Thermoplastic resin, its manufacturing method and use

Abstract

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

Description

[Technical Field]

[0001] The present invention relates to a thermoplastic resin containing a specific aromatic dicarboxylic acid component (arene dicarboxylic acid component) as a polymerization component, and a method for producing the same and uses thereof. [Background technology]

[0002] A method for producing a liquid crystalline polyester using an aromatic dicarboxylic acid component by melt polymerization, etc., is known. As the aromatic dicarboxylic acid component, JP 2013-28700 A (Patent Document 1) and JP 2013-28746 A (Patent Document 2) describe an aromatic dicarboxylic acid component represented by the following formula (2):

[0003] Formula (2):R 21 -CO-Ar 2 -CO-R 22 (In the formula, Ar 2 represents a phenylene group, naphthylene group, biphenylylene group, etc., and R 21 and R 22 represents a hydroxyl group, an alkoxyl group, an aryloxyl group, an acyloxyl group, or a halogen atom, and Ar 1 Each hydrogen atom in the group represented by the formula (I) may be substituted with a halogen atom, an alkyl group or an aryl group).

[0004] Furthermore, Japanese Patent Application Laid-Open No. 2013-7004 (Patent Document 3) describes an aromatic dicarboxylic acid component represented by the following formula (2').

[0005] Formula (2'):G 2 -CO-Ar 2 -CO-G 2 (In the formula, Ar 2 is a 2,6-naphthylene group, a 1,4-phenylene group, a 1,3-phenylene group, or a 4,4'-biphenylylene group; G 2 are each a hydroxyl group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, or a halogen atom;2 One or more hydrogen atoms therein may be independently substituted with a halogen atom, an alkyl group or an aryl group). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2013-28700 A [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-28746 [Patent Document 3] Japanese Patent Application Laid-Open No. 2013-7004 Summary of the Invention [Problem to be solved by the invention]

[0007] In the examples of Patent Documents 1 to 3, liquid crystal polyesters are prepared using terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, etc. as aromatic dicarboxylic acid components, and the use of a specific aromatic dicarboxylic acid component having an aryl group is not anticipated. Furthermore, Patent Documents 1 to 3 do not describe or suggest the use of the obtained liquid crystal polyesters for optical applications such as optical members.

[0008] With the recent development of small or mobile devices (information terminals) such as smartphones and tablet PCs, the performance of optical components that perform optical functions such as image display and camera functions of these devices is improving. Therefore, the optical materials used to form such optical components are also required to have higher performance.

[0009] Therefore, an object of the present invention is to provide a thermoplastic resin that exhibits a high refractive index and high heat resistance, a method for producing the same, and uses thereof. [Means for solving the problem]

[0010] As a result of intensive research to achieve the above object, the present inventors have found that when a thermoplastic resin is prepared using a specific aromatic dicarboxylic acid component (arene dicarboxylic acid component) having an aryl group as a polymerization component, the resulting resin exhibits a high refractive index and high heat resistance, and have completed the present invention.

[0011] That is, the thermoplastic resin of the present invention is a thermoplastic resin containing a dicarboxylic acid unit (A), and the dicarboxylic acid unit (A) has at least a first dicarboxylic acid unit (A1) represented by the following formula (1):

[0012] [ka]

[0013] (In the formula, Z 1 represents a monocyclic or fused polycyclic arene ring, Z 2 indicates an arene ring, and R 1 represents a substituent, k1 represents an integer of 0 or more, m represents an integer of 1 or more, R 2 represents a substituent, and k2 represents an integer of 0 or more).

[0014] In the formula (1), Z 1 is monocyclic or fused polycyclic C 6-14 is an arene ring, Z 2 C 6-14 It may be an arene ring, and m may be an integer of 1 to 3.

[0015] In the formula (1), Z 1 is a benzene ring or a naphthalene ring, Z 2 may be at least one arene ring selected from a benzene ring, a naphthalene ring, and a biphenyl ring, and m may be an integer of 1 or 2. The proportion of the first dicarboxylic acid units (A1) may be about 1 to 50 mol % based on the total dicarboxylic acid units (A).

[0016] The dicarboxylic acid unit (A) may contain a second dicarboxylic acid unit (A2) represented by the following formula (2).

[0017] [ka]

[0018] (In the formula, R 3 represents a substituent, k3 represents an integer of 0 to 8, A 1a and A 1b represent independently a divalent hydrocarbon group which may have a substituent.

[0019] In the formula (2), R 3 may be an aryl group, k3 may be an integer of 0 to 4, A 1a and A 1b may be a straight or branched chain alkylene group.

[0020] The second dicarboxylic acid unit (A2) is represented by the formula (2), 3 The second dicarboxylic acid unit (A2-2) may contain at least a dicarboxylic acid unit (A2-2) in which k is an aryl group and k3 is an integer of 1 or greater. The proportion of the dicarboxylic acid unit (A2-2) may be, for example, about 1 to 100 mol % based on the total amount of the second dicarboxylic acid unit (A2).

[0021] The ratio of the first dicarboxylic acid unit (A1) to the second dicarboxylic acid unit (A2) may be the former / latter (molar ratio)=about 5 / 95 to 90 / 10.

[0022] The dicarboxylic acid units (A) may contain an aliphatic dicarboxylic acid unit as a third dicarboxylic acid unit (A3).

[0023] The third dicarboxylic acid unit (A3) may contain a structural unit derived from a linear or branched alkanedicarboxylic acid having 2 to 20 carbon atoms.

[0024] The ratio of the first dicarboxylic acid unit (A1) to the third dicarboxylic acid unit (A3) may be the former / latter (molar ratio)=about 5 / 95 to 90 / 10, The ratio of the second dicarboxylic acid unit (A2) to the third dicarboxylic acid unit (A3) may be the former / latter (molar ratio)=about 10 / 90 to 95 / 5.

[0025] The thermoplastic resin may be a polyester resin further containing a diol unit (B). The diol unit (B) may contain at least one diol unit selected from a first diol unit (B1) represented by the following formula (3) and a second diol unit (B2) represented by the following formula (4).

[0026] [ka]

[0027] (In the formula, R 4 represents a substituent, k4 represents an integer of 0 to 8, Z 3a and Z 3b each independently represents an arene ring, R 5a and R 5b each independently represents a substituent, k5a and k5b each independently represents an integer of 0 or more, A 2a and A 2b each independently represents a linear or branched alkylene group, and n2a and n2b each independently represent an integer of 0 or 1 or more.

[0028] [ka]

[0029] (In the formula, A 3 represents a linear or branched alkylene group, and n3 represents an integer of 1 or more.

[0030] In the formula (3), Z 3a and Z 3b is a monocyclic or fused polycyclic arene ring, A 2a and A 2b is linear or branched C 2-6 It is an alkylene group, and n2a and n2b may be integers of about 0 to 10. In the formula (4), A 3 is linear or branched C 2-6 It may be an alkylene group, and n3 may be an integer of about 1 to 4.

[0031] The diol unit (B) may contain both the first diol unit (B1) and the second diol unit (B2). The ratio of the first diol unit (B1) to the second diol unit (B2) (molar ratio) may be about 1 / 99 to 99 / 1. The weight-average molecular weight Mw of the thermoplastic resin may be, for example, about 6,000 to 250,000, and preferably about 10,000 to 200,000.

[0032] The present invention includes a method for producing the thermoplastic resin by polymerizing polymerization components containing at least a first dicarboxylic acid component corresponding to the first dicarboxylic acid unit (A1), and a molded article containing the thermoplastic resin. The molded article may be an optical member such as an optical lens.

[0033] The present invention may also solve the following problems as a secondary object.

[0034] That is, another object of the present invention is to provide a thermoplastic resin that can achieve a good balance between the optical properties of a high refractive index and low birefringence (low absolute value of birefringence), which are in a trade-off relationship with each other, and also a good balance between high heat resistance and high moldability (or productivity), which are in a trade-off relationship with each other, as well as a production method and uses thereof.

[0035] Yet another object of the present invention is to provide a thermoplastic resin that can be easily or efficiently prepared to have a high molecular weight even if it contains a polymerization component with low reactivity (polymerization reactivity), as well as a production method and uses thereof.

[0036] In this specification and claims, the terms "dicarboxylic acid unit" and "structural unit derived from a dicarboxylic acid component" refer to a unit (or divalent group) obtained by removing OH (hydroxyl group) from each of the two carboxyl groups of the corresponding dicarboxylic acid, and the term "dicarboxylic acid component" (including compounds exemplified as dicarboxylic acid components) is sometimes used synonymously with the corresponding "dicarboxylic acid unit." Similarly, the terms "diol unit" and "structural unit derived from a diol component" refer to a unit (or divalent group) obtained by removing hydrogen atoms from each of the two hydroxyl groups of the corresponding diol component, and the term "diol component" (including compounds exemplified as diol components) is sometimes used synonymously with the corresponding "diol unit."

[0037] In the present specification and claims, the term "dicarboxylic acid component" refers to a dicarboxylic acid and its ester-forming derivatives. Examples of the ester-forming derivatives include alkyl esters, acid halides such as acid chlorides, and acid anhydrides. Examples of the alkyl esters include lower alkyl esters, such as C alkyl esters, methyl esters, ethyl esters, and t-butyl esters. 1-4 Alkyl esters, etc. The ester-forming derivatives may be monoesters (half esters) or diesters.

[0038] In this specification and claims, the number of carbon atoms in a substituent is represented by C1, C6, C 10 For example, an alkyl group with 1 carbon atom is represented as "C1 alkyl," and an aryl group with 6 to 10 carbon atoms is represented as "C 6-10 It is indicated as "aryl". [Effects of the Invention]

[0039] The thermoplastic resin of the present invention has a high refractive index and high heat resistance because it contains a specific arene dicarboxylic acid component having an aryl group as a polymerization component. Furthermore, as the aromatic ring structure (benzene ring structure) increases, not only does birefringence tend to increase, but the glass transition temperature (Tg) also tends to increase, resulting in a decrease in moldability (productivity). Therefore, it is difficult to achieve both a high refractive index and low birefringence, as well as high heat resistance and high moldability. However, the present invention achieves a good balance between these properties. Furthermore, the specific arene dicarboxylic acid component having an aryl group can be easily and efficiently polymerized, despite its expected low polymerization reactivity due to the effects of steric hindrance caused by the rigidity and bulkiness of its chemical structure. [Brief explanation of the drawings]

[0040] [Figure 1] FIG. 1 is a 1H-NMR spectrum of diethyl 2,5-di(2-naphthyl)terephthalate (DNTPA-E) obtained in Synthesis Example 1. [Figure 2] FIG. 2 is a 1H-NMR spectrum of dimethyl 2-(2-naphthyl)terephthalate (MNTPA-M) obtained in Synthesis Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0041] [Thermoplastic resin] The thermoplastic resin may contain at least a first dicarboxylic acid unit (A1) represented by the following formula (1) as the dicarboxylic acid unit (A). Examples of such thermoplastic resins include polyamide-based resins and polyester-based resins, with polyester-based resins being preferred because they have low water absorption and can be effectively used as optical components. Examples of polyester-based resins include polyester resins and polyester carbonate resins, with polyester resins being preferred from the viewpoint of moldability.

[0042] (Dicarboxylic acid unit (A)) First Dicarboxylic Acid Unit (A1)

[0043] [ka]

[0044] (In the formula, Z 1 represents a monocyclic or fused polycyclic arene ring, Z 2 indicates an arene ring, and R 1 represents a substituent, k1 represents an integer of 0 or more, m represents an integer of 1 or more, R 2 represents a substituent, and k2 represents an integer of 0 or more.

[0045] In the formula (1), Z 1 The arene ring (aromatic hydrocarbon ring) represented by the formula (I) may be a monocyclic arene ring such as a benzene ring or a fused polycyclic arene ring.

[0046] The fused polycyclic arene ring includes, for example, fused bicyclic arene rings, fused tricyclic arene rings, and other fused bicyclic to tetracyclic arene rings. The fused bicyclic arene ring includes fused bicyclic C rings such as naphthalene rings and indene rings. 10-16 Examples of the fused tricyclic arene ring include an anthracene ring and a phenanthrene ring. Preferred fused polycyclic arene rings are fused polycyclic C 10-16 arene rings, more preferably fused polycyclic C 10-14 An arene ring is preferred, and a naphthalene ring is particularly preferred.

[0047] Preferred Z 1 is a monocyclic or fused polycyclic C 6-14 An arene ring is preferred, and a benzene ring or a naphthalene ring is more preferred. A benzene ring is particularly preferred because it can provide a good balance of optical properties such as a high refractive index, a low Abbe number, and low birefringence, as well as high heat resistance, high moldability, and polymerization reactivity (or high molecular weight).

[0048] Z of the two carbonyl groups [-C(=O)-] that form the main chain of a thermoplastic resin (or the two carboxyl groups in the corresponding dicarboxylic acid) 1 The bonding position (substitution position) to Z is not particularly limited. 1 is a benzene ring, it may be, for example, in the 1,2-position (o-position), 1,3-position (m-position), or 1,4-position (p-position) relationship, and the 1,4-position (p-position) is preferred in terms of achieving a good balance of optical properties, high heat resistance, high moldability, polymerization reactivity, and the like.

[0049] Z 2 Examples of the arene ring represented by the formula (I) include monocyclic arene rings such as a benzene ring, and polycyclic arene rings. Polycyclic arene rings include fused polycyclic arene rings and ring-assembled arene rings.

[0050] The fused polycyclic arene ring includes, for example, the Z 1 The preferred fused polycyclic arene rings are fused polycyclic C 10-16 arene rings, more preferably fused polycyclic C 10-14 An arene ring is preferred, and a naphthalene ring is particularly preferred.

[0051] Examples of the ring-assembled arene ring include biarene rings (or biaryl rings), terarene rings (or teraryl rings), etc. Examples of the biarene ring include biphenyl rings, binaphthyl rings, phenylnaphthalene rings, etc. 6-12 Examples of the phenylnaphthalene ring include a 1-phenylnaphthalene ring and a 2-phenylnaphthalene ring. Examples of the terarene ring include a terphenyl ring. 6-12 A preferred ring-assembly arene ring is a biphenyl ring or the like. 6-10 It is an arene ring.

[0052] In this specification and claims, the term "ring assembly arene ring" refers to two or more ring systems (monocyclic or fused polycyclic arene ring systems) directly connected by single bonds (single bonds) or double bonds, and the number of bonds directly connecting the rings is one less than the number of ring systems. Therefore, for example, phenylnaphthalene rings and binaphthyl rings are classified as ring assembly arene rings as described above, and even though they have a fused polycyclic arene ring skeleton, they are clearly distinguished from "fused polycyclic arene rings" such as naphthalene rings (non-ring assembly arene rings).

[0053] Preferred Z 2 is C 6-14 The arene ring is at least one type of arene ring selected from a benzene ring, a naphthalene ring, and a biphenyl ring, and is more preferably a fused polycyclic arene ring such as a naphthalene ring, since it can satisfy optical properties such as a high refractive index, a low Abbe number, and a low birefringence, high heat resistance, high moldability, and polymerization reactivity (or a high molecular weight) in a well-balanced manner. 2 The size of Z 2 The number of carbon atoms (or the number of benzene rings) is Z 1 may be equal to or smaller than Z 1 If it is too large, the polymerization reactivity may decrease, but Z 1 It seems that it is easier to balance and satisfy each characteristic when it is larger than Z. 2 The number of benzene ring skeletons that make up Z 1 One more aspect than Z, among others 2 is the naphthalene ring and Z 1 In general, birefringence tends to increase as the number of benzene ring skeletons constituting the arene ring increases, but the structural unit represented by formula (1) appears to be able to effectively suppress an excessive increase in birefringence even when the number of benzene ring skeletons is large, while achieving a balanced improvement in properties such as a high refractive index, a low Abbe number, and high heat resistance.

[0054] Z 2 Z in 1 The bonding position with Z is not particularly limited. 2is a naphthalene ring, this naphthalene ring Z 2 Either the 1st or 2nd position (1-naphthyl group or 2-naphthyl group) of 1 It may be bonded to the position 2 (2-naphthyl group) preferably.

[0055] Also, Z 1 Z in 2 The bond position with the group [-Z 2 -(R 1 ) k1 The substitution position of Z is not particularly limited as long as it is a position other than the two carbonyl groups [—C(═O)—]. 1 is a benzene ring, and this benzene ring Z 1 When the two carbonyl groups [-C(=O)-] are bonded to Z in a 1,4-position (p-position) relationship and the number of substitutions m is 2, the optical properties, high heat resistance, high moldability, polymerization reactivity, etc. can be well balanced. 2 is the benzene ring Z 1 2nd place (Z 2 It is preferred that they are bonded in a p-position.

[0056] R 1 is preferably a substituent inert to the polymerization reaction (non-polymerizable group), for example, an alkyl group, specifically, a linear or branched C group such as a methyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, or a hexyl group. 1-10 alkyl groups; cycloalkyl groups which may have an alkyl group such as a propylcyclohexyl group or a pentylcyclohexyl group; halogen atoms such as a fluorine atom, a chlorine atom or a bromine atom; haloalkyl groups (or halogenated alkyl groups), for example, mono- to perhaloalkyl groups such as a trifluoromethyl group or a bromomethyl group; haloalkoxy groups such as a trifluoromethoxy group; alkoxy groups, for example, linear or branched C groups such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a pentyloxy group, a hexyloxy group or a heptyloxy group; 1-10alkoxy groups; aralkyloxy groups such as benzyloxy groups; acyl groups such as acetyl groups; dialkylaminocarbonyl groups such as dimethylaminocarbonyl groups and diethylaminocarbonyl groups; alkylthio groups such as methylthio groups and isopropylthio groups; alkylsulfonyl groups such as methylsulfonyl groups; substituted amino groups, for example, mono- or dialkylamino groups such as dimethylamino groups and diethylamino groups, mono- or diarylamino groups such as diphenylamino groups, and mono- or diacylamino groups such as acetylamino groups; dialkylaminoalkyl groups such as dimethylaminomethyl groups; trialkylsilyl groups such as trimethylsilyl groups; cyano groups; cyanoalkyl groups such as cyanomethyl groups; and nitro groups.

[0057] When k1 is 1 or more, a typical R 1 Examples of the alkyl group include an alkyl group, a halogen atom, a haloalkyl group, an alkoxy group, an aralkyloxy group, and an acyl group, and preferably C 1-4 Alkyl groups such as alkyl groups, linear or branched C 1-4 Alkoxy groups such as alkoxy groups.

[0058] R 1 The number of substitutions k1 in the ring Z can be any integer greater than or equal to 0. 2 The number of R is preferably 0 or 1, particularly 0. When k1 is 2 or more, the number of R is 2 or more. 1 The types of R may be the same or different. 1 The substitution position of is not particularly limited.

[0059] group [-Z 2 -(R 1 ) k1 The number of substitutions m in the ring Z 1The value of m can be appropriately selected depending on the type of resin. For example, it may be an integer of about 1 to 6, and preferably an integer of 1 to 4, an integer of 1 to 3, or an integer of 1 to 2, in the following stepwise order. m is particularly preferably 2, since it provides a balanced combination of optical properties, high heat resistance, high moldability, and polymerization reactivity. If m is too small, it may be difficult to achieve a balanced combination of optical properties such as a high refractive index and high heat resistance. As mentioned above, birefringence generally increases with an increase in the number of benzene ring structures. However, in the structural unit represented by formula (1), even if m is increased, it appears possible to effectively suppress an excessive increase in birefringence while achieving a balanced improvement in properties such as a high refractive index, a low Abbe number, and high heat resistance. On the other hand, if m is too large, the glass transition temperature (Tg) may increase excessively, resulting in a decrease in moldability, and a decrease in polymerization reactivity, which may prevent the polymer from being polymerized to a high molecular weight. Therefore, m may be 1 for applications requiring higher polymerization reactivity (or a high molecular weight).

[0060] When m is 2 or more, two or more groups [-Z 2 -(R 1 ) k1 ] type (i.e., each Z 2 , R 1 and the types of k1, and combinations thereof) may be the same or different from each other, but are preferably the same.

[0061] R 2 is the R 1 The substituent is preferably a non-polymerizable group that is inactive in the polymerization reaction, and examples thereof include hydrocarbon groups such as alkyl groups, cycloalkyl groups, and aralkyl groups (excluding aryl groups). Examples of the alkyl group include linear or branched C groups such as methyl groups, ethyl groups, isopropyl groups, and n-butyl groups. 1-6 Examples of cycloalkyl groups include C alkyl groups such as cyclohexyl groups. 5-10 Examples of aralkyl groups include C aryl groups such as benzyl groups. 6-10 Aryl C 1-6 When k2 is 1 or more, preferred R 2is an alkyl group, and may be a straight or branched C 1-4 Alkyl groups are preferred.

[0062] R 2 The number of substitutions k2 in the ring Z can be any integer greater than or equal to 0. 1 For example, k2 may be an integer of about 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0. When k2 is 2 or more, R 2 The types of R may be the same or different. 2 The substitution position of is not particularly limited.

[0063] The total value of the number of substitutions m and k2 (also referred to as m+k2) may be 1 or more, and the upper limit of m+k2 is 1 Depending on the type of Z 1 The upper limit of m+k2 is the number of hydrogen atoms that can be substituted (or bonded) to Z. 1 is 4 for a benzene ring and 6 for a naphthalene ring.

[0064] Representative examples of the first dicarboxylic acid component (A1) corresponding to the first dicarboxylic acid unit (A1) include, for example, Z 1 is monocyclic or fused polycyclic C 6-10 arene rings, Z 2 C 6-12 arene rings, and the dicarboxylic acid component [mono or di(C 6-12 Aryl) monocyclic or fused polycyclic C 6-10 arene-dicarboxylic acid component], specifically, mono- or di(C terephthalic acid) such as 2-phenyl-terephthalic acid, 2,5-diphenyl-terephthalic acid, 2-(1-naphthyl)-terephthalic acid, 2,5-di(1-naphthyl)-terephthalic acid, 2-(2-naphthyl)-terephthalic acid, and 2,5-di(2-naphthyl)-terephthalic acid. 6-10 aryl)benzenedicarboxylic acids and ester-forming derivatives thereof.

[0065] The first dicarboxylic acid unit (A1) may be contained alone or in combination of two or more. Among the first dicarboxylic acid units (A1), mono- or di-naphthyl terephthalic acid is preferred in that it can satisfy the optical properties, heat resistance, moldability, polymerization reactivity, etc. in a well-balanced manner, and mono- or di-(2-naphthyl) terephthalic acid such as 2-(2-naphthyl)-terephthalic acid and 2,5-di(2-naphthyl)-terephthalic acid is more preferred, and units derived from di-(2-naphthyl)-terephthalic acid such as 2,5-di(2-naphthyl)-terephthalic acid are particularly preferred.

[0066] When the first dicarboxylic acid unit (A1) contains these preferred first dicarboxylic acid units (A1), the proportion thereof is, for example, about 10 to 100 mol %, preferably 50 mol % or more, 70 mol % or more, 90 mol % or more, and more preferably 100 mol %, based on the total first dicarboxylic acid units (A1). That is, the first dicarboxylic acid unit (A1) contains only the above preferred first dicarboxylic acid units (A1), particularly mono- or di-(C) dicarboxylic acid units such as mono- or di-naphthyl terephthalic acid. 6-10 It is preferred that the copolymer is substantially composed of units derived from (aryl)benzenedicarboxylic acid alone.

[0067] The first dicarboxylic acid component (A1) may be a commercially available product or may be synthesized by a conventional method such as a coupling reaction. The coupling reaction is not particularly limited. When using the Suzuki-Miyaura cross-coupling reaction, for example, the group [-Z 2 -(R 1 ) k1 a dicarboxylic acid component in which the group [-Z] is substituted with a coupling reactive group such as a halogen atom, specifically a halogenated arenedicarboxylic acid component such as dimethyl bromoterephthalate or diethyl 2,5-dibromoterephthalate; 2 -(R 1 ) k1and a boron compound such as a boronic acid or boronic acid ester corresponding to the above-mentioned 2-amino-3-phenylboronic acid, specifically an areneboronic acid such as 2-naphthylboronic acid; in the presence of a base such as a metal carbonate, specifically an alkali metal carbonate such as potassium carbonate; and a transition metal catalyst such as a palladium catalyst or its precursor, specifically a palladium catalyst precursor such as palladium acetate [Pd(OAc)2]; and, if necessary, a ligand such as a phosphine, a phase transfer catalyst, and a solvent, followed by a coupling reaction under an inert gas atmosphere such as a nitrogen atmosphere.

[0068] Second Dicarboxylic Acid Unit (A2) The dicarboxylic acid unit (A) may or may not contain a second dicarboxylic acid unit (A2) represented by the following formula (2) as necessary. When the second dicarboxylic acid unit (A2) is contained, birefringence tends to be easily reduced while maintaining a relatively high refractive index, and polymerization reactivity tends to be easily improved even when the polymer has a rigid fluorene skeleton.

[0069] [ka]

[0070] (In the formula, R 3 represents a substituent, k3 represents an integer of 0 to 8, A 1a and A 1b represent independently a divalent hydrocarbon group which may have a substituent.

[0071] In the formula (2), R 3 The substituent represented by is preferably a substituent inactive to the polymerization reaction (non-polymerizable group), 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.

[0072] Examples of the alkyl group include linear or branched C alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl groups. 1-12The aryl group includes a C alkyl group such as a phenyl group and a naphthyl group. 6-12 Examples include an aryl group.

[0073] These substituents R 3 Among these, when the number of substitutions k3 is 1 or more, a cyano group, a halogen atom, an alkyl group or an aryl group is preferred, an alkyl group or an aryl group is more preferred, and an aryl group is particularly preferred. Preferred alkyl groups are linear or branched C 1-8 alkyl group, more preferably a linear or branched C 1-4 The aryl group is preferably a phenyl group or a naphthyl group, more preferably a naphthyl group, especially a 2-naphthyl group.

[0074] The number of substitutions k3 may be, for example, an integer of about 0 to 6, and preferred ranges are, in the following stepwise order, integers of 0 to 4, integers of 0 to 3, and integers of 0 to 2, more preferably 0 or 1, and particularly preferably 0. 3 is an aryl group, the number of substitutions k3 may be an integer of 1 to 6, and is preferably an integer of 1 to 4, an integer of 1 to 3, an integer of 1 to 2, and particularly preferably 2.

[0075] In addition, the group R 3 When the number of substitutions k3 is 2 or more, two or more groups R 3 The types of R may be the same or different from each other, but are preferably the same. 3 The bonding position (substitution position) of is not particularly limited, and examples thereof include the 2-position, 7-position, and 2,7-position of the fluorene ring, with the 2,7-position being preferred.

[0076] Base A 1a and A 1b Examples of the hydrocarbon group represented by the formula (I) include linear or branched alkylene groups, such as methylene, ethylene, trimethylene, propylene, 1,2-butanediyl, and 2-methylpropane-1,3-diyl groups. 1-8Preferred alkylene groups include linear or branched C alkylene groups such as methylene, ethylene, trimethylene, propylene, and 2-methylpropane-1,3-diyl. 1-6 alkylene groups, and more preferably linear or branched C 1-4 It is an alkylene group.

[0077] The substituent that the hydrocarbon group may have is preferably a non-polymerizable group that is inert to the polymerization reaction, and examples thereof include aryl groups such as a phenyl group, and cycloalkyl groups such as a cyclohexyl group. 1a and A 1b Examples of the alkyl group include a 1-phenylethylene group and a 1-phenylpropane-1,2-diyl group.

[0078] Base A 1a and A 1b is linear or branched chain C 2-4 Alkylene groups are preferred, and among these, linear or branched C alkylene groups such as ethylene and propylene groups are preferred. 2-3 An alkylene group, particularly an ethylene group, is preferred. 1a and A 1b The types may be different from each other, but are preferably the same.

[0079] Representative second dicarboxylic acid components (A2) corresponding to the second dicarboxylic acid unit (A2) represented by the formula (2) include dicarboxylic acid components (A2-1) in which k3 is 0, dicarboxylic acid components (A2-2) in which k3 is 1 or more and R 3 Examples of the dicarboxylic acid component (A2-2) include a dicarboxylic acid component containing an aryl group. 1a and A 1b is linear or branched C 2-6 Alkylene group, k3 is 0 to 2, R 3 corresponds to an aryl group.

[0080] Specific examples of the dicarboxylic acid component (A2-1) include: 1a and A1b is linear or branched C 2-6 Examples include alkylene groups and components where k3 is 0. For example, 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)fluorene and 9,9-bis(2-carboxypropyl)fluorene. 2-6 alkyl)fluorene; and ester-forming derivatives thereof.

[0081] Specific examples of the dicarboxylic acid component (A2-2) include: 1a and A 1b is linear or branched C 2-6 alkylene group, k3 is 1 or more, preferably 1 to 3, particularly 2, R 3 corresponds to an aryl group, for example, 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)-2,7-diphenylfluorene, 9,9-bis(2-carboxyethyl)-2,7-di(2-naphthyl)fluorene, 9,9-bis(2-carboxypropyl)-2,7-di(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-2,7-di(1-naphthyl)fluorene, and 9,9-bis(2-carboxyethyl)-3,6-di(2-naphthyl)fluorene. 2-6 Alkyl)-diC 6-10 aryl-fluorenes; and ester-forming derivatives thereof.

[0082] The second dicarboxylic acid units (A2) derived from these second dicarboxylic acid components (A2) may be contained alone or in combination of two or more. For example, in order to achieve a good balance of optical properties, heat resistance, and moldability, it is preferred to combine the second dicarboxylic acid units (A2) containing the dicarboxylic acid components (A2-1) and (A2-2) with the first dicarboxylic acid units (A1).

[0083] Preferred second dicarboxylic acid units (A2) include 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)fluorene, which is the dicarboxylic acid component (A2-1). 2-4alkyl)fluorene; 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)-2,7-di(2-naphthyl)fluorene, which is the dicarboxylic acid component (A2-2) 2-4 alkyl)-dinaphthylfluorene, and 9,9-bis(carboxy C such as 9,9-bis(2-carboxyethyl)fluorene. 2-3 Alkyl)fluorene;9,9-bis(carboxy C 2-3 A unit derived from 9,9-bis(2-carboxyethyl)-2,7-di(2-naphthyl)fluorene is more preferred, and a unit derived from 9,9-bis(carboxy C)-dinaphthylfluorene such as 9,9-bis(2-carboxyethyl)-2,7-di(2-naphthyl)fluorene is more preferred because it can provide a good balance of optical properties such as a high refractive index, a low Abbe number, and a low birefringence, as well as heat resistance and moldability. 2-3 Alkyl)-dinaphthylfluorene is particularly preferred.

[0084] When the second dicarboxylic acid unit (A2) contains these preferred second dicarboxylic acid units (A2), the proportion thereof is, for example, about 10 to 100 mol %, preferably 50 mol % or more, 70 mol % or more, 90 mol % or more, and more preferably 100 mol %, based on the total second dicarboxylic acid units (A2). That is, the second dicarboxylic acid unit (A2) may contain only the preferred second dicarboxylic acid units (A2), particularly 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)fluorene. 2-4 It is preferable that the alkyl group is substantially formed solely from units derived from alkylfluorene.

[0085] The proportion of the dicarboxylic acid component (A2-1) relative to the total second dicarboxylic acid units (A2) is, for example, about 10 to 100 mol %, preferably 50 mol % or more, 70 mol % or more, 90 mol % or more, stepwise thereafter, and more preferably 100 mol %.

[0086] Furthermore, combining a second dicarboxylic acid unit (A2) containing at least a dicarboxylic acid component (A2-2) with a first dicarboxylic acid unit (A1) appears to facilitate a well-balanced satisfaction of optical properties, heat resistance, moldability, etc. The proportion of the dicarboxylic acid component (A2-2) relative to the total second dicarboxylic acid unit (A2) is, for example, about 1 to 100 mol%, preferably 3 to 80 mol%, 5 to 50 mol%, 8 to 40 mol%, 10 to 30 mol%, and 15 to 25 mol% in the following stepwise manner. When the proportion of the dicarboxylic acid component (A2-2) is within this range, it appears that a better balance of optical properties such as a high refractive index, a low Abbe number, and low birefringence, as well as heat resistance and moldability, can be achieved.

[0087] The ratio of the dicarboxylic acid component (A2-1) to the dicarboxylic acid component (A2-2) is not particularly limited and can be selected from a molar ratio of the former / the latter of 0 / 100 to 100 / 0, for example, 1 / 99 to 99 / 1, and preferably the following stepwise ratios: 20 / 80 to 97 / 3, 50 / 50 to 95 / 5, 60 / 40 to 92 / 8, 70 / 30 to 90 / 10, and 75 / 25 to 85 / 15. Combining the second dicarboxylic acid unit (A2) containing at least both dicarboxylic acid components (A2-1) and (A2-2) with the first dicarboxylic acid unit (A1) makes it easier to achieve a better balance of optical properties, heat resistance, moldability, and other properties. In particular, when the ratio of (A2-1) to (A2-2) is within the above range, it appears that an even better balance of optical properties such as a high refractive index, a low Abbe number, and low birefringence, as well as heat resistance and moldability, can be achieved.

[0088] Third Dicarboxylic Acid Unit (A3) The dicarboxylic acid unit (A) may or may not contain a third dicarboxylic acid unit (A3), which is a structural unit derived from an aliphatic dicarboxylic acid component, as necessary. The inclusion of the third dicarboxylic acid unit (A3) appears to be able to suppress an excessive increase in the glass transition temperature and improve moldability.

[0089] Furthermore, when the third dicarboxylic acid unit (A3) is combined with the first dicarboxylic acid unit (A1), preferably with the first dicarboxylic acid unit (A1) and the second dicarboxylic acid unit (A2), and more preferably with the first dicarboxylic acid unit (A1) and the dicarboxylic acid unit (A2-2), a resin with a high refractive index, a low Abbe number, and low birefringence can be obtained, despite the inclusion of aliphatic dicarboxylic acid-derived structural units that tend to lower the refractive index. Therefore, a resin with an excellent balance of optical properties, heat resistance, and moldability can be easily and efficiently prepared.

[0090] Examples of the aliphatic dicarboxylic acid component for forming the third dicarboxylic acid unit (A3) include linear or branched alkanedicarboxylic acids, specifically, C alkanedicarboxylic acids such as succinic acid, adipic acid, suberic acid, sebacic acid, and decanedicarboxylic acid. 2-12 Alkane-dicarboxylic acids, etc.; linear or branched unsaturated aliphatic dicarboxylic acids, specifically C such as maleic acid, fumaric acid, and itaconic acid 2-10 Alkene-dicarboxylic acids and ester-forming derivatives thereof are included. The aliphatic dicarboxylic acid component may be either linear or branched, with linear being preferred.

[0091] These third dicarboxylic acid units (A3) can be used alone or in combination of two or more. Of these third dicarboxylic acid units (A3), preferred are structural units derived from linear or branched alkanedicarboxylic acids, and more preferred are structural units derived from alkanedicarboxylic acids having the following carbon numbers (including the carbon atoms of the carboxyl group) in the following order: 2 to 20, 4 to 18, 6 to 16, 7 to 14, and 8 to 12, in particular 9 to 11 carbon atoms such as sebacic acid.

[0092] The proportion of structural units derived from alkanedicarboxylic acids such as sebacic acid (preferably the proportion of third dicarboxylic acid units (A3)) is, for example, about 10 to 100 mol %, preferably 50 mol % or more, 70 mol % or more, 90 mol % or more, and more preferably 100 mol %, based on the total third dicarboxylic acid units (A3).

[0093] Fourth Dicarboxylic Acid Unit (A4) The dicarboxylic acid unit (A) may or may not contain a fourth dicarboxylic acid unit (A4) that is different from the first dicarboxylic acid unit (A1), the second dicarboxylic acid unit (A2), and the third dicarboxylic acid unit (A3) [that does not belong to the category of the first to third dicarboxylic acid units (A1) to (A3)], as necessary.

[0094] Examples of the fourth dicarboxylic acid unit (A4) include structural units derived from aromatic dicarboxylic acid components (excluding the first dicarboxylic acid unit (A1) and the second dicarboxylic acid unit (A2)), alicyclic dicarboxylic acid components, etc.

[0095] Examples of the aromatic dicarboxylic acid component include monocyclic aromatic dicarboxylic acids, polycyclic aromatic dicarboxylic acids, and ester-forming derivatives thereof. Examples of the monocyclic aromatic dicarboxylic acids include benzene dicarboxylic acids such as phthalic acid, terephthalic acid, and isophthalic acid; alkyl benzene dicarboxylic acids, specifically, C alkyl benzene dicarboxylic acids such as 4-methylisophthalic acid; 1-4 alkyl-benzenedicarboxylic acids and the like.

[0096] Examples of polycyclic aromatic dicarboxylic acids include condensed polycyclic aromatic dicarboxylic acids, specifically condensed polycyclic C dicarboxylic acids such as naphthalenedicarboxylic acid, anthracenedicarboxylic acid, and phenanthrenedicarboxylic acid. 10-24 Arene-dicarboxylic acids, preferably fused polycyclic C 10-14arene-dicarboxylic acids, etc.; biaryl dicarboxylic acids, specifically, bi-C such as 2,2'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, and 3,3'-dicarboxy-1,1'-binaphthyl 6-10 Aryl-dicarboxylic acids, etc.; Bis(carboxyalkoxy)bis(C) 6-10 Aryl, specifically bis(carboxy C such as 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl 1-4 Alkoxy)BiC 6-10 Aryl, etc.; Bis[(carboxyalkoxy)-C 6-10 aryl]alkanes, specifically bis[(carboxy C 1-4 Alkoxy)-C 6-10 Aryl)C 1-6 Alkanes, etc.; diarylalkanedicarboxylic acids, specifically, di-C such as 4,4'-diphenylmethanedicarboxylic acid 6-10 Aryl C 1-6 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; diaryl ether dicarboxylic acids, specifically, di(C) such as 4,4'-diphenyl ether dicarboxylic acid 6-10 aryl) ether-dicarboxylic acids; diarylsulfonedicarboxylic acids, specifically, di(C) such as 4,4'-diphenylsulfonedicarboxylic acid; 6-10 aryl) sulfone-dicarboxylic acids and the like.

[0097] Examples of the naphthalenedicarboxylic acid include 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid.

[0098] 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, bi- or tricycloalkane dicarboxylic acids such as decalin dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid, tricyclodecane dicarboxylic acid, etc.; cycloalkene dicarboxylic acids, specifically, C such as cyclohexene dicarboxylic acid, etc. 5-10 Examples thereof include cycloalkene-dicarboxylic acids; bridged cyclic cycloalkene dicarboxylic acids, specifically bi- or tricycloalkene dicarboxylic acids such as norbornene dicarboxylic acid; and ester-forming derivatives thereof.

[0099] The proportion of the fourth dicarboxylic acid units (A4) is, for example, less than 50 mol%, preferably 30 mol% or less, and more preferably 10 mol% or less, based on the total dicarboxylic acid units (A). It is preferable that the fourth dicarboxylic acid units (A4) are substantially not contained, and when the fourth dicarboxylic acid units (A4) are contained, the proportion may be, for example, about 0.1 to 5 mol%.

[0100] The proportion of the first dicarboxylic acid units (A1) may be selected from the range of, for example, about 1 to 100 mol%, specifically about 1 to 50 mol%, based on the total dicarboxylic acid units (A). To achieve a good balance of optical properties such as a high refractive index, a low Abbe number, and a low birefringence, high heat resistance, high moldability, and polymerization reactivity (or high molecular weight), the proportion is preferably 5 to 75 mol%, 10 to 60 mol%, 15 to 50 mol%, 17 to 40 mol%, and 20 to 30 mol%; for applications where a balance between optical properties, high heat resistance, and high moldability is particularly important, the proportion is preferably 50 to 100 mol%, 60 to 95 mol%, 70 to 90 mol%, and 75 to 85 mol%. If the proportion of the first dicarboxylic acid units (A1) is too high, polymerization reactivity may decrease, making it difficult to increase the molecular weight, or Tg may increase excessively, reducing moldability (productivity). On the other hand, if the amount is too small, it may be difficult to obtain optical properties such as a high refractive index and a low Abbe number, and high heat resistance.

[0101] The total proportion of the first dicarboxylic acid units (A1) and the second dicarboxylic acid units (A2) may be, for example, 1 mol% or more, specifically, may be selected from the range of about 10 to 100 mol%, based on the total dicarboxylic acid units (A), and is preferably 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, and particularly preferably 100 mol%.

[0102] The total proportion of the first dicarboxylic acid units (A1), the second dicarboxylic acid units (A2) and the third dicarboxylic acid units (A3) may be, for example, 1 mol% or more, specifically, may be selected from the range of about 10 to 100 mol%, based on the total dicarboxylic acid units (A), and is preferably 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, and particularly preferably 100 mol%.

[0103] The ratio of the first dicarboxylic acid unit (A1) to the second dicarboxylic acid unit (A2) (also referred to as A1 / A2) may be selected, for example, from a range of about A1 / A2 (molar ratio) = 1 / 99 to 100 / 0, specifically about 5 / 95 to 90 / 10. In order to achieve a good balance of optical properties such as a high refractive index, a low Abbe number, and a low birefringence, high heat resistance, high moldability, and high polymerization reactivity (or high molecular weight), the ratio may be preferably in the following stepwise order: 5 / 95 to 75 / 25, 10 / 90 to 60 / 40, 15 / 85 to 50 / 50, 17 / 83 to 40 / 60, or 20 / 80 to 30 / 70. However, in order to achieve a better balance of the above properties, the following stepwise ratios are more preferred: 5 / 95 to 30 / 70, 8 / 92 to 25 / 75, and 10 / 90 to 20 / 80; and for applications where a high refractive index is particularly important while still achieving a good balance of optical properties, high heat resistance, and high moldability, the following stepwise ratios are preferred: 50 / 50 to 100 / 0, 60 / 40 to 95 / 5, 70 / 30 to 90 / 10, and 75 / 25 to 85 / 15, but more preferably 1 / 99 to 50 / 50, 5 / 95 to 40 / 60, 10 / 90 to 30 / 70, and 15 / 85 to 25 / 75. If the proportion of the second dicarboxylic acid unit (A2) is too low, it may be difficult to increase the molecular weight, which may result in a decrease in moldability and an insufficient reduction in birefringence. On the other hand, if the proportion of the second dicarboxylic acid unit (A2) is too high, optical properties such as a high refractive index and a low Abbe number may not be obtained, and heat resistance may decrease.

[0104] The ratio of the first dicarboxylic acid unit (A1) to the third dicarboxylic acid unit (A3) (also referred to as A1 / A3) (molar ratio) may be selected, for example, from about 1 / 99 to 100 / 0, specifically from about 5 / 95 to 90 / 10, preferably from the following stepwise ratios: 10 / 90 to 70 / 30, 20 / 80 to 55 / 45, 30 / 70 to 45 / 55, and 35 / 65 to 40 / 60. If the proportion of the third dicarboxylic acid unit (A3) is too high, optical properties and heat resistance may be reduced. Furthermore, if the proportion of the first dicarboxylic acid unit (A1) is too high, polymerization reactivity may be reduced, making it difficult to achieve a high molecular weight, or Tg may be excessively elevated, resulting in reduced moldability (productivity).

[0105] The ratio of the second dicarboxylic acid units (A2) to the third dicarboxylic acid units (A3) (also referred to as A2 / A3) (molar ratio) may be selected, for example, from about 0 / 100 to 100 / 0, specifically from about 10 / 90 to 95 / 5, and preferably from the following stepwise ratios: 30 / 70 to 90 / 10, 55 / 45 to 85 / 15, and 65 / 35 to 75 / 25. If the proportion of the second dicarboxylic acid units (A2) is too high, the optical properties and heat resistance may be reduced, while if the proportion of the third dicarboxylic acid units (A3) is too high, the optical properties and heat resistance may be reduced. Within the preferred ranges, it is easy to achieve a good balance between the optical properties, heat resistance, and moldability.

[0106] The proportion of the dicarboxylic acid units (A) [total amount of the first to fourth dicarboxylic acid units (A1) to (A4)] relative to the total amount of structural units of the thermoplastic resin (total amount of units derived from all monomer components constituting the thermoplastic resin) may be, for example, 1 mol % or more, specifically about 10 to 50 mol %, and preferably 20 to 50 mol %, 30 to 50 mol %, and 40 to 50 mol % in the following stepwise manner.

[0107] [Diol unit (B)] The thermoplastic resin is preferably a polyester resin containing diol units (B) in addition to dicarboxylic acid units (A). The diol units (B) are not particularly limited, but preferably contain at least one diol unit selected from the group consisting of a first diol unit (B1) represented by the following formula (3) and a second diol unit (B2) represented by the following formula (4), and more preferably contain both.

[0108] First Diol Unit (B1) The diol unit (B) may or may not contain a first diol unit (B1) represented by the following formula (3), as necessary: ​​When the first diol unit (B1) is contained, the optical properties (high refractive index, low Abbe number, and low birefringence) can be improved in a balanced manner, while the heat resistance can be improved.

[0109] [ka]

[0110] (In the formula, R 4 represents a substituent, k4 represents an integer of 0 to 8, Z 3a and Z 3b each independently represents an arene ring, R 5a and R 5b each independently represents a substituent, k5a and k5b each independently represents an integer of 0 or more, A 2a and A 2b each independently represents a linear or branched alkylene group, and n2a and n2b each independently represent an integer of 0 or 1 or more.

[0111] In the formula (3), Z 3a and Z 3b Examples 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. Polycyclic arene rings include fused polycyclic arene rings and ring-assembled arene rings.

[0112] The fused polycyclic arene ring includes, for example, the Z 1 The preferred fused polycyclic arene rings are fused polycyclic C 10-16 arene rings, more preferably fused polycyclic C 10-14 An arene ring is preferred, and a naphthalene ring is particularly preferred.

[0113] Examples of the ring-assembled arene ring include the Z 2 Examples of the ring-assembled arene ring include the same rings as those exemplified in the section 1. 6-10 An arene ring is exemplified, and a biphenyl ring is particularly preferred.

[0114] Z 3a and Z 3bThe types of Z may be the same or different from each other, and are preferably the same. 3a and Z 3b is a C ring such as a benzene ring, naphthalene ring, or biphenyl ring. 6-12 arene rings, and more preferably C rings such as benzene rings and naphthalene rings. 6-10 arene rings, particularly naphthalene rings.

[0115] In addition, Z bonded to the 9-position of the fluorene ring 3a and Z 3b The substitution position of is not particularly limited, and for example, Z 3a , Z 3b When Z is a benzene ring, it may be at any position. 3a , Z 3b is a naphthalene ring, it is either the 1-position or the 2-position, preferably the 2-position, and Z 3a , Z 3b When is a biphenyl ring, it is at the 2-, 3- or 4-position, preferably the 3-position.

[0116] R 4 The substituent represented by the formula (2) is preferably a non-polymerizable group that is inactive in the polymerization reaction, and examples thereof include the group R 3 and the like, including preferred embodiments thereof.

[0117] Also, R 4 The number of substitutions k4 is the same as k3 described in the section on formula (2), including preferred embodiments, and is particularly preferably 0. When the number of substitutions k4 is 2 or more, two or more groups R 4 The types of groups R may be the same or different, and are preferably the same. 4 The bonding position (substitution position) of is not particularly limited, and examples thereof include the 2-position, 7-position, and 2,7-position of the fluorene ring, with the 2,7-position being preferred.

[0118] R 5a and R 5bThe substituent represented by the formula (I) is preferably a non-polymerizable group that is inactive in the polymerization reaction, and examples thereof include halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups (or groups R h ); a group -OR corresponding to the above hydrocarbon group, such as an alkoxy group, a cycloalkyloxy group, an aryloxy group, or an aralkyloxy group; h (In the formula, R h represents the hydrocarbon group; a group -SR corresponding to the hydrocarbon group, such as an alkylthio group, a cycloalkylthio group, an arylthio group, or an aralkylthio group. h (In the formula, R h represents the hydrocarbon group); acyl group; nitro group; cyano group; substituted amino group, and the like.

[0119] R h Examples of the alkyl group represented by the formula (I) include a linear or branched C alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, and a t-butyl group. 1-10 Alkyl groups, preferably linear or branched C 1-6 Alkyl groups, more preferably linear or branched C 1-4 Examples include alkyl groups.

[0120] R h Examples of the cycloalkyl group represented by the formula (I) include C cyclopentyl group, cyclohexyl group, etc. 5-10 Examples include a cycloalkyl group.

[0121] R h Examples of the aryl group represented by the formula (I) include C phenyl group, alkylphenyl group, biphenylyl group, naphthyl group, etc. 6-12 Examples of the alkylphenyl group include a methylphenyl group (tolyl group) and a dimethylphenyl group (xylyl group).

[0122] R h Examples of the aralkyl group represented by the formula (I) include C aryl groups such as benzyl and phenethyl groups.6-10 Aryl-C 1-4 Examples include alkyl groups.

[0123] Group -OR h The hydrocarbon group R h and preferred embodiments thereof, for example, linear or branched C groups such as methoxy groups. 1-10 C such as alkoxy group, cyclohexyloxy group 5-10 C such as cycloalkyloxy group, phenoxy group 6-10 C such as aryloxy group, benzyloxy group 6-10 Aryl-C 1-4 Examples thereof include an alkyloxy group.

[0124] Group-SR h The hydrocarbon group R h and preferred embodiments thereof, for example, linear or branched C groups such as methylthio groups. 1-10 C such as alkylthio group, cyclohexylthio group 5-10 C such as cycloalkylthio group, thiophenoxy group (phenylthio group) 6-10 C such as arylthio group, benzylthio group 6-10 Aryl-C 1-4 Examples include an alkylthio group.

[0125] Examples of the acyl group include C acetyl groups. 1-6 Examples include an acyl group.

[0126] Examples of the substituted amino group include mono- or di-alkylamino groups, mono- or bis(alkylcarbonyl)amino groups, etc. Examples of the mono- or di-alkylamino group include mono- or di-C groups such as dimethylamino groups. 1-4 Examples of the mono- or bis(alkylcarbonyl)amino group include mono- or bis(C 1-4 alkyl-carbonyl)amino groups.

[0127] Representative R5a and R 5b Examples of R include halogen atoms, hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups, alkoxy groups, acyl groups, nitro groups, cyano groups, and substituted amino groups. When the number of substitutions k5a and k5b is 1 or more, preferred R 5a , R 5b Examples of the alkyl group include an alkyl group, a cycloalkyl group, an aryl group, and an alkoxy group, and more preferably a linear or branched C 1-6 C such as alkyl group and cyclohexyl group 5-8 C such as cycloalkyl group and phenyl group 6-14 Linear or branched C such as aryl group, methoxy group 1-4 Among these, alkyl groups and aryl groups are preferred, and in particular, straight-chain or branched C groups such as methyl groups are preferred. 1-4 C such as alkyl group and phenyl group 6-10 An aryl group is preferred. 5a , R 5b is an aryl group, R 5a , R 5b are rings Z 3a , Z 3b may form the ring assembly arene ring together with

[0128] R 5a , R 5b The substitution numbers k5a and k5b of the ring Z 3a , Z 3b The number of k5a and k5b can be appropriately selected depending on the type of R, and may be, for example, an integer of about 0 to 6, preferably an integer of 0 to 4, more preferably an integer of 0 to 2, even more preferably 0 or 1, and particularly preferably 0. k5a and k5b may be different from each other, but are preferably the same. When k5a is 2 or more, two or more R 5a may be the same or different from each other, and k5b and R 5b The same applies to R 5a , R 5b The types of R may be the same or different from each other. 5a , R5b The substitution position of Z is not particularly limited. 3a , Z 3b In the above, the substituent may be any substituent other than the ether bond (—O—) forming the main chain and the bonding position with the 9-position of the fluorene ring. For example, Z 3a , Z 3b may be substituted at the ortho position (carbon atom adjacent to the bonding position of the ether bond) relative to the ether bond (—O—).

[0129] Alkylene Group A 2a , A 2b 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 preferably straight-chain or branched-chain C 2-4 Alkylene groups, more preferably linear or branched C groups such as ethylene groups and propylene groups 2-3 Alkylene groups, especially ethylene groups, are preferred.

[0130] Alkyleneoxy group [-(A 2a O)-], [-(A 2b The repeat numbers (number of moles added) n2a and n2b of the formula [O)-] may each be 0 or greater and can be selected, for example, from a range of about 0 to 15, preferably in the following stepwise order: 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, and 0 to 1. Furthermore, when the repeat numbers n2a and n2b are 1 or greater, polymerization reactivity is easily improved, and they can be selected, for example, from a range of about 1 to 15, preferably in the following stepwise order: 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, and 1 to 2, with 1 being particularly preferred.

[0131] In the present specification and claims, the "number of repetitions (number of moles added)" may be an average value (arithmetic mean value, additive mean value) or an average number of moles added, and preferred embodiments may be the same as the above-mentioned preferred range of integers. If n2a and n2b are too large, the heat resistance and refractive index may decrease. Furthermore, n2a and n2b may be the same or different. When n2a is 2 or more, two or more alkyleneoxy groups [-(A 2a The types of n2b and the group [-(A 2b The same applies to A 2a and A 2b The types may be the same or different from each other.

[0132] The group [-O-(A 2a O) n2a -], [-O-(A 2b O) n2b -] (i.e., the ether bond forming the main chain) 3a , Z 3b The substitution position for Z is not particularly limited. 3a , Z 3b The group [-O-(A 2a O) n2a -], [-O-(A 2b O) n2b -] Ring Z 3a , Z 3b The substitution position for Z 3a , Z 3b When Z is a benzene ring, it is preferably substituted at the 2-, 3- or 4-position of the phenyl group bonded to the 9-position of the fluorene ring, among which the 3- or 4-position, and particularly the 4-position. 3a , Z 3b When Z is a naphthalene ring, it is often substituted at any one of the 5- to 8-positions of the naphthyl group bonded to the 9-position of the fluorene ring. For example, the 1- or 2-position of the naphthalene ring is substituted with the 9-position of the fluorene ring (substitution in a 1-naphthyl or 2-naphthyl relationship), and it is preferred that Z be substituted with the 1,5- or 2,6-position, particularly 2,6-position, relative to this substitution position.3a , Z 3b is a ring-assembled arene ring, the group [-O-(A 2a O) n2a -], [-O-(A 2b O) n2b The substitution position of Z - is not particularly limited, and may be, for example, substituted on the arene ring bonded to the 9-position of the fluorene or on the arene ring adjacent to this arene ring. 1 , Z 2 is a biphenyl ring (or Z 3a , Z 3b is a benzene ring, k5a and k5b are 1, R 5a , R 5b is a phenyl group), the 3- or 4-position of the biphenyl ring, preferably the 3-position, may be bonded to the 9-position of the fluorene. When the 3-position of the biphenyl ring is bonded to the 9-position of the fluorene, the group [—O—(A 2a O) n2a -], [-O-(A 2b O) n2b The substitution position of -] may be, for example, any of the 2-, 4-, 5-, 6-, 2'-, 3'-, and 4'-positions of the biphenyl ring, preferably the 6- or 4'-position, and particularly preferably the 6-position.

[0133] Examples of the first diol component (B1) corresponding to the first diol unit (B1) include 9,9-bis(hydroxyaryl)fluorenes in which n2a and n2b are 0 in the formula (3); and 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes in which n2a and n2b are 1 or more, for example, about 1 to 10.

[0134] In this specification and claims, unless otherwise specified, the term "(poly)alkoxy" is used to mean both an alkoxy group and a polyalkoxy group.

[0135] Examples of 9,9-bis(hydroxyaryl)fluorenes include 9,9-bis(hydroxyphenyl)fluorene, 9,9-bis(alkyl-hydroxyphenyl)fluorene, 9,9-bis(aryl-hydroxyphenyl)fluorene, and 9,9-bis(hydroxynaphthyl)fluorene.

[0136] Examples of 9,9-bis(hydroxyphenyl)fluorene include 9,9-bis(4-hydroxyphenyl)fluorene.

[0137] Examples of the 9,9-bis(alkyl-hydroxyphenyl)fluorene include 9,9-bis[(mono- or di-)C]fluorene such as 9,9-bis(4-hydroxy-3-methylphenyl)fluorene and 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene. 1-4 alkyl-hydroxyphenyl]fluorene and the like.

[0138] Examples of 9,9-bis(aryl-hydroxyphenyl)fluorene include 9,9-bis(C 6-10 aryl-hydroxyphenyl)fluorene.

[0139] Examples of 9,9-bis(hydroxynaphthyl)fluorene include 9,9-bis(6-hydroxy-2-naphthyl)fluorene and 9,9-bis(5-hydroxy-1-naphthyl)fluorene.

[0140] Examples of 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes include 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorene, 9,9-bis[alkyl-hydroxy(poly)alkoxyphenyl]fluorene, 9,9-bis[aryl-hydroxy(poly)alkoxyphenyl]fluorene, and 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorene.

[0141] Examples of the 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[hydroxy(mono- to deca)C such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene and 9,9-bis[4-(2-hydroxypropoxy)phenyl]fluorene. 2-4 alkoxy-phenyl]fluorene and the like.

[0142] Examples of the 9,9-bis[alkyl-hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[(mono- or di-)C such as 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene, and 9,9-bis[4-(2-hydroxypropoxy)-3-methylphenyl]fluorene. 1-4 Alkyl-hydroxy (mono or deca)C 2-4 alkoxy-phenyl]fluorene and the like.

[0143] Examples of the 9,9-bis[aryl-hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[C such as 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene and 9,9-bis(4-(2-hydroxypropoxy)-3-phenylphenyl)fluorene. 6-10 Aryl-hydroxy(mono or deca)C 2-4 alkoxy-phenyl]fluorene and the like.

[0144] Examples of the 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorene include 9,9-bis[hydroxy(mono- to deca)C such as 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, 9,9-bis[5-(2-hydroxyethoxy)-1-naphthyl]fluorene, and 9,9-bis[6-(2-hydroxypropoxy)-2-naphthyl]fluorene. 2-4 Alkoxy-naphthyl]fluorene and the like.

[0145] These first diol units (B1) may be contained alone or in combination of two or more. Preferred first diol units (B1) include 9,9-bis[hydroxy(mono- to penta)C 2-4 Alkoxy C 6-10 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes such as 9,9-bis[hydroxy(poly)alkoxyaryl]fluorene, more preferably 9,9-bis[hydroxyC 2-4 Alkoxy C 6-10 aryl]fluorene, more preferably 9,9-bis[hydroxy C such as 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene. 2-3 It is a unit derived from alkoxy-naphthyl]fluorene.

[0146] When the first diol unit (B1) contains these preferred first diol units (B1), the proportion thereof is, for example, about 10 to 100 mol %, preferably 50 mol % or more, 70 mol % or more, 90 mol % or more, and more preferably 100 mol %, based on the total first diol units (B1). That is, when the first diol unit (B1) contains only the above-mentioned preferred first diol units (B1), in particular, 9,9-bis[hydroxy C] such as 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, 2-3 It is preferable that the fluorene-based polymer is substantially composed of units derived from alkoxy-naphthylfluorene.

[0147] Second Diol Unit (B2) The diol unit (B) may or may not contain a second diol unit (B2) represented by the following formula (4), as necessary: ​​When the diol unit (B2) is contained, the polymerization reaction proceeds efficiently, making it easier to adjust the molecular weight to a high level, and the thermoplastic resin is endowed with flexibility or toughness, thereby improving moldability and handleability.

[0148] [ka]

[0149] (In the formula, A3 represents a linear or branched alkylene group, and n3 represents an integer of 1 or more.

[0150] In the formula (4), A 3 Examples of the alkylene group represented by the formula (I) include C groups such as an ethylene group, a propylene group, a trimethylene group, a 1,2-butanediyl group, a 1,3-butanediyl group, a tetramethylene group, a 1,5-pentanediyl group, a 1,6-hexanediyl group, a 1,8-octanediyl group, and a 1,10-decanediyl group. 2-12 Preferred linear or branched alkylene groups A 3 The following steps are taken: 2-10 Alkylene group, C 2-8 Alkylene group, C 2-6 Alkylene group, C 2-4 C alkylene groups, more preferably ethylene groups, propylene groups, etc. 2-3 An alkylene group is preferred, with an ethylene group being particularly preferred.

[0151] Alkyleneoxy group [-(A 3 The repeat number n3 of the alkyleneoxy group (-A)- may be selected from the range of about 1 to 10, for example, and is preferably 1 to 4, 1 to 3, 1 to 2, and particularly preferably 1. The repeat number n3 may be an average value (arithmetic mean value or additive mean value), and preferred embodiments are the same as the range of integers described above. When n3 is 2 or more, two or more alkyleneoxy groups (-A)- may be selected from the range of about 1 to 10, for example, and is preferably 1 to 4, 1 to 3, 1 to 2, and particularly preferably 1. 3 The types of O-) may be different from each other, but are preferably the same.

[0152] Examples of the second diol component (B2) corresponding to the second diol unit (B2) represented by the formula (4) include alkanediols (or alkylene glycols), polyalkanediols (or polyalkylene glycols), and the like.

[0153] Examples of alkylene glycols include those represented by the formula (4) where n3 is 1 and A 3corresponding to the alkylene group exemplified above, specifically, linear or branched C alkylene compounds such as ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, tetramethylene glycol (or 1,4-butanediol), 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, and 1,10-decanediol. 2-12 alkylene glycol, etc., and a preferred embodiment is 3 The same applies to

[0154] The polyalkylene glycol may be, for example, a polyalkylene glycol represented by the formula (4) in which n3 is 2 or more, preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 to 4; 3 corresponding to the alkylene group exemplified above, specifically, di- or deca-linear or branched C alkylenes such as diethylene glycol, dipropylene glycol, and triethylene glycol. 2-12 alkylene glycols, and the like, preferably di- or hexa-straight or branched chain C 2-6 Alkylene glycol, more preferably di- or tetra-linear or branched C 2-4 Alkylene glycols are included.

[0155] The second diol unit (B2) formed by these second diol components (B2) may be contained alone or in combination of two or more. A preferred second diol unit (B2) is a linear or branched C diol, which is easily able to maintain high heat resistance. 2-6 alkylene glycols such as alkylene glycols, preferably linear or branched C 2-4 Alkylene glycol, more preferably linear or branched C alkylene glycol such as ethylene glycol or propylene glycol 2-3 It is preferred that the alkylene glycol contains units derived from alkylene glycol, particularly ethylene glycol.

[0156] When the second diol units (B2) contain these preferred second diol units (B2), the proportion thereof is, for example, about 10 to 100 mol%, preferably 50 mol% or more, 70 mol% or more, 90 mol% or more, and more preferably 100 mol% based on the total second diol units (B2). That is, it is preferred that the second diol units (B2) are substantially composed only of the preferred second diol units (B2), particularly, only of units derived from alkylene glycols such as ethylene glycol.

[0157] Third Diol Unit (B3) The diol unit (B) may not necessarily be contained, but may or may not contain a third diol unit (B3) different from the first diol unit (B1) and the second diol unit (B2), as necessary.

[0158] Examples of the third diol unit (B3) include structural units derived from aromatic diols (excluding the first diol unit (B1)), alicyclic diols, and alkylene oxide (or alkylene carbonate, haloalkanol) adducts of these diol components.

[0159] Examples of aromatic diols include dihydroxyarenes such as hydroquinone and resorcinol; aromatic aliphatic diols such as benzenedimethanol; bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol C, bisphenol G, and bisphenol S; and biphenols such as p,p'-biphenol.

[0160] Examples of alicyclic diols include cycloalkanediols such as cyclohexanediol; bis(hydroxyalkyl)cycloalkanes such as cyclohexanedimethanol; and hydrogenated products of the above aromatic diols such as hydrogenated bisphenol A.

[0161] Examples of alkylene oxide (or corresponding alkylene carbonate, haloalkanol) adducts of these diol components include C 2-4 C alkylene oxide adducts, preferably ethylene oxide adducts, propylene oxide adducts, etc. 2-3 Examples thereof include alkylene oxide adducts, and the number of moles added is not particularly limited.Specific examples include adducts in which about 2 to 10 moles of ethylene oxide are added to 1 mole of bisphenol A.

[0162] The diol unit (B) may contain these third diol units (B3) either alone or in combination of two or more.

[0163] The proportion of the third diol units (B3) is, for example, less than 50 mol%, preferably 30 mol% or less, and more preferably 10 mol% or less, based on the total diol units (B). It is preferable that the diol units (B) are substantially free of the third diol units (B3). When the diol units (B3) are contained, the proportion may be, for example, about 0.1 to 5 mol%.

[0164] The total proportion of the first diol units (B1) and the second diol units (B2) can be selected, for example, from 1 mol% or more, specifically from a range of about 10 to 100 mol%, based on the total diol units (B). Preferred ranges are 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, and particularly 100 mol%.

[0165] The diol unit (B) preferably contains at least one selected from the first diol unit (B1) and the second diol unit (B2), and more preferably contains both. The ratio of the first diol unit (B1) to the second diol unit (B2) (also referred to as B1 / B2) (molar ratio) of the first diol unit (B1) to the second diol unit (B2) may be, for example, about 1 / 99 to 99 / 1, specifically about 10 / 90 to 90 / 10. In order to achieve a good balance of optical properties such as a high refractive index, a low Abbe number, and a low birefringence, high heat resistance, high moldability, and polymerization reactivity (or high molecular weight), the ratio is preferably set to the following stepwise ratios: 40 / 60 to 95 / 5, 50 / 50 to 90 / 10, 60 / 40, etc. In applications where a high refractive index is particularly important while maintaining a balance between optical properties, high heat resistance, and high moldability, the ratios may be preferably in the following stepwise order: 10 / 90 to 75 / 25, 15 / 85 to 65 / 35, 25 / 75 to 55 / 45, and 35 / 65 to 45 / 55, but more preferably in the following stepwise order: 20 / 80 to 95 / 5, 30 / 70 to 90 / 10, 40 / 60 to 80 / 20, 50 / 50 to 70 / 30, and 55 / 45 to 65 / 35. If the proportion of the first diol units (B1) is too low, the refractive index may decrease, the Abbe number may increase, and heat resistance may decrease. If the proportion of the second diol units (B2) is too low, the moldability (or productivity) may decrease, or it may be difficult to increase the molecular weight.

[0166] Carbonate unit (C) When the thermoplastic resin is a polyester resin containing diol units (B), it does not necessarily contain them, but if necessary, it may further contain carbonate units (C) to form a polyester carbonate resin.

[0167] In this specification and claims, the term "carbonate unit" refers to a structural unit derived from a carbonate bond-forming component that can form a carbonate bond [-O-C(=O)-O-] by reacting with a diol component, i.e., a carbonyl group [-C(=O)-]. In other words, a carbonate bond can be formed together with the terminal oxygen atoms of two diol units that are adjacently bonded to the carbonate unit (carbonyl group).

[0168] Therefore, the carbonate bond-forming component (C) may be any compound that can form a carbonate bond by reacting with the diol component, and typical examples of the carbonate bond-forming component (C) include phosgenes such as phosgene and triphosgene, and carbonate diesters such as diphenyl carbonate.

[0169] These carbonate bond-forming components (C) can be used alone or in combination of two or more. Among these carbonate bond-forming components (C), carbonic acid diesters such as diphenyl carbonate are preferred from the viewpoint of safety.

[0170] The ratio of the total amount of dicarboxylic acid units (A) and carbonate units (C) to the diol units (B) in the thermoplastic resin (molar ratio) is 1 / 0.8 to 1 / 1.2, preferably 1 / 0.9 to 1 / 1.1, and is preferably approximately equimolar. The ratio of dicarboxylic acid units (A) to carbonate units (C) (also referred to as A / C) (molar ratio) may be selected from the range of about 99 / 1 to 1 / 99, for example, 90 / 10 to 10 / 90, preferably in the following stepwise manner: 80 / 20 to 20 / 80, 70 / 30 to 30 / 70, and 60 / 40 to 40 / 60. If the proportion of carbonate units (C) is too high, the refractive index and heat resistance may be reduced.

[0171] Other structural units (D) The thermoplastic resin does not necessarily contain a structural unit (D) other than the dicarboxylic acid unit (A), the diol unit (B), and the carbonate unit (C), but may contain such a unit, if necessary, within a range that does not impair the effects of the present invention.

[0172] Examples of other structural units (D) include structural units derived from hydroxycarboxylic acid components, corresponding lactone components, and polyfunctional polymerizable components having three or more polymerizable groups (carboxyl groups and / or hydroxyl groups).

[0173] Examples of the hydroxycarboxylic acid component include aromatic hydroxycarboxylic acids such as hydroxybenzoic acid; aliphatic hydroxycarboxylic acids (hydroxyalkanoic acids) such as lactic acid, 3-hydroxybutyric acid, and 6-hydroxyhexanoic acid; and ester-forming derivatives thereof. Examples of the corresponding lactone component include lactones corresponding to hydroxyalkanoic acids, such as ε-caprolactone. The thermoplastic resin may be a crystalline polymer, but in particular for applications such as optical lenses and other optical components, it is preferable to use a non-liquid crystal polymer that does not contain units derived from aromatic hydroxycarboxylic acids such as hydroxybenzoic acid, and in particular an amorphous polymer, because this makes it easier to reduce birefringence.

[0174] Examples of polyfunctional polymerization components having a total of three or more polymerizable groups (carboxyl groups and / or hydroxyl groups) include trivalent or higher polycarboxylic acids such as trimellitic acid and pyromellitic acid; trivalent or higher polyhydric alcohols such as glycerin and pentaerythritol; and the like.

[0175] The proportion of such other structural units (D) relative to all structural units (the total amount of dicarboxylic acid units (A), diol units (B), carbonate units (C) and other structural units (D)) is, for example, 50 mol% or less, preferably 0 to 30 mol%, 0 to 10 mol%, 0.01 to 5 mol% in steps thereafter, and it is preferable that other structural units (D) are not substantially contained.

[0176] [Method of manufacturing thermoplastic resin] The method for producing a thermoplastic resin (or polycondensation) is not particularly limited except that a dicarboxylic acid component (A) containing at least the first dicarboxylic acid component (A1) is used as a polymerization component, and a conventional method can be used depending on the type of resin and other polymerization components (copolymerization components), etc. For example, in the case of a polyester-based resin such as a polyester resin, it can be produced by reacting a dicarboxylic acid component (A) corresponding to each of the dicarboxylic acid units described above with a diol component (B) corresponding to the diol unit described above, and, if necessary, a carbonate bond-forming component (C), etc., and 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, or an interfacial polymerization method, with a melt polymerization method being preferred.

[0177] The reaction may be carried out in the presence or absence of a solvent depending on the polymerization method. For example, in solution polymerization and interfacial polymerization, conventional solvents such as high-boiling polar solvents and halogenated solvents such as halogenated hydrocarbons may be used. If the solvent remains in the obtained thermoplastic resin, it may corrode the mold during molding. Therefore, from the viewpoint of improving moldability (productivity), polymerization carried out in the absence of a solvent, such as melt polymerization, is preferred.

[0178] Furthermore, in the interfacial polymerization method, salts, for example, inorganic salts such as sodium chloride, are generated as by-products, and these salts may cause turbidity in the obtained thermoplastic resin or its molded article. Therefore, particularly for applications requiring high transparency, such as optical components, it is preferable to use a production method that does not generate salts as by-products.

[0179] Therefore, from the viewpoint of reducing troubles and defects during molding and improving moldability (productivity), particularly the moldability of optical components such as optical lenses, a melt polymerization method (or molten polymer) is most preferred, since it can effectively prevent residual or mixed-in solvents, salts, etc. In the present invention, even a melt polymerization method can prepare a high molecular weight thermoplastic resin, and in particular, a high molecular weight thermoplastic resin can be easily or efficiently prepared despite the inclusion of a polymerization component that is expected to have low polymerization reactivity, such as the first dicarboxylic acid component (A1).

[0180] The ratio of the dicarboxylic acid component (A) to the diol component (B) is usually, for example, 1 / 1.2 to 1 / 0.8, preferably 1 / 1.1 to 1 / 0.9 (molar ratio), but this range is not necessarily required. At least one component selected from each dicarboxylic acid component (A) and each diol component (B) may be used in excess of the intended introduction ratio. For example, the second diol component (B2), such as ethylene glycol, which can be distilled from the reaction system, may be used in excess of the ratio (or introduction ratio) introduced into the polyester resin.

[0181] When the carbonate bond-forming component (C) is used, the ratio of the total amount of the dicarboxylic acid component (A) and the carbonate bond-forming component (C) to the diol component (B) is, for example, the former / latter (molar ratio) = 1 / 1.2 to 1 / 0.8, preferably 1 / 1.1 to 1 / 0.9. Taking into consideration volatilization and decomposition during the reaction, the carbonate bond-forming component (C) may be used in a slight excess relative to the planned introduction rate, for example, 0.1 to 5 mol %, preferably 2 to 3 mol % excess of the carbonate bond-forming component (C) relative to the total amount of the dicarboxylic acid units (A) and the carbonate units (C) (total amount planned to be introduced into the resin).

[0182] The reaction may be carried out in the presence of a catalyst. Conventional esterification catalysts, such as metal catalysts, can be used as the catalyst. Examples of metal catalysts include metal compounds containing alkali metals such as sodium; alkaline earth metals such as magnesium, calcium, and barium; transition metals such as titanium, manganese, and cobalt; metals in Group 12 of the periodic table such as zinc and cadmium; metals in Group 13 of the periodic table such as aluminum; metals in Group 14 of the periodic table such as germanium and lead; and metals in Group 15 of the periodic table such as antimony. Examples of metal compounds include alkoxides; organic acid salts such as acetates and propionates; inorganic acid salts such as borates and carbonates; oxides, and hydrates thereof. Representative metal compounds 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 (or titanium(IV) tetrabutoxide), titanium oxalate, and potassium titanium oxalate; manganese compounds such as manganese acetate tetrahydrate; and calcium compounds such as calcium acetate monohydrate.

[0183] These catalysts can be used alone or in combination of two or more. When using multiple catalysts, each catalyst can be added according to the progress of the reaction. Among these catalysts, manganese acetate tetrahydrate, calcium acetate monohydrate, germanium dioxide, titanium (IV) tetrabutoxide, etc. are preferred. The amount of catalyst used is, for example, 0.01 × 10 per mole of dicarboxylic acid component (A). -4 ~100×10 -4 moles, preferably 0.1 x 10 -4 ~40×10 -4 It is a mole.

[0184] The reaction may be carried out in the presence of a stabilizer such as a heat stabilizer or an antioxidant, if necessary. A heat stabilizer is usually used, and examples thereof include phosphorus compounds such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dibutyl phosphate (or dibutyl phosphate), phosphorous acid, trimethyl phosphite, and triethyl phosphite. Among these, 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 (A). -4 ~100×10 -4 moles, preferably 0.1 x 10 -4 ~40×10 -4 It is a mole.

[0185] The reaction may be 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 can be carried out at a pressure of about 100 Pa. The transesterification reaction can be carried out in an inert gas atmosphere such as nitrogen gas, and the polycondensation reaction can be carried out under reduced pressure. The reaction temperature can be selected depending on the polymerization method. For example, the reaction temperature in the melt polymerization method is 150 to 320°C, preferably 250 to 310°C, and more preferably 270 to 300°C.

[0186] After the reaction is completed, the produced thermoplastic resin may be separated and purified by a conventional method, for example, a separation and purification means such as washing, extraction, concentration, reprecipitation, centrifugation, filtration, column chromatography, adsorption, or a combination of these means.

[0187] [Characteristics and uses of thermoplastic resins] (characteristic) The thermoplastic resin, which contains the first dicarboxylic acid unit (A1), exhibits a higher refractive index and a higher Tg (heat resistance) than conventional thermoplastic resins containing arene dicarboxylic acid units such as terephthalic acid units, and also has a good balance of optical properties such as a high refractive index, a low Abbe number, and low birefringence, as well as high heat resistance, high moldability, and high polymerization reactivity (or high molecular weight).

[0188] The thermoplastic resin has a high refractive index, and its refractive index nD can be selected from the range of, for example, about 1.65 to 1.75 at a temperature of 20°C and a wavelength of 589 nm, and is preferably 1.66 to 1.7, 1.67 to 1.69, and 1.675 to 1.685 in the following stepwise order. In applications where a higher refractive index is important, the refractive index may be, for example, 1.68 to 1.7, preferably 1.685 to 1.695, more preferably 1.69 to 1.72, and particularly preferably 1.7 to 1.71.

[0189] The Abbe number of the thermoplastic resin at a temperature of 20°C may be, for example, about 20 or less, preferably in the following stepwise manner: 17 to 19.5, 17.5 to 19, 17.5 to 18.5, and more preferably in the following stepwise manner: 13 to 18, 13 to 17.5, 13.3 to 17, 13.4 to 16, and 13.5 to 15. Because thermoplastic resins can effectively reduce the Abbe number, they can be effectively used in applications requiring a low Abbe number, such as optical components in various cameras, such as camera lenses, and in particular, as concave lenses (concave lenses in various camera optical systems configured by combining multiple convex and concave lenses) for reducing (or canceling) chromatic aberration (bleeding) that occurs in convex lenses.

[0190] The birefringence of a thermoplastic resin may be evaluated by measuring the birefringence (triple birefringence) of a stretched film obtained by uniaxially stretching a film formed from the thermoplastic 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, 75 × 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 stepwise order: 0 to 60×10 -4 , 10×10 -4 ~50×10 -4 , 20×10 -4 ~45×10 -4 , 30×10 -4 ~40×10 -4 More preferably, the following stepwise range is used: 0 to 30×10 -4 , 0 to 20 × 10 -4 , 0 to 15 × 10 -4, 0 to 10 x 10 -4 , 0 to 5 × 10 -4 Although the thermoplastic resin contains many benzene ring skeletons (arene ring skeletons), it unexpectedly exhibits low birefringence, and therefore can achieve both low birefringence and high refractive index, which are usually in a trade-off relationship.

[0191] Thermoplastic resins have high heat resistance, with glass transition temperatures (Tg) ranging from, for example, approximately 120 to 200°C, preferably 140 to 180°C. In order to achieve both high heat resistance and moldability, Tg values ​​are preferably set in the following stepwise order: 145 to 175°C, 150 to 170°C, and 155 to 165°C. If Tg is too low, heat resistance is reduced, resulting in increased discoloration (or coloration) during production and / or use, or increased deformation in high-temperature environments after molding into a predetermined shape, potentially making the resin unusable for applications requiring high thermal stability. If Tg is too high, moldability or fluidity is reduced, making it difficult to achieve a smooth surface during molding by injection molding or other methods, potentially making the resin unusable for optical components such as optical lenses. Despite containing many benzene ring skeletons (arene ring skeletons), the thermoplastic resins surprisingly suppress excessive increases in Tg and exhibit high moldability, thereby achieving both moldability and heat resistance, which are usually in a trade-off relationship.

[0192] Despite having a rigid and bulky skeleton such as the first dicarboxylic acid unit (A1) represented by formula (1), the thermoplastic resin can be surprisingly easily and efficiently prepared to have a high molecular weight. The weight-average molecular weight Mw of the thermoplastic resin can be measured by gel permeation chromatography (GPC) or the like, and is, in polystyrene equivalent, for example, about 5,000 to 300,000, specifically 6,000 to 250,000, and preferably 10,000 to 200,000. From the viewpoint of moldability and the like, more preferably, the following stepwise values ​​are used: 25,000 to 150,000, 30,000 to 120,000, 40,000 to 100,000, 50,000 to 80,000, and 60,000 to 70,000. If the weight-average molecular weight Mw is too low, moldability (productivity) may be reduced or applications may be limited.

[0193] In this specification and claims, the refractive index nD, Abbe number, triple birefringence, glass transition temperature Tg, and weight average molecular weight Mw can be measured by the methods described in the examples below.

[0194] (Molded body) The molded article only needs to contain at least the thermoplastic resin, and has a good balance of excellent optical properties (high refractive index, low Abbe number, low birefringence, etc.), high heat resistance, high moldability, high molecular weight, etc., and can therefore be effectively used as optical components such as optical films (optical sheets) and optical lenses, in particular optical lenses.

[0195] The molded article may contain conventional additives, such as fillers or reinforcing agents, colorants such as dyes and pigments, conductive agents, flame retardants, plasticizers, lubricants, mold release agents, antistatic agents, dispersants, flow control agents, leveling agents, antifoaming agents, surface modifiers, hydrolysis inhibitors, carbon materials, stabilizers, and stress-reducing agents. Examples of stabilizers include antioxidants, UV 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. The total proportion of these additives may be, for example, 50 parts by mass or less, preferably 30 parts by mass or less, 0 to 10 parts by mass, and approximately 0.1 to 5 parts by mass, per 100 parts by mass of the thermoplastic resin.

[0196] The molded article can be produced by, for example, injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, pressure molding, casting molding, or the like.

[0197] The shape of the molded body is not particularly limited, and examples thereof include one-dimensional structures such as linear, fibrous, and thread-like structures, two-dimensional structures such as film-like, sheet-like, and plate-like structures, and three-dimensional structures such as concave or convex lens-like, rod-like, and hollow (tubular) structures.

[0198] Thermoplastic resins are useful for forming optical films (or optical sheets) because they have various excellent optical properties. The films (optical films) can be produced by forming (or molding) the thermoplastic resins using a conventional film-forming method, such as a casting method (solvent casting method), a melt extrusion method, or a calendar method.

[0199] The average thickness of the film can be selected from the range of about 1 to 1000 μm depending on the application, and is, for example, 1 to 200 μm, preferably 5 to 150 μm, and more preferably 10 to 120 μm.

[0200] The film may be unstretched or stretched, and even if stretched, it can maintain low birefringence. Such stretched films may be either uniaxially stretched or biaxially stretched.

[0201] The stretching ratio in each direction in uniaxial or biaxial stretching is, for example, 1.1 to 10 times, preferably 1.2 to 8 times, and more preferably 1.5 to 6 times. In the case of biaxial stretching, equal stretching, for example, 1.5 to 5 times stretching in both the longitudinal and transverse directions, or unbalanced stretching, for example, 1.1 to 4 times stretching in the longitudinal direction and 2 to 6 times stretching in the transverse direction, may be used. In the case of uniaxial stretching, longitudinal stretching, for example, 2.5 to 8 times stretching in the longitudinal direction, or transverse stretching, for example, 1.2 to 5 times stretching in the transverse direction, may be used.

[0202] 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.

[0203] Such a stretched film can be obtained by stretching a film (or an unstretched film) after film formation. 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, either a tenter method (flat method) or a tube method may be used, although the tenter method, which has excellent uniformity in stretched thickness, is preferred. [Example]

[0204] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. Details of evaluation items and raw materials are shown below.

[0205] [Evaluation method] ( 1 H-NMR) 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 H-NMR spectrum was measured.

[0206] For the resin samples, the integral values ​​of the peaks derived from each monomer used in the polymerization were determined based on the obtained spectrum, and the proportion of each monomer component (structural unit) introduced into the polymer (polymer composition ratio) was calculated.

[0207] (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 atmosphere at a temperature increase rate of 10°C / min.

[0208] (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).

[0209] (Refractive index nD) The sample was heat-pressed at 200-240°C to form a film with a thickness of 200-300 μm. This film was cut into strips measuring 20-30 mm in length and 10 mm in width to obtain test pieces. The refractive index nD of the obtained test pieces at 589 nm (D line) was measured using a multi-wavelength Abbe refractometer (Atago Co., Ltd., "DR-M4 (circulating constant temperature water bath 60-C3)") at a measurement temperature of 20°C and diiodomethane as the contact liquid.

[0210] (Abbe number) Using the test piece for which the refractive index nD at 589 nm (D line) was measured, 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). The Abbe number was calculated from the refractive indices nF, nD, and nC at each wavelength using the following formula.

[0211] (Abbe number) = (nD-1) / (nF-nC).

[0212] (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 10 mm x 50 mm strips and uniaxially stretched at a temperature of glass transition temperature (Tg) + 10°C at a stretch ratio of 3x at 25 mm / min to obtain test specimens. 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 value was divided by the thickness of the measurement site to calculate the birefringence (or triple birefringence).

[0213] [Raw materials] (Dicarboxylic acid component) DNTPA-E: diethyl 2,5-di(2-naphthyl)terephthalate, synthesized according to Synthesis Example 1 described below MNTPA-M: dimethyl 2-(2-naphthyl)terephthalate, synthesized according to Synthesis Example 2 described below DMT: dimethyl terephthalate FDP-m: 9,9-bis(2-methoxycarbonylethyl)fluorene [or 9,9-bis(2-carboxyethyl)fluorene or dimethyl ester of fluorene-9,9-dipropionic acid], 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. DNFDP-m: 2,7-di(2-naphthyl)-9,9-bis(2-methoxycarbonylethyl)fluorene, synthesized according to Example 1B (2-DNFDP-m) described in WO 2020 / 213470 SA-m: dimethyl sebacate (Diol component) BNEF: 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, synthesized according to Synthesis Example 1 described in JP-A-2018-59074 1,5-PDO: 1,5-pentanediol EG: Ethylene glycol (carbonate bond forming component) DPC: Diphenyl carbonate

[0214] [Synthesis Example 1] Synthesis of diethyl 2,5-di(2-naphthyl)terephthalate (DNTPA-E) In a 300 mL three-neck flask, 49.4 g (130 mmol) of diethyl 2,5-dibromoterephthalate, 45.9 g (260 mmol) of 2-naphthylboronic acid, 36.9 g (260 mmol) of potassium carbonate, and 1.5 g (7 mmol) of palladium acetate were placed and heated under nitrogen. After the nitrogen substitution, 420 mL of 2-methoxyethanol and 140 mL of water were added and reacted at 25°C for 3 hours. 700 mL of chloroform was added to the resulting gray suspension and extracted. The organic layer was washed three times with 200 mL of distilled water and dried over anhydrous magnesium sulfate. Then, the organic layer was filtered through Celite and concentrated. 700 mL of methyl isobutyl ketone was added to the resulting crude crystals, heated to 120°C to dissolve, and then allowed to cool to 20°C to precipitate crystals. The precipitated crystals were separated by filtration, dissolved again in 700 mL of methyl isobutyl ketone, and recrystallized under the same temperature conditions to obtain 44.0 g of DNTPA-E represented by the following formula (yield 71%). 1 The H-NMR spectrum results are shown below and in Figure 1.

[0215] [ka]

[0216] 1 H-NMR (300MHz, CDCl3); δ(ppm)7.97(s,2H),7.91-7.88(m,8H),7.54-7.49(m,6H),4.10(q,J=7.0Hz,4H),0.92(t,J=7.5Hz,6H).

[0217] [Synthesis Example 2] Synthesis of dimethyl 2-(2-naphthyl)terephthalate (MNTPA-M) A 1000 mL three-neck flask was charged with 25.1 g (92 mmol) of dimethyl bromoterephthalate, 16.7 g (97 mmol) of 2-naphthylboronic acid, 13.4 g (97 mmol) of potassium carbonate, and 1.0 g (4.5 mmol) of palladium acetate. After nitrogen substitution, 300 mL of 2-methoxyethanol and 100 mL of water were added and the mixture was allowed to react at 25°C for 3 hours. 300 mL of chloroform was added to the resulting gray suspension for extraction. The organic layer was washed twice with 300 mL of distilled water and dried over anhydrous magnesium sulfate. The organic layer was then filtered through Celite and concentrated. 100 mL of methyl isobutyl ketone was added to the resulting crude crystals, which were then heated to 120°C to dissolve the crystals, and then allowed to cool to 20°C to precipitate crystals, yielding 16.0 g of MNTPA-M, represented by the following formula (yield: 54%). The resulting MNTPA-M 1 The H-NMR spectrum results are shown below and in Figure 2.

[0218] [ka]

[0219] 1 H-NMR (300MHz, CDCl3): δ (ppm) 8.17-7.92 (m, 2H), 7.89-7.83 (m, 5H), 7.53-7.42 (m, 3H), 3.96 (s, 3H), 3.62 (s, 3H).

[0220] [Comparative Example 1] The reactor was charged with DMT (5.83 g (30 mmol)) and FDP-m (23.69 g (70 mmol)) as dicarboxylic acid components, BNEF (40.40 g (75 mmol)) as diol components, EG (13.97 g (225 mmol)), and titanium (IV) tetrabutoxide (8.5 mg (15 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 (12.6 mg (60 μmol)) was added as a thermal stabilizer, and the temperature was gradually raised to 280 °C and 130 Pa, the pressure was reduced, and the polycondensation reaction was carried out while removing the EG. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0221] [Example 1] The reactor was charged with DNTPA-E (14.22 g (30 mmol)) and FDP-m (23.69 g (70 mmol)) as dicarboxylic acid components, BNEF (40.40 g (75 mmol)) as diol components, and EG (13.97 g (225 mmol)). Titanium (IV) tetrabutoxide (8.5 mg (15 μmol)) was used 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 (12.6 mg (60 μmol)) was added as a thermal stabilizer, and the temperature was gradually increased to 280 ° C and 130 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.

[0222] [Example 2] The reactor was charged with MNTPA-M (9.60 g (30 mmol)) and FDP-m (23.69 g (70 mmol)) as dicarboxylic acid components, BNEF (40.40 g (75 mmol)) as diol components, EG (13.97 g (225 mmol)), and titanium (IV) tetrabutoxide (8.5 mg (15 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 (12.6 mg (60 μmol)) was added as a thermal stabilizer, and the temperature was gradually raised to 280 ° C and 130 Pa, the pressure was reduced, and the polycondensation reaction was carried out while removing the EG. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0223] [Example 3] The reactor was charged with DNTPA-E (37.92 g (80 mmol)) and FDP-m (6.77 g (20 mmol)) as dicarboxylic acid components, BNEF (21.55 g (40 mmol)) as diol components, EG (16.14 g (260 mmol)), and titanium (IV) tetrabutoxide (8.5 mg (15 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 (12.6 mg (60 μmol)) was added as a thermal stabilizer, and the temperature was gradually raised to 280 ° C and 130 Pa, the pressure was reduced, and the polycondensation reaction was carried out while removing the EG. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0224] The polymer composition ratios (proportions (molar ratios) of constituent units derived from each polymerization component used in the preparation) and the evaluation results of each physical property value of each polyester resin obtained in Comparative Example 1 and Examples 1 to 3 are shown in Table 1. The values ​​in parentheses in the column for polymer composition ratio in Table 1 indicate the charged composition ratio (molar ratio) of each corresponding polymerization component.

[0225] [Table 1]

[0226] As is clear from the results in Table 1, Examples 1 to 3 had a better balance of optical properties and heat resistance than Comparative Example 1. Specifically, Examples 1 and 2, which used DNTPA-E or MNTPA-M instead of DMT in Comparative Example 1, had improved refractive indexes and reduced Abbe numbers, likely due to the inclusion of more aromatic ring structures (benzene ring structures) in their chemical structures than DMT. Furthermore, although the aromatic ring structures generally tend to increase birefringence, the birefringence was surprisingly low. Thus, Examples 1 and 2 achieved a better balance of high refractive index and low birefringence than Comparative Example 1. Therefore, they can be effectively used for optical lenses. Furthermore, while the rigid aromatic ring structures tend to increase Tg, the Examples exhibited relatively high heat resistance without excessively increasing Tg, providing an excellent balance between heat resistance and moldability.

[0227] Furthermore, Example 3, which uses a high proportion of DNTPA-E, exhibits a higher refractive index and a lower Abbe number than Examples 1 and 2 and Comparative Example 1, possibly due to the high proportion of the aromatic ring skeleton. However, Tg does not increase excessively, and the balance between heat resistance and moldability is also excellent. However, perhaps because DNTPA-E has low polymerization reactivity due to the influence of the two naphthyl groups, it seems that it is difficult to increase the molecular weight when used in large amounts. Therefore, for applications requiring a high molecular weight, Examples 1 and 2 are preferred, as they have an excellent balance of properties and can be made into a high molecular weight.

[0228] [Example 4] The reactor was charged with DNTPA-E (7.12 g (15 mmol)), DNFDP-m (8.86 g (15 mmol)), FDP-m (23.69 g (70 mmol)) as dicarboxylic acid components, BNEF (40.40 g (75 mmol)), EG (13.97 g (225 mmol)) as diol components, and titanium (IV) tetrabutoxide (8.5 mg (15 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 (12.6 mg (60 μmol)) was added as a thermal stabilizer, and the temperature was gradually increased to 280 °C and 130 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.

[0229] [Example 5] The reactor was charged with DNTPA-E (7.12 g (15 mmol)), DNFDP-m (35.44 g (60 mmol)), SA-m (5.76 g (25 mmol)) as dicarboxylic acid components, BNEF (32.32 g (60 mmol)) as diol components, EG (14.90 g (240 mmol)), and titanium (IV) tetrabutoxide (8.5 mg (15 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 (12.6 mg (60 μmol)) was added as a thermal stabilizer, and the temperature was gradually increased to 280 ° C and 130 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.

[0230] [Example 6] A reactor was charged with DNTPA-E (7.12 g (15 mmol)) and DNFDP-m (20.67 g (35 mmol)) as dicarboxylic acid components, DPC (10.71 g (50 mmol)) as carbonate bond forming component, BNEF (40.40 g (75 mmol)) and 1,5-PDO (2.60 g (25 mmol)) as diol components, and titanium (IV) tetrabutoxide (8.5 mg ( The contents were gradually heated to 240°C under a nitrogen atmosphere, stirred, and subjected to a transesterification reaction. After removing the alcohol component produced by the transesterification reaction, dibutyl phosphate (12.6 mg (60 μmol)) was added as a heat stabilizer, and the temperature was gradually increased to 280°C and 130 Pa, the pressure was reduced, and a polycondensation reaction was carried out while removing phenol. After the reaction was completed, the contents were removed from the reactor, and a polyester carbonate resin was obtained.

[0231] The polymer composition ratios (proportions (molar ratios) of constituent units derived from each polymerization component used in the preparation) of the polyester resins obtained in Examples 4 to 6 and the evaluation results of each physical property value are shown in Table 2. The values ​​in parentheses in the column for polymer composition ratio in Table 2 indicate the charged composition ratios (molar ratios) of the corresponding polymerization components.

[0232] [Table 2]

[0233] In Examples 5 and 6, 1 Although it was difficult to accurately calculate the polymer composition ratios due to overlapping peaks in the H-NMR spectrum, the polymer composition ratios in Example 5 were estimated to be DNTPA-E / DNFDP-m / SA-m (molar ratio) = 15 / 65 / 25 and BNEF / EG (molar ratio) = approximately 60 / 40. In Example 6, since no distillation of monomer components (polymerization components) was confirmed, the polymer composition ratio was estimated to be approximately the same as the charged composition ratio.

[0234] As is clear from the results in Table 2, Examples 4 to 6 all exhibited an excellent balance of optical properties and heat resistance. In particular, Example 4 not only exhibited excellent optical properties, such as a high refractive index, a low Abbe number, and low birefringence compared to Example 1, but also exhibited relatively high heat resistance without an excessive increase in Tg. It also had a high molecular weight and relatively good moldability, resulting in an excellent balance between heat resistance and moldability. Similarly, Example 5 also possessed a good balance of all of the above properties. Although Example 5 had a slightly higher birefringence than Example 4, it surprisingly had a high refractive index and a low Abbe number, despite containing structural units derived from SA-m, an aliphatic dicarboxylic acid component, and in particular, the refractive index was significantly improved to 1.7 or more. Furthermore, Example 6 also showed an excellent balance of optical properties and heat resistance, even for polyester carbonate resins. Therefore, it is particularly useful as an optical material for optical lenses and the like. [Industrial Applicability]

[0235] The thermoplastic resin of the present invention can be used in a variety of applications, including coating agents or coating films, specifically, paints, inks, and protective films for electronic devices and liquid crystal components; adhesives, pressure-sensitive adhesives; resin fillers; electric and electronic materials or electric 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, and EMI shielding films; and mechanical materials or mechanical components (equipment), specifically, automotive materials or components, aerospace-related materials or components, and sliding members.

[0236] Furthermore, thermoplastic resins can be effectively used as optical components because they can balance optical properties such as a high refractive index, a low Abbe number, and low birefringence with heat resistance and moldability (productivity).

[0237] Representative optical members include optical films (optical sheets) such as films for liquid crystal displays and organic EL displays; optical lenses such as lenses for glasses and cameras; prisms, holograms, and optical fibers.

[0238] 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.

[0239] 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. Because thermoplastic resins can reduce the Abbe number, they may be suitably used in lenses that require a low Abbe number, such as camera lenses. Typical examples of devices or apparatuses that incorporate 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). Because thermoplastic resins have high heat resistance, they may be used in applications where use in high-temperature environments is anticipated, such as in-vehicle optical lenses.

Claims

1. A thermoplastic resin that is a polyester-based resin containing dicarboxylic acid units (A) and diol units (B), The dicarboxylic acid unit (A) contains at least a first dicarboxylic acid unit (A1) represented by the following formula (1) and a second dicarboxylic acid unit (A2) represented by the following formula (2), The diol unit (B) comprises at least a first diol unit (B1) represented by the following formula (3) and a second diol unit (B2) represented by the following formula (4): 【Chemistry 1】 (In the formula, Z １ represents a monocyclic or fused polycyclic arene ring, Z ２ represents an arene ring, and R １ represents a substituent, k1 represents an integer of 0 or more, m represents an integer of 1 or more, R ２ represents a substituent, and k2 represents an integer of 0 or more. 【Chemistry 2】 (wherein R 3 represents a substituent, k3 represents an integer of 0 to 8, A 1a and A 1b independently represent a divalent hydrocarbon group which may have a substituent. 【Transformation 3】 (wherein R 4 represents a substituent, k4 represents an integer of 0 to 8, Z 3a and Z 3b independently represent an arene ring; R 5a and R 5b independently represent a substituent; k5a and k5b independently represent an integer of 0 or more; A 2a and A 2b independently represent a linear or branched alkylene group, and n2a and n2b independently represent an integer of 0 or 1 or more. 【Chemistry 4】 (In the formula, A 3 represents a linear or branched alkylene group, and n3 represents an integer of 1 or more.)

2. In the formula (1), Z １ is a monocyclic or fused polycyclic arene ring having 6 to 14 carbon atoms, Z ２ 2. The thermoplastic resin according to claim 1, wherein is an arene ring having 6 to 14 carbon atoms, and m is an integer of 1 to 3.

3. In the formula (1), Z １ is a benzene ring or a naphthalene ring, Z ２ is at least one arene ring selected from a benzene ring, a naphthalene ring, and a biphenyl ring, and m is an integer of 1 to 2; 3. The thermoplastic resin according to claim 1, wherein the proportion of the first dicarboxylic acid units (A1) is 1 to 50 mol % based on the total dicarboxylic acid units (A).

4. In the formula (2), R ３ is an aryl group, k3 is an integer of 0 to 4, A １ａ and A １ｂ The thermoplastic resin according to any one of claims 1 to 3, wherein is a linear or branched alkylene group.

5. The second dicarboxylic acid unit (A2) is represented by the formula (2), ３ is an aryl group and contains at least a dicarboxylic acid unit (A2-2) in which k3 is an integer of 1 or more, The thermoplastic resin according to any one of claims 1 to 4, wherein the proportion of the dicarboxylic acid units (A2-2) is 1 to 100 mol% based on the total of the second dicarboxylic acid units (A2).

6. The thermoplastic resin according to any one of claims 1 to 5, wherein a ratio of the first dicarboxylic acid unit (A1) to the second dicarboxylic acid unit (A2) (former / latter) (molar ratio) is 5 / 95 to 90 / 10.

7. The thermoplastic resin according to any one of claims 1 to 6, wherein the dicarboxylic acid units (A) contain an aliphatic dicarboxylic acid unit as a third dicarboxylic acid unit (A3).

8. The thermoplastic resin according to claim 7, wherein the third dicarboxylic acid unit (A3) contains a structural unit derived from a linear or branched alkanedicarboxylic acid having 2 to 20 carbon atoms.

9. a molar ratio of the first dicarboxylic acid unit (A1) to the third dicarboxylic acid unit (A3) is 5 / 95 to 90 / 10; The thermoplastic resin according to claim 7 or 8, wherein the ratio of the second dicarboxylic acid unit (A2) to the third dicarboxylic acid unit (A3) (molar ratio) is 10 / 90 to 95 / 5.

10. In the formula (3), Z ３ａ and Z ３ｂ is a monocyclic or fused polycyclic arene ring, A ２ａ and A ２ｂ has 2 to 6 carbon atoms, and n2a and n2b are integers of 0 to 10; In the formula (4), A ３ The thermoplastic resin according to any one of claims 1 to 9, wherein n3 is an integer of 1 to 4 and n4 is a carbon number of 2 to 6.

11. A thermoplastic resin described in any one of claims 1 to 10, wherein the ratio of the first diol unit (B1) to the second diol unit (B2) is the former / latter (molar ratio) = 1 / 99 to 99 / 1.

12. The thermoplastic resin according to any one of claims 1 to 11, having a weight average molecular weight Mw of 6,000 to 250,000.

13. A method for producing a thermoplastic resin described in any one of claims 1 to 12, by polymerizing polymerization components including at least a first dicarboxylic acid component corresponding to the first dicarboxylic acid unit (A1), a second dicarboxylic acid component corresponding to the second dicarboxylic acid unit (A2), a first diol component corresponding to the first diol unit (B1), and a second diol component corresponding to the second diol unit (B2).

14. A molded article comprising the thermoplastic resin according to any one of claims 1 to 12.

15. The molded article according to claim 14, which is an optical element.

16. The molded article according to claim 14 or 15, which is an optical lens.

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