl groups or alkenyl groups is 1 to 3, preferably 1 or 2, and particularly 1.

[0149] The branched aliphatic component having a plurality of branched chains (branched alkyl groups or alkenyl groups) in one molecule is a branched aliphatic component having a plurality of the first branched chains, i.e., alkyl groups having 3 or more carbon atoms (linear or branched C 3-30 Alkyl group) or alkenyl group (linear or branched C 3-30 alkenyl group); and may include at least one first branched chain and at least one second branched chain; preferably one first branched chain and one second branched chain.

[0150] Examples of the second branched chain (branched alkyl group or alkenyl group) include a methyl group, an ethyl group, and a vinyl group each having 1 or 2 carbon atoms.

[0151] In a branched aliphatic component having multiple branched chains, the total number of carbon atoms in the multiple branched chains may be, for example, 4 to 20, preferably 4 to 18, further preferably 5 to 15, and even more preferably 5 to 12.

[0152] Furthermore, the multiple branched chains (particularly two branched chains) may be branched from the same carbon atom on the chain (straight chain portion or main chain) connecting the carbon atoms to which the two reactive groups (carboxyl groups and / or hydroxyl groups) are bonded, or may be branched from different carbon atoms (for example, adjacent carbon atoms). When the multiple branched chains are branched from different carbon atoms, an alkylene group having 1 to 6 carbon atoms, preferably 1 to 4, more preferably 1 to 3 carbon atoms, and especially one or two alkylene groups (methylene groups or ethylene groups) may be present between the substitution positions of the multiple branched chains.

[0153] [Aliphatic dicarboxylic acid component] Aliphatic dicarboxylic acid components (alkanedicarboxylic acid or alkenedicarboxylic acid components) are roughly classified into aliphatic dicarboxylic acid components (first aliphatic dicarboxylic acid components) having at least one branched chain (or branched structure) of the specified chain length, and second aliphatic dicarboxylic acid components not having the branched chain (or branched structure).

[0154] The first aliphatic dicarboxylic acid component may have, as a branched chain, the linear or branched alkyl group, for example, C 3-24 Alkyl groups, preferably C 4-24 alkyl group, more preferably C 6-22 Alkyl groups, more preferably C 8-20 It is sufficient if the dicarboxylic acid has an alkyl group or an alkenyl group, and examples thereof include branched alkylene-dicarboxylic acids (or branched alkane-dicarboxylic acids), branched alkenylene-dicarboxylic acids, and dimer acids. Examples of branched alkylene-dicarboxylic acids (or branched alkane-dicarboxylic acids) include branched C 6-32 Alkylene-dicarboxylic acids, preferably branched C 8-26 Alkylene-dicarboxylic acids, more preferably branched C 10-24 Alkylene-dicarboxylic acids, especially C 10-20 Examples of branched chain alkenylene dicarboxylic acids include branched chain C 6-32 Alkenylene-dicarboxylic acids, preferably branched C 8-26 Alkenylene-dicarboxylic acids, more preferably branched C 10-24 Alkenylene-dicarboxylic acids, especially C 10-20 Examples include alkenylene dicarboxylic acids.

[0155] Dimer acids include C oleic acid and linoleic acid. 16-20 Examples include dimers of unsaturated fatty acids, particularly dicarboxylic acids having 36 carbon atoms. The dimer acid may be an acyclic, monocyclic, polycyclic, or aromatic dimer acid, as represented by the following formula: The dimer acid may be used alone or as a mixture thereof.

[0156] [ka]

[0157] Representative first aliphatic dicarboxylic acid components include C succinic anhydrides such as octyl succinic anhydride, decyl succinic anhydride, dodecyl succinic anhydride, tridecyl succinic anhydride, tetradecyl succinic anhydride, pentadecyl succinic anhydride, hexadecyl succinic anhydride, heptadecyl succinic anhydride, octadecyl succinic anhydride, and isooctadecyl succinic anhydride. 10-20 Alkylenedicarboxylic acid anhydrides; C such as octenylsuccinic anhydride, decenylsuccinic anhydride, and dodecenylsuccinic anhydride 10-20 Examples include alkenylene-dicarboxylic acid anhydrides; and compounds corresponding to these compounds which further have at least one first branched chain and / or second branched chain.

[0158] These first aliphatic dicarboxylic acid components can be used alone or in combination of two or more. A preferred first aliphatic dicarboxylic acid component is one having C 3-22 C with alkyl group 5-24 Alkylene-dicarboxylic acids, more preferably C 8-22 C with alkyl group 10-24 Alkylene dicarboxylic acids, especially C as branched chains 10-20 C with alkyl group 12-22 Examples include alkylene-dicarboxylic acids.

[0159] Examples of the second aliphatic dicarboxylic acid component include alkanedicarboxylic acids, specifically, C carboxylic acids such as succinic acid, adipic acid, sebacic acid, and decanedicarboxylic acid. 2-12 Alkane dicarboxylic acids, etc.; unsaturated aliphatic dicarboxylic acids, specifically C such as maleic acid, fumaric acid, and itaconic acid 2-10 The second aliphatic dicarboxylic acid component may be a single component or a combination of two or more components. A preferred second aliphatic dicarboxylic acid component is C 2-10 Alkane-dicarboxylic acids, more preferably C2-8 Alkane-dicarboxylic acids, especially C such as adipic acid 2-6 It is an alkane-dicarboxylic acid.

[0160] In the aromatic thermoplastic resin, the ratio (molar ratio) of the units of the first aliphatic dicarboxylic acid component to the units of the second aliphatic dicarboxylic acid component (former / latter) may be 60 / 40 to 100 / 0, preferably 70 / 30 to 100 / 0, and more preferably 80 / 20 to 100 / 0.

[0161] [Aliphatic diol component] Aliphatic diol components (alkanediol or alkenediol components) can be roughly divided into branched aliphatic diol components (first aliphatic diol components) having a branched chain (or branched structure) of at least a predetermined chain length, and second aliphatic diol components not having the branched structure.

[0162] The first aliphatic diol component (branched aliphatic diol component) may have the linear or branched alkyl group as a branch chain. The branched aliphatic diol component may be, for example, a branched C 5-32 Alkanediol or branched chain C 5-32 Examples of alkylene diols include branched chain C alkylene diols, preferably branched chain C alkylene diols, 6-32 Alkylenediol, branched C 8-26 Alkylenediol, branched C 10-24 Alkylenediol, C 10-20 Examples include alkylene diols; branched chain C 6-20 Alkylene diols, preferably branched C 6-18 Alkanediols, more preferably branched C 6-16 Alkanediols, especially branched C 6-14 Alkanediols, especially branched C 6-12 Examples include alkylene diols.

[0163] A typical first aliphatic diol component is one having C as a branched chain. 3-22 C with alkyl group 5-20 Alkanediol or C 5-20Alkylene diols, for example, 1,2-C alkylene diols such as 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, 1,2-decanediol, 1,2-dodecanediol, and 1,2-isohexadecanediol 5-16 Alkanediols: 1,3-C such as 2-ethyl-1,3-hexanediol and 2-ethyl-2-butyl-1,3-propanediol 5-18 Among these first aliphatic diol components, C 1 having one or two branched chains and an alkyl group having a total carbon number of 3 to 16 in the branched chains is preferred. 5-18 Alkanediols are preferred, for example 1,2-C 6-16 Alkanediols, 1,3-C 6-16 Alkanediols and the like.

[0164] The first aliphatic diol component may be a diol having multiple alkyl groups as branched chains in one molecule. Examples of such diol components include comb-shaped diols having branched alkyl groups, such as N,N-di-(3-(2-ethylhexyloxy)-2-hydroxypropyl)-2-ethylhexylamine.

[0165] These first aliphatic diol components can be used alone or in combination of two or more. A preferred first aliphatic diol component is one having C 3-14 Alkyl groups, preferably C 4-14 C with alkyl group 6-18 Alkylene diols, more preferably C 3-12 Alkyl groups, more preferably C 4-12 C with alkyl group 6-14 Alkylene diols, especially C as branched chains 3-10 Alkyl groups, preferably C 4-10 C with alkyl group 6-12 An example of the first aliphatic diol component is alkylene diol. In addition, the preferred first aliphatic diol component may have a first branched chain and a second branched chain as branched chains, and the first branched chain is C 3-10 C having an alkyl group and a second branched chain 6-12Examples include alkylene diols.

[0166] Examples of the second aliphatic diol component include alkanediols (or alkylene glycols), polyalkanediols (or polyalkylene glycols), etc. Examples of the alkanediol include linear or branched alkanediols, such as ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, tetramethylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, and 1,10-decanediol. 2-12 Examples of polyalkylene glycols include linear or branched alkylene glycols, for example, di- to tetra-C alkylene glycols such as diethylene glycol, dipropylene glycol, and triethylene glycol. 2-6 Alkylene glycol, preferably di- to tetra-C 2-4 Alkylene glycols are included.

[0167] These second aliphatic diol components can be used alone or in combination of two or more. A preferred second aliphatic diol component is a linear or branched alkylene glycol, preferably C 2-6 Alkylene glycol, more preferably C 2-4 Alkylene glycols, especially ethylene glycol and propylene glycol, 2-3 Alkylene glycols, especially ethylene glycol.

[0168] In the aromatic thermoplastic resin, the ratio (molar ratio) of the units of the first aliphatic diol component to the units of the second aliphatic diol component (former / latter) can be selected within the range of 20 / 80 to 100 / 0, preferably 25 / 75 to 95 / 5, more preferably 30 / 70 to 90 / 10, and particularly preferably 35 / 65 to 85 / 15.

[0169] [Aliphatic hydroxycarboxylic acid component] Aliphatic hydroxycarboxylic acid components (hydroxyalkanecarboxylic acid or hydroxyalkenecarboxylic acid components) can be broadly divided into branched aliphatic hydroxycarboxylic acid components (first aliphatic hydroxycarboxylic acid components) having a branched chain (or branched structure) of at least a certain chain length, and second aliphatic hydroxycarboxylic acid components not having the branched structure.

[0170] The first aliphatic hydroxycarboxylic acid component (branched aliphatic hydroxycarboxylic acid component) may have the linear or branched alkyl or alkenyl group as a branched chain, and the branched hydroxy C 4-32 Alkane-carboxylic acids (e.g., branched hydroxy C 4-30 The first aliphatic hydroxycarboxylic acid component may be a branched hydroxy C 4-28 Alkane-carboxylic acids, more preferably branched hydroxy C 5-26 Alkane-carboxylic acids, especially branched hydroxy C 6-24 Examples include alkane-carboxylic acids.

[0171] Representative first aliphatic hydroxycarboxylic acid components include hydroxy C such as 10-hydroxylauric acid, 2-hydroxymyristic acid, 3-hydroxymyristic acid, 4-hydroxypalmitic acid (4-hydroxyhexadecanoic acid), 7-hydroxypalmitic acid, 10-hydroxystearic acid (10-hydroxyoctadecanoic acid), and 12-hydroxystearic acid. 4-22 Examples include alkane-carboxylic acids.

[0172] These first aliphatic hydroxycarboxylic acid components can be used alone or in combination of two or more. A preferred first aliphatic hydroxycarboxylic acid component is one having C 3-14 Alkyl groups, preferably C 4-14 Hydroxy C with alkyl group 4-32 Alkane-carboxylic acids (or the hydroxy C corresponding to these alkanes) 4-32Alkene-carboxylic acid), more preferably C as branched chain 3-12 Hydroxy C with alkyl group 4-28 Alkane-carboxylic acids, especially C as branched chains 3-10 Hydroxy C with alkyl group 4-22 Examples include alkane-carboxylic acids.

[0173] Examples of the second aliphatic hydroxycarboxylic acid component include hydroxy C such as glycolic acid, 2-hydroxypropanoic acid (lactic acid), 2-hydroxybutanoic acid (2-hydroxybutyric acid), 3-hydroxybutanoic acid (3-hydroxybutyric acid), 4-hydroxybutanoic acid, 2-hydroxypentanoic acid (2-hydroxyvaleric acid), 4-hydroxypentanoic acid, 5-hydroxypentanoic acid, 2-hydroxy-2-methyl-pentanoic acid, 4-hydroxyhexanoic acid, 6-hydroxyhexanoic acid, 6-hydroxyheptanoic acid, 7-hydroxyheptanoic acid, 8-hydroxyoctanoic acid, 9-hydroxynonanoic acid, and 10-hydroxydecanoic acid. 1-12 Examples include alkane-carboxylic acids; or lactone components, acid halides, or lower alkyl esters equivalent to these hydroxyalkanecarboxylic acids.

[0174] These second aliphatic hydroxycarboxylic acid components can be used alone or in combination of two or more. Preferred second aliphatic hydroxycarboxylic acid components are hydroxy C 2-8 Alkane-carboxylic acids, preferably hydroxy C 2-6 It is an alkane-carboxylic acid.

[0175] In the aromatic thermoplastic resin, the ratio (molar ratio) of the units of the first aliphatic hydroxycarboxylic acid component to the units of the second aliphatic hydroxycarboxylic acid component (former / latter) can be selected within the range of 20 / 80 to 100 / 0, preferably 25 / 75 to 95 / 5, more preferably 30 / 70 to 90 / 10, and particularly preferably 35 / 65 to 85 / 15.

[0176] The branched aliphatic component is at least one selected from the group consisting of a first aliphatic dicarboxylic acid component, a first aliphatic diol component, and a first hydroxycarboxylic acid component, and preferably a branched C 6-20 Alkanediols and branched C 10-20 Alkylene-dicarboxylic acid (or branched chain C 10-20 alkane-dicarboxylic acid), and at least one branched chain is selected from linear or branched C 3-18 Alkyl groups, preferably C 4-18 It may be at least one type having an alkyl group, or both components (first aliphatic dicarboxylic acid component and first aliphatic diol component) may be used in combination. In the aromatic thermoplastic resin, the ratio of the units of the first aliphatic dicarboxylic acid component to the units of the first aliphatic diol component (molar ratio) can be selected from a wide range of from 100 / 0 to 0 / 100, preferably from 90 / 10 to 0 / 100, and more preferably from 70 / 30 to 5 / 95.

[0177] Furthermore, when a first hydroxycarboxylic acid component is contained as the branched aliphatic component, the ratio of the sum of the units of the first aliphatic dicarboxylic acid component and the units of the first aliphatic diol component to the first hydroxycarboxylic acid component (former / latter) (molar ratio) can be selected from a wide range of 99 / 1 to 0 / 100, preferably 90 / 10 to 0 / 100, and more preferably 70 / 30 to 5 / 95.

[0178] In the aromatic thermoplastic resin, the ratio of all branched aliphatic component units to all units of the dicarboxylic acid component, diol component, and hydroxycarboxylic acid component is 1 to 35 mol%, preferably 2 to 30 mol%, more preferably 3 to 25 mol%, and particularly 4 to 20 mol%, and may be 3 to 20 mol%, particularly 5 to 15 mol%. Introducing branched aliphatic component units can significantly improve the melt viscosity and reduce or adjust the absolute value of birefringence while maintaining the heat resistance and optical properties of the aromatic thermoplastic resin. If the proportion of branched aliphatic components is too low, the melt viscosity or moldability of the aromatic thermoplastic resin will not be significantly improved. If the proportion is too high, the melt viscosity will decrease, but the refractive index and glass transition temperature will tend to decrease slightly. The ratio of branched aliphatic dicarboxylic acid units to all units of the dicarboxylic acid component, the ratio of branched aliphatic diol units to all units of the diol component, and the ratio of branched aliphatic hydroxycarboxylic acid units to all units of the hydroxycarboxylic acid component may each be 0 to 30 mol%, preferably 2 to 25 mol%, more preferably 3 to 20 mol%, particularly 4 to 15 mol%, and is also effective when it is 3 to 10 mol%, particularly 4 to 8 mol%.

[0179] The aromatic thermoplastic resin may be a resin obtained by reacting at least the dicarboxylic acid component and the diol component, such as a polyester resin or a polyester carbonate resin. A preferred aromatic thermoplastic resin is a polyester resin that has a high refractive index and glass transition temperature (or heat resistance) and is useful for reducing the absolute value of birefringence and melt viscosity.

[0180] Although the aromatic thermoplastic resin does not necessarily contain a carbonate unit, a polyester carbonate resin may be formed by introducing a carbonate unit together with a diol unit. In this specification and claims, the term "carbonate unit" refers to a structural unit derived from a carbonate bond-forming component, i.e., a carbonyl group [—C(═O)—], which forms a carbonate bond together with the terminal oxygen atoms of the two diol component units bonded adjacent to this carbonyl group. Therefore, the carbonate bond-forming component may be any compound capable of forming a carbonate bond upon reaction with two diol components. Representative carbonate bond-forming components include, for example, phosgenes such as phosgene and triphosgene, and carbonate diesters such as diphenyl carbonate. From the standpoint of safety, carbonate diesters such as diphenyl carbonate are preferred.

[0181] The ratio of dicarboxylic acid component units to diol component units in the aromatic polyester resin and the ratio of the total amount of dicarboxylic acid units and carbonate units to diol component units in the aromatic polyester carbonate resin (molar ratio) are 1 / 0.8 to 1 / 1.2, preferably 1 / 0.9 to 1 / 1.1, and preferably approximately equimolar. The ratio of dicarboxylic acid component units to carbonate units in the aromatic polyester carbonate resin (molar ratio) may be selected from the range of 99 / 1 to 1 / 99, or may be 95 / 5 to 10 / 90, 90 / 10 to 20 / 80, 80 / 20 to 30 / 70, or 70 / 30 to 40 / 60. If the ratio of carbonate units is too high, the refractive index and heat resistance may be reduced.

[0182] [Method of manufacturing aromatic thermoplastic resin] The aromatic thermoplastic resin can be produced by reacting at least one aromatic component selected from an aromatic dicarboxylic acid component and an aromatic diol component with at least one aliphatic component selected from an aliphatic dicarboxylic acid component, an aliphatic diol component, and an aliphatic hydroxycarboxylic acid component. In the present invention, in such a method, the aliphatic component contains at least one branched C 3-24 The aromatic thermoplastic resin is prepared by reacting a branched aliphatic component having an alkyl group.

[0183] Furthermore, if necessary, a carbonate bond-forming component may be reacted to produce an aromatic polyester carbonate resin. That is, the thermoplastic resin of the present invention includes an aromatic polyester resin and an aromatic polyester carbonate resin.

[0184] The aromatic thermoplastic resin of the present invention can be prepared by a conventional method, specifically, a melt polymerization method such as a transesterification method or a direct polymerization method, a solution polymerization method, an interfacial polymerization method, etc., and the melt polymerization method is preferred. The reaction may be carried out in the presence or absence of a solvent depending on the polymerization method.

[0185] The ratios (or charge ratios) of the dicarboxylic acid component, diol component, and hydroxycarboxylic acid component used in the preparation of the aromatic polyester resin, and the ratio of the total amount of the dicarboxylic acid component and carbonate bond-forming component to the diol component used in the preparation of the aromatic polyester carbonate resin, may be within the range of the molar ratio of the constituent units of the aromatic thermoplastic resin. For example, the charge ratio of the dicarboxylic acid component to the diol component does not necessarily need to be within the range of the constituent unit ratios described above, and at least one component selected from the dicarboxylic acid component and the diol component may be in excess of the amount introduced into the aromatic thermoplastic resin. For example, in the melt polymerization method, the amount of an aliphatic diol component such as ethylene glycol that can be distilled from the reaction system may be in excess of the amount introduced into the resin. The amount of the carbonate bond-forming component (C) used may be slightly in excess of the total amount of dicarboxylic acid units and carbonate units (total amount introduced into the resin), for example, 1 to 5 mol %, preferably 2 to 3 mol %.

[0186] The reaction may be carried out in the presence of a catalyst. Conventional esterification catalysts, such as metal catalysts, can be used as catalysts. Metal catalysts may be, for example, alkoxides; organic acid salts such as acetates and propionates; inorganic acid salts such as borates and carbonates; oxides; or hydrates thereof. Representative metal catalysts include germanium compounds such as germanium dioxide, germanium hydroxide, germanium oxalate, germanium tetraethoxide, and germanium-n-butoxide; antimony compounds such as antimony trioxide, antimony acetate, and antimony ethylene glycolate; titanium compounds such as tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate (titanium(IV) tetrabutoxide), titanium oxalate, and potassium titanium oxalate; manganese compounds such as manganese acetate tetrahydrate; and calcium compounds such as calcium acetate monohydrate.

[0187] These catalysts can be used alone or in combination of two or more. Among these catalysts, manganese acetate, calcium acetate or their hydrates, germanium dioxide, titanium (IV) tetrabutoxide, etc. are preferred. The amount of catalyst used is, for example, 0.01 × 10 per mole of the dicarboxylic acid component. -4 ~100×10 -4 moles, preferably 0.1 x 10 -4 ~40×10 -4 It is a mole.

[0188] The reaction may be carried out in the presence of a stabilizer such as a heat stabilizer or an antioxidant, if necessary. In the melt polymerization method, a heat stabilizer is usually used, and examples thereof include phosphorus compounds such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dibutyl phosphate (dibutyl phosphate or dibutyl phosphate), phosphorous acid, trimethyl phosphite, and triethyl phosphite. Among these stabilizers, dibutyl phosphate is often used. The amount of the heat stabilizer used is, for example, 0.01 × 10 per mole of the dicarboxylic acid component. -4 ~100×10 -4 moles, preferably 0.1 x 10 -4 ~40×10 -4 It is a mole.

[0189] The reaction is usually carried out in an atmosphere of an inert gas, such as nitrogen gas, or a rare gas such as helium or argon. Alternatively, the reaction may be carried out under reduced pressure, for example, at a pressure of 1×10 2 ~1×10 4 The reaction temperature can be selected depending on the polymerization method, and for example, the reaction temperature in the melt polymerization method is 150 to 320°C, preferably 180 to 310°C, and more preferably 200 to 300°C.

[0190] [Characteristics and Molded Products of Aromatic Thermoplastic Resins] (characteristic) Generally, introducing an aromatic ring into a resin increases the refractive index and the glass transition temperature, but tends to decrease moldability (or productivity) and increase birefringence. Therefore, it is difficult to improve moldability and reduce birefringence while increasing the refractive index and heat resistance. In contrast, the aromatic thermoplastic resin of the present invention contains the aromatic dicarboxylic acid unit and the aromatic diol component unit, and therefore has a high refractive index and high heat resistance. In particular, the inclusion of a branched aliphatic component unit significantly reduces the melt viscosity while maintaining a high refractive index and high heat resistance, and also reduces or adjusts the absolute value of birefringence and reduces the Abbe number. Therefore, the two trade-offs between heat resistance and moldability can be achieved simultaneously, i.e., a high refractive index, a low Abbe number, and an absolute value of birefringence. In particular, the aromatic thermoplastic resin of the present invention contains aromatic component units as the main units, and despite its high refractive index and heat resistance, it can improve moldability and efficiently mold even thin components.

[0191] The glass transition temperature Tg of the aromatic thermoplastic resin may be, for example, in the range of 100 to 250°C, preferably 110 to 230°C, 120 to 210°C, 130 to 200°C, and 135 to 190°C in the following stepwise manner. To achieve high moldability while simultaneously achieving optical properties such as a high refractive index, a low Abbe number, and a low absolute value of birefringence, as well as high heat resistance, the glass transition temperature Tg of the thermoplastic resin is more preferably 135 to 185°C, 140 to 180°C, 145 to 170°C, and 150 to 165°C in the following stepwise manner, and particularly 155 to 165°C. If the glass transition temperature Tg is too low, the heat resistance may decrease, and the resin may deteriorate or discolor during molding and / or use, or may be prone to deformation in high-temperature environments. This may render the resin unusable in applications requiring high heat resistance (or thermal stability), such as automotive optical lenses. On the other hand, even if the glass transition temperature Tg is high, the moldability such as injection molding is high, and uniform molded articles without distortion can be molded without using special molds.

[0192] The refractive index nD of the aromatic thermoplastic resin can be selected, for example, from the range of 1.62 to 1.75 at a temperature of 20° C. and a wavelength of 589 nm, preferably in the following stepwise ranges of 1.63 to 1.74, 1.64 to 1.73, and particularly 1.65 to 1.72.

[0193] The Abbe number of the aromatic thermoplastic resin at a temperature of 20°C is, for example, 20 or less. Since the Abbe number generally tends to decrease with increasing refractive index, the resin of the present invention, which exhibits a high refractive index, can be effectively used in applications requiring a lower Abbe number, such as optical components in various cameras, specifically, camera lenses that use a combination of concave and convex lenses. The optical systems of various cameras typically use a combination of multiple concave and convex lenses to reduce (or cancel) the chromatic aberration (blurring) that occurs in convex lenses using a concave lens with a low Abbe number. The aromatic thermoplastic resin of the present invention is fully capable of meeting the low Abbe number required for the concave lens. The Abbe number of the aromatic thermoplastic resin for such applications at a temperature of 20°C is, for example, 23 or less, preferably 22 or less, more preferably 10 to 21, even more preferably 13 to 20, and particularly preferably 15 to 18.

[0194] The birefringence of an aromatic thermoplastic resin may be evaluated by measuring the birefringence (triple birefringence) of a stretched film obtained by uniaxially stretching a film formed from the resin alone at a stretching temperature of glass transition temperature Tg + 10°C, a stretching speed of 25 mm / min, and a stretching ratio of 3. The absolute value of the triple birefringence of the stretched film is, for example, 300 × 10 at a measurement temperature of 20°C and a wavelength of 600 nm. -4 The range can be selected from the following ranges, preferably in the following steps: 200 × 10 -4 Below, 100 x 10 -4 Below, 50 x 10 -4 Below, 40 x 10 -4 Below, 30 x 10 -4 Below, 25 x 10 -4 Below, 20 x 10 -4 or less, and more preferably 15×10 -4 Below, particularly preferably 10 × 10 -4 Normally, the triple birefringence is 0 to 15 × 10-4 , e.g., 0.001 x 10 -4 ~10×10 -4 is.

[0195] The weight average molecular weight Mw of the aromatic thermoplastic resin can be measured by gel permeation chromatography (GPC) or the like, and may be, for example, 10,000 to 500,000, preferably 20,000 to 200,000, further preferably 30,000 to 150,000, even more preferably 40,000 to 100,000, and most preferably 35,000 to 70,000, and particularly preferably 40,000 to 65,000, in terms of polystyrene.

[0196] The melt viscosity of the aromatic thermoplastic resin, measured at a temperature of 260°C, a frequency of 20 Hz, and an angular velocity of 126 rad / sec, is 250 Pa·s or less, preferably 230 Pa·s or less, more preferably 200 Pa·s or less, and particularly preferably 150 Pa·s or less. Specifically, when measured under the above conditions, the melt viscosity is, for example, 10 to 250 Pa·s, preferably in the following stepwise order: 15 to 230 Pa·s, 20 to 220 Pa·s, 50 to 210 Pa·s, 100 to 200 Pa·s, and 110 to 140 Pa·s. Even when the amount of branched aliphatic component introduced is large, the melt viscosity can be reduced while suppressing a decrease in heat resistance (or glass transition temperature) and a decrease in refractive index. Furthermore, the absolute value of birefringence can be adjusted and reduced by introducing the branched aliphatic component.

[0197] The saturated water absorption of the aromatic thermoplastic resin can be measured using a method conforming to JIS K 7209. For example, it can be calculated from the weight of a dried plate molded from the resin alone and the weight increase after long-term storage in water at a predetermined temperature or in a high-humidity environment. Measurements are preferably performed under an environment of 85°C and 95% RH, as this shortens the time required for saturation, i.e., for weight gain due to water absorption to cease. Under these measurement conditions, the weight increase after 7 days (saturated water absorption) is 0.66 wt% or less, preferably 0.64 wt% or less, and more preferably 0.62 wt% or less. Specifically, the weight increase after 7 days under the above measurement conditions (saturated water absorption) may be, for example, 0.50 to 0.66 wt%, preferably 0.52 to 0.64 wt%, and more preferably 0.55 to 0.62 wt%.

[0198] In this specification and claims, the glass transition temperature Tg, refractive index nD, Abbe number, birefringence (stretched 3 times), weight average molecular weight Mw, melt viscosity, and saturated absorptance can be measured by the methods described in the examples below.

[0199] (Molded body) The molded article of the present invention contains at least the aromatic thermoplastic resin and exhibits excellent moldability despite its high heat resistance, making it suitable for use in a variety of molded articles. Such molded articles may also contain conventional additives. Depending on the intended use of the molded article, additives may include, for example, fillers or reinforcing agents, colorants such as dyes and pigments, conductive agents, flame retardants, plasticizers, lubricants, mold release agents, antistatic agents, dispersants, surfactants, flow control agents, leveling agents, antifoaming agents, surface modifiers, hydrolysis inhibitors, carbon materials, stabilizers, and stress-reducing agents. Examples of stabilizers include antioxidants, ultraviolet absorbers, and heat stabilizers. Examples of stress-reducing agents include silicone oil, silicone rubber, various plastic powders, and various engineering plastic powders. These additives may be used alone or in combination.

[0200] The molded article may be produced by casting, but thermoforming methods such as injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, and pressure molding can also be used.

[0201] The shape of the molded body is not particularly limited, and examples thereof include one-dimensional structures such as linear, fibrous (or fiber-like) and thread-like structures, two-dimensional structures such as film-like, sheet-like and plate-like structures, and three-dimensional structures such as concave or convex lens-like, rod-like, hollow (tubular) and three-dimensional shapes.

[0202] The molded article of the present invention has excellent optical properties despite its high heat resistance, and is therefore suitable as an optical component, and can be used as an optical component such as an optical film (or optical sheet) or an optical lens. In particular, the aromatic thermoplastic resin has high melt moldability or melt fluidity, and therefore is highly moldable and suitable for preparing a molded article with a thin and uniform thickness. Therefore, the present invention also includes a film (optical film or optical sheet) formed from the aromatic thermoplastic resin.

[0203] The average thickness of such a film can be selected, for example, within the range of 1 to 1000 μm depending on the application, and is, for example, 2 to 250 μm, preferably 5 to 200 μm, and more preferably 10 to 150 μm. Such a film (optical film) may be produced by a conventional film-forming method, for example, a casting method (solvent casting method), but can also be produced by film-forming (or molding) using a thermoforming method such as a melt extrusion method or a calendar method.

[0204] In the present invention, low birefringence can be maintained even after stretching. Therefore, the film may be a stretched film, for example, either a uniaxially stretched film or a biaxially stretched film. Such a stretched film can be obtained by subjecting a film (or an unstretched film) after film formation to a stretching treatment. The stretching method is not particularly limited, and in the case of uniaxial stretching, either a wet stretching method or a dry stretching method may be used, and in the case of biaxial stretching, a tube method may be used, but a tenter method (flat method) which provides excellent uniformity in stretched thickness is preferred.

[0205] The stretching ratio in each direction in uniaxial or biaxial stretching is, for example, 1.1 to 10 times, preferably 1.2 to 6 times, and more preferably 1.5 to 3 times. Biaxial stretching may be equal stretching, for example, stretching 1.5 to 5 times in both the longitudinal and transverse directions, or asymmetric stretching, for example, stretching 1.1 to 4 times in the longitudinal direction and 2 to 6 times in the transverse direction. Uniaxial stretching may be longitudinal stretching, for example, stretching 2.5 to 8 times in the longitudinal direction, or transverse stretching, for example, stretching 1.2 to 5 times in the transverse direction. The average thickness of the stretched film is, for example, 1 to 150 μm, preferably 3 to 120 μm, and more preferably 5 to 100 μm.

[0206] The molded article may be joined or adhered to another substrate, and the type and material of the substrate are not particularly limited, and may be, for example, a one-dimensional, two-dimensional, or three-dimensional substrate formed from a resin material, a ceramic material, a metal material, etc. For example, when the molded article is in the form of a film, it may be laminated on a two-dimensional substrate such as a film to form a laminate or a laminate film.

[0207] Representative examples of the two-dimensional substrate include a ceramic substrate such as a glass substrate, a resin film or sheet, etc., and are usually transparent substrates. The resin film or sheet as the substrate may be formed from, for example, a polyolefin resin such as a chain olefin resin or a cyclic olefin resin (or a cycloolefin resin); a (meth)acrylic resin; a styrene resin; a polyester resin such as a polyalkylene arylate resin, a polyarylate resin, or a polycarbonate resin; or a polyamide resin. [Example]

[0208] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. The evaluation methods used in the examples and comparative examples are as follows.

[0209] [Evaluation method] (Thermoplastic resin composition) The sample was dissolved in deuterated chloroform containing tetramethylsilane as an internal standard, and the NMR spectrum was measured using a nuclear magnetic resonance spectrometer (BRUKER "AVANCE III HD"). 1 The H-NMR spectrum was measured. The integral values ​​of the peaks derived from each reaction component were determined for the obtained spectrum, and the proportion of each reaction component (structural unit) introduced into the thermoplastic resin was calculated.

[0210] (glass transition temperature Tg) Measurement was carried out using a differential scanning calorimeter ("EXSTAR6000 DSC6220 ASD-2" manufactured by SII NanoTechnology Inc.) in a nitrogen gas atmosphere at a temperature increase rate of 10°C / min.

[0211] (molecular weight) The sample was dissolved in chloroform, and the weight average molecular weight Mw in terms of polystyrene was determined using gel permeation chromatography ("HLC-8320GPC" manufactured by Tosoh Corporation).

[0212] (Refractive index nD) The refractive index was measured as follows. The sample was heat-pressed at 200 to 240°C to form a film with a thickness of 200 to 300 μm. This film was cut into strips measuring 20 to 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 ("DR-M4 (circulating constant temperature water bath 60-C3)" manufactured by Atago Co., Ltd.) at a measurement temperature of 20°C and diiodomethane as a contact liquid.

[0213] (Abbe number) Using the test piece for measuring the refractive index (the test piece for measuring the refractive index nD at 589 nm (D line)), the refractive indices nF and nC were measured in the same manner as for the refractive index nD, except that the measurement wavelengths were changed to 486 nm (F line) and 656 nm (C line). From the obtained refractive indices nF, nD, and nC at each wavelength, the Abbe number was calculated using the following formula.

[0214] (Abbe number) = (nD-1) / (nF-nC).

[0215] (Birefringence (stretched 3 times)) The samples were heat-pressed at 200-240°C to form films with thicknesses of 200-600 μm. These films were cut into strips measuring 10 mm wide x 50 mm long and uniaxially stretched in the machine direction at a temperature of glass transition temperature (Tg) + 10°C at a stretch ratio of 3 at a speed of 25 mm / min (stretching from 50 mm to 150 mm in the machine direction). The retardation of the resulting test specimens was measured using a retardation film and optical material testing device (Otsuka Electronics Co., Ltd., "RETS-100") at a temperature of 20°C and a wavelength of 600 nm using the parallel Nicol rotation method. The measured value was divided by the thickness of the measurement site to calculate the birefringence (or triple birefringence).

[0216] (melt viscosity) The melt viscosity was measured at a temperature of 260°C, a frequency of 20 Hz, and an angular velocity of 126 (rad / sec) using a dynamic viscoelasticity measuring device (Rheosol-G5000, manufactured by UBM Corporation).

[0217] (saturated water absorption rate) The sample was hot-pressed at 180-200°C to form a 1 mm thick plate. This plate was cut into a rectangular shape measuring 40 mm wide x 60 mm long to prepare a test piece. This test piece was dried at a temperature of 90°C for 24 hours, and the weight of the dried test piece was measured. It was then placed in a thermo-hygrostat (Isuzu Manufacturing Co., Ltd., model "HPAV-120-20") set at a temperature of 85°C and a humidity of 95% RH, and the weight of the test piece was measured after 7 days. The saturated water absorption was calculated using the following formula.

[0218] (Saturated water absorption rate) = 100 × (weight of test piece after 7 days at 85°C, 95% RH - weight of test piece after drying) / (weight of test piece after drying).

[0219] [Resin raw materials (polymerization reaction components)] (Dicarboxylic acid component) First Aromatic Dicarboxylic Acid Component FDP-m: 9,9-bis(2-methoxycarbonylethyl)fluorene represented by the following formula (synthesized in the same manner as in Example 1 of JP-A-2005-89422, except that methyl acrylate [37.9 g (0.44 mol)] was used instead of t-butyl acrylate).

[0220] [ka]

[0221] 2-DNFDP-m: 9,9-bis(2-methoxycarbonylethyl)-2,7-di(2-naphthyl)fluorene represented by the following formula (synthesized according to Example 1A of Patent Document 3)

[0222] [ka]

[0223] DPFDP-m: 9,9-bis(2-methoxycarbonylethyl)-2,7-diphenylfluorene represented by the following formula (synthesized in the same manner as in Example 1A of Patent Document 3, except that phenylboronic acid was used instead of 2-naphthylboronic acid).

[0224] [ka]

[0225] Branched Aliphatic Dicarboxylic Acid Component (First Aliphatic Dicarboxylic Acid Component) Octadecyl SA: Octadecyl succinic anhydride (C 22 H 40 O3) (In the table, “C 18 -Suc A) Dodecyl SA: Dodecyl succinic anhydride (C 16 H 28 O3) (In the table, “C 12 -Suc A)

[0226] (Diol component) First Aromatic Diol Component BNEF: 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (synthesized according to Synthesis Example 1 in JP 2018-59074 A) Branched aliphatic diol component (first aliphatic diol component) 1,2-dodecanediol (in the table, "1,2-C 12 (represented as "diol") 1,2-octanediol (referred to as "1,2-C8diol" in the table) 1,2-Hexanediol (referred to as "1,2-C6diol" in the table) 2-Ethyl-2-butyl-1,3-propanediol (referred to as "C2,C4-1,3-C3diol" in the table) 2-Ethyl-1,3-hexanediol (referred to as "C2-1,3-C6diol" in the table) Second Aliphatic Diol Component EG: Ethylene glycol (represented as "EG" in the table) 1,5-Pentanediol (represented as "(1,5-C5diol)" in the table)

[0227] (Hydroxycarboxylic acid components (HCAs)) 12-hydroxystearic acid (see "12-OH C" in the table) 18 (represented as "A")

[0228] (carbonate bond forming component) Diphenyl carbonate

[0229] The chemical formulas and abbreviations of the branched aliphatic dicarboxylic acid component, branched aliphatic diol component (first aliphatic diol component), second aliphatic diol component, and hydroxycarboxylic acid component used in the examples and comparative examples are shown in Figures 1 and 2.

[0230] [Examples and Comparative Examples] Comparative Example 1 The reactor was charged with FDP-m (25.38 g (75 mmol)) and 2-DNFDP-m (14.77 g (25 mmol)) as dicarboxylic acid components, BNEF (45.78 g (85 mmol)) as diol components, EG (13.35 g (215 mmol)), and titanium (IV) tetrabutoxide (3.4 mg (10 μmol)) as a catalyst for the transesterification and polycondensation reactions. The mixture was gradually heated to 240 °C under a nitrogen atmosphere and stirred to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, dibutyl phosphate (21.0 mg (100 μmol)) was added as a thermal stabilizer, and the temperature was gradually raised to 288 °C and 150 Pa, the pressure was reduced, and the polycondensation reaction was carried out while removing the EG. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0231] Examples 1 to 7 A polyester resin was obtained in the same manner as in Comparative Example 1, except that BNEF, a branched aliphatic diol component (first aliphatic diol component), and EG were used in the proportions shown in Table 1 as the diol components.

[0232] Comparative Example 2 The reactor was charged with FDP-m (33.84 g (100 mmol)) as a dicarboxylic acid component, BNEF (40.40 g (75 mmol)) as a diol component, EG (13.97 g (225 mmol)), and titanium (IV) tetrabutoxide (3.4 mg (10 μmol)) as a catalyst for the transesterification and polycondensation reactions. The mixture was gradually heated to 240 °C under a nitrogen atmosphere and stirred to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, dibutyl phosphate (16.8 mg (80 μmol)) was added as a thermal stabilizer, and the temperature was gradually raised to 280 °C and 150 Pa, the pressure was reduced, and the polycondensation reaction was carried out while removing the EG. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0233] Examples 8 to 10 A polyester resin was obtained in the same manner as in Comparative Example 2, except that FDP-m was used as the dicarboxylic acid component and BNEF and EG were used as the diol components in the proportions shown in Table 1.

[0234] Comparative Example 3 A polyester resin was obtained in the same manner as in Comparative Example 1, except that FDP-m and 2-DNFDP-m were used as dicarboxylic acid components, and BNEF and EG were used as diol components in the proportions shown in Table 3. In Table 3, the "*" in Example 16 indicates the total amount of 1,2-octanediol (1,2-C8diol) and 1,2-hexanediol (1,2-C6diol) ( 1 The total molar ratio calculated by H-NMR was 13 mol %.

[0235] Examples 11 to 16 A polyester resin was obtained in the same manner as in Comparative Example 3, except that BNEF, a branched aliphatic diol component (first aliphatic diol component), and EG were used in the proportions shown in Table 3 as the diol components.

[0236] Comparative Example 4 A polyester resin was obtained in the same manner as in Comparative Example 1, except that FDP-m and DPFDP-m as dicarboxylic acid components and BNEF and EG as diol components were used in the proportions shown in Table 5.

[0237] Examples 17 to 19 A polyester resin was obtained in the same manner as in Comparative Example 4, except that BNEF, a branched aliphatic diol component, and EG were used in the proportions shown in Table 5 as the diol component.

[0238] Example 20 A reactor was charged with FDP-m (20.30 g (60 mmol)) and DNFDP-m (17.72 g (30 mmol)) as dicarboxylic acid components, diphenyl carbonate (2.27 g (10.6 mmol)) as a carbonate bond-forming component, BNEF (44.71 g (83 mmol)), 1,2-octanediol (1.32 g (9 mmol)), and 1,5-pentanediol (0.83 g (8 mmol)) as diol components, and titanium (IV) tetrabutoxide (3.4 mg (10 μmol)) as a catalyst for the transesterification and polycondensation reactions. The mixture was gradually heated to 240°C under a nitrogen atmosphere, stirred, and the transesterification reaction was carried out. After removing the alcohol component produced by the transesterification reaction, dibutyl phosphate (16.8 mg (80 μmol)) was added as a heat stabilizer, and the temperature was gradually increased to 280°C and 150 Pa, the pressure was reduced, and a polycondensation reaction was carried out while removing EG. After the reaction was completed, the contents were removed from the reactor to obtain a polyester carbonate resin.

[0239] The proportions of each reaction component in the examples and comparative examples are shown in Tables 1, 3, 5, and 7, and the evaluation results of each polyester resin obtained are shown in Tables 2, 4, 6, and 8. In Tables 1, 3, 5, and 7, "HCAs" means "hydroxycarboxylic acid component." In addition, in Tables 1, 3, 5, and 7, the composition ratio (molar ratio) of the constituent units derived from the reaction components in the polyester resin is shown in parentheses along with the charged composition (molar ratio) of each reaction component in the dicarboxylic acid component and diol component. 1 The molar ratios are calculated by H-NMR.

[0240] [Table 1]

[0241] [Table 2]

[0242] [Table 3]

[0243] [Table 4]

[0244] [Table 5]

[0245] [Table 6]

[0246] [Table 7]

[0247] [Table 8]

[0248] As is clear from Tables 1 to 8, copolymerization of a branched aliphatic component can reduce the absolute value of birefringence while maintaining a high refractive index, and can reduce the melt viscosity while maintaining a high glass transition temperature. In particular, copolymerization of a first aliphatic diol component can reduce not only the melt viscosity but also the absolute value of birefringence while maintaining a high refractive index and a high glass transition temperature.

[0249] Furthermore, as is clear from a comparison of Examples 1 to 4 with Examples 5 to 6 in Tables 1 and 2, copolymerizing a branched aliphatic component having alkyl groups with multiple predetermined carbon atoms can significantly reduce the melt viscosity while maintaining a high refractive index, low birefringence, and a high glass transition temperature. Furthermore, as is clear from a comparison of Examples 1 to 4 with Example 7, copolymerizing a branched aliphatic component containing a hydroxycarboxylic acid component unit, even in small amounts, can reduce the absolute value of birefringence while maintaining a high refractive index, thereby reducing the melt viscosity while maintaining a high glass transition temperature. Furthermore, a comparison of Example 2 with Example 5 indicates that the longer the chain length of the linear portion of the branched aliphatic component, the more effectively the melt viscosity is reduced.

[0250] Furthermore, as is clear from Tables 1 to 6, the present invention can reduce the saturated water absorption of the resin, possibly due to the copolymerization of a specific branched aliphatic component. Therefore, molded articles containing the aromatic thermoplastic resin of the present invention can suppress dimensional changes and refractive index fluctuations caused by water absorption, and can be effectively used in optical applications (such as optical lenses) that require precision in shape. [Industrial Applicability]

[0251] The aromatic thermoplastic resin of the present invention not only exhibits excellent optical properties such as a high refractive index, a low Abbe number, and a low birefringence, but also low water absorption and high heat resistance, and has a low melt viscosity and high moldability. Therefore, it may be used in a variety of applications, for example, coating agents or coating films, specifically, paints, inks, and protective films for electronic devices and liquid crystal components; adhesives, pressure-sensitive adhesives; resin fillers; electrical and electronic materials or electrical and electronic components (electrical and electronic devices), specifically, antistatic agents, carrier transport agents, light-emitting bodies, organic photoreceptors, thermosensitive recording materials, photochromic materials, hologram recording materials, charging trays, conductive sheets, optical disks, inkjet printers, digital paper, color filters, organic EL elements, organic semiconductor lasers, dye-sensitized solar cells, sensors, EMI shielding films, etc.; and mechanical materials or mechanical parts (equipment), specifically, automotive materials or parts, aerospace-related materials or parts, sliding members, etc.

[0252] The aromatic thermoplastic resin of the present invention has a good balance of excellent optical properties, high heat resistance, and low water absorption, and therefore can be particularly effectively used as an optical component. Typical examples of the optical component include optical films (optical sheets) such as films for liquid crystal displays and organic electroluminescence displays; optical lenses such as lenses for glasses and cameras; prisms, holograms, and optical fibers.

[0253] Examples of optical films include polarizing films, polarizing elements and polarizing plate protective films that constitute polarizing films, retardation films, alignment films (alignment films), viewing angle widening (compensation) films, diffuser plates (films), prism sheets, light guide plates, brightness enhancement films, near-infrared absorbing films, reflective films, anti-reflection (AR) films, reflection reducing (LR) films, anti-glare (AG) films, transparent conductive (ITO) films, anisotropic conductive films (ACF), electromagnetic shielding (EMI) films, films for electrode substrates, films for color filter substrates, barrier films, color filter layers, black matrix layers, and adhesive layers or release layers between optical films. These optical films can be effectively used as optical films for displays such as liquid crystal displays (LCDs), organic light-emitting diode displays (OLEDs), plasma displays (PDPs), field emission displays (FEDs), and electronic paper.Specific devices or apparatuses include televisions; personal computers (PCs) such as desktop PCs, notebook PCs, and tablet PCs; smartphones, mobile phones; car navigation systems; and devices or apparatuses equipped with flat panel displays (FPDs) such as touch panels.

[0254] Examples of optical lenses include eyeglass lenses, contact lenses, camera lenses, VTR zoom lenses, pickup lenses, Fresnel lenses, solar concentrating lenses, objective lenses, and rod lens arrays. In particular, optical lenses are suitable for use in lenses that require a low Abbe number, such as camera lenses. Typical examples of devices or apparatuses incorporating such optical lenses include small or mobile devices with camera functions, such as smartphones, mobile phones, and digital cameras; and in-vehicle cameras, such as drive recorders and backup cameras (rear cameras). Aromatic thermoplastic resins with high heat resistance can be suitable for use in applications where high-temperature environments are anticipated, such as in-vehicle optical lenses.

Claims

1. An aromatic thermoplastic resin comprising, as polymerization components, at least one aromatic component selected from an aromatic dicarboxylic acid component and an aromatic diol component, and at least one aliphatic component selected from an aliphatic dicarboxylic acid component, an aliphatic diol component, and an aliphatic hydroxycarboxylic acid component, The aromatic dicarboxylic acid component is represented by the following formula (1): 【Chemistry 1】 (wherein Z 1a and Z 1b independently represent an arene ring, R 1a and R 1b independently represent a substituent, k1 and k2 independently represent an integer of 0 to 4, R 2a and R 2b independently represent a substituent, m1 and m2 independently represent an integer of 0 or more, n1 and n2 independently represent an integer of 0 to 4, A 1a and A 1b independently represent a linear or branched alkylene group, and X 1a and X 1b independently represent a hydroxyl group, an alkoxy group, or a halogen atom). The compound includes a compound represented by the structural unit derived from the aliphatic component contains one or more branched chains, and at least one of the branched chains contains a linear or branched alkyl group having 3 to 30 carbon atoms; or a branched aliphatic component-derived structural unit containing a linear or branched alkenyl group having 3 to 30 carbon atoms; An aromatic thermoplastic resin which is a polyester resin or a polyester carbonate resin.

2. 2. The aromatic thermoplastic resin according to claim 1, wherein the aromatic dicarboxylic acid component comprises a compound represented by the following formula (1-1a), (1-2a) or (1-2b): 【Chemistry 2】 (In the formula, R １ａ and R １ｂ each independently represents a halogen atom, a cyano group, or a linear or branched alkyl group having 1 to 6 carbon atoms; k1 and k2 each independently represent an integer of 0 to 2; A １ａ and A １ｂ each independently represents a linear or branched alkylene group having 1 to 8 carbon atoms; X １ａ and X １ｂ are the same as the formula (1) in claim 1.

3. The aromatic thermoplastic resin according to claim 1 or 2, wherein the aromatic diol component comprises a compound represented by the following formula (3): 【Transformation 3】 (In the formula, R ４ represents a substituent, r represents an integer of 0 to 8, and Z ３ａ and Z ３ｂ each independently represents an arene ring; R ５ａ and R ５ｂ each independently represents a substituent; s1 and s2 each independently represents an integer of 0 or more; A ３ａ and A ３ｂ each independently represents a linear or branched alkylene group, and t1 and t2 each independently represent an integer of 0 or greater.

4. The aromatic thermoplastic resin according to any one of claims 1 to 3, wherein the aromatic diol component comprises a compound represented by the following formula (3-1) or (3-2): 【Chemistry 4】 (In the formula, R ４ represents a linear or branched alkyl group having 1 to 4 carbon atoms, r represents 0 or 1, and R ５ａ and R ５ｂ each independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms; s1 and s2 each independently represent an integer of 0 to 2; A ３ａ and A ３ｂ each independently represents a linear or branched alkylene group having 1 to 4 carbon atoms, and t1 and t2 each independently represent an integer of 0 to 10.

5. The aromatic thermoplastic resin according to any one of claims 1 to 4, wherein the structural units derived from the aromatic component include structural units derived from both the aromatic dicarboxylic acid component and the aromatic diol component.

6. The aromatic thermoplastic resin according to any one of claims 1 to 5, wherein the structural unit derived from the branched aliphatic component has, as a branched chain, a linear or branched alkyl group having 3 to 22 carbon atoms; or a linear or branched alkenyl group having 3 to 22 carbon atoms.

7. The aromatic thermoplastic resin according to any one of claims 1 to 6, wherein the structural unit derived from the branched aliphatic component is a structural unit derived from at least one selected from a branched alkanediol having 6 to 20 carbon atoms, a branched alkylenedicarboxylic acid having 12 to 22 carbon atoms, and a branched hydroxyalkanecarboxylic acid having 7 to 25 carbon atoms, and has, as at least one branched chain, a linear or branched alkyl group having 3 to 18 carbon atoms; or a linear or branched alkenyl group having 3 to 18 carbon atoms.

8. The aromatic thermoplastic resin according to any one of claims 1 to 7, wherein the branched aliphatic component comprises at least one selected from a branched aliphatic dicarboxylic acid component, a branched aliphatic diol component, and a branched aliphatic hydroxycarboxylic acid component, and the proportion of all structural units derived from the branched aliphatic component to all structural units derived from the dicarboxylic acid component, the diol component, and the hydroxycarboxylic acid component is 1 to 35 mol%.

9. The aromatic thermoplastic resin according to any one of claims 1 to 8, wherein the branched aliphatic component comprises a 1,2-alkanediol having 6 to 16 carbon atoms and / or a 1,3-alkanediol having 6 to 16 carbon atoms, and the proportion of the structural units derived from the 1,2-alkanediol having 6 to 16 carbon atoms and / or the structural units derived from the 1,3-alkanediol having 6 to 16 carbon atoms relative to all structural units derived from the dicarboxylic acid component, the diol component, and the hydroxycarboxylic acid component is 3 to 25 mol%.

10. 10. A method for producing the aromatic thermoplastic resin according to any one of claims 1 to 9, comprising reacting the aromatic dicarboxylic acid component and the aromatic diol component with at least one aliphatic component selected from the aliphatic dicarboxylic acid component, the aliphatic diol component, and the aliphatic hydroxycarboxylic acid component, wherein the aromatic dicarboxylic acid component and the aromatic diol component are reacted with a branched aliphatic component containing one or more branched chains, at least one of the branched chains having a linear or branched alkyl group having 3 to 30 carbon atoms; or a linear or branched alkenyl group having 3 to 30 carbon atoms.

11. A molded article comprising the aromatic thermoplastic resin according to any one of claims 1 to 9.

12. The molded article according to claim 11, which is an optical element.

13. The molded article according to claim 11 or 12, which is an optical film or an optical lens.

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