Fluorene compounds, as well as their manufacturing methods and uses.

Abstract

To provide a compound or a salt thereof having a high refractive index and high heat resistance, a resin using such a compound or a salt thereof as a raw material, and a method for producing them and use of them.SOLUTION: There is prepared a compound represented by the following formula (1) or a salt thereof. [wherein, Z1a and Z1b each independently represent a substituted or unsubstituted arene ring, Z2a and Z2b each independently represent a substituted or unsubstituted arene ring, A1a and A1b each independently represent an alkylene group and R3a and R3b each independently represent a hydroxyl group, a group [-ORh] (wherein, Rh represents a hydrocarbon group) or a halogen atom.]SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to compounds having a 9,9-bisarylfluorene skeleton (or salts thereof), derivatives thereof, and methods for producing the same and their uses. [Background technology]

[0002] Many small devices or mobile devices, such as smartphones and tablet PCs, are equipped with optical functions such as cameras in addition to image display capabilities, and the performance requirements for optical components are increasing as these devices become more sophisticated. While many resin materials are used for optical components, offering advantages over optical glass in terms of lightness, impact resistance (flexibility), and moldability (productivity), existing resin materials may not always be sufficient to meet the increasingly stringent requirements.

[0003] For example, imaging lens units installed in devices with camera functions are required to be miniaturized as the devices themselves become thinner and more multifunctional, while at the same time, they are required to have higher resolution as image sensors become more pixelated. Therefore, various efforts are made in the selection of lens configuration, shape, and materials for imaging lens units, and the optical design is made to be compact and capable of correcting various aberrations with high imaging performance. Generally, imaging lens units are composed of multiple lenses with different Abbe numbers and refractive indices. For example, they are often composed of a combination of a high Abbe number lens and a low Abbe number lens. However, there are limitations to the types of resin materials that can be used for optical lenses, which limits the design of diverse and highly effective lens units. Therefore, from the perspective of increasing design freedom and improving functionality or performance, it is considered important to broaden the range of material selection, and there is a need for the development of various optical resin materials with different optical properties such as Abbe number.

[0004] In addition, as an index representing the wavelength dispersion characteristics different from the Abbe number, the partial dispersion ratio θgF is known. In a material with a high partial dispersion ratio θgF (showing a large anomalous dispersion characteristic), chromatic aberration (the deviation of the imaging position depending on the wavelength) can be effectively corrected or reduced. Therefore, in International Publication No. 2019 / 131258 (Patent Document 1), Japanese Unexamined Patent Application Publication No. 2020-158723 (Patent Document 2), and International Publication No. 2017 / 146022 (Patent Document 3), resins or resin compositions showing a high partial dispersion ratio θgF have been proposed.

[0005] In addition, Japanese Unexamined Patent Application Publication No. 2009-256332 (Patent Document 4) and Japanese Unexamined Patent Application Publication No. 2009-256333 (Patent Document 5) disclose specific carboxylic acids having a 9,9-bisarylfluorene skeleton.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0007] Patent Document 1 discloses an optical resin material for chromatic aberration correction containing a specific benzotriazole-based compound or phenyltriazine-based compound in a predetermined ratio. In the examples, it is described that these compounds were mixed with a di- or tetra(meth)acrylate resin and then cured to prepare an optical resin material.

[0008] However, the refractive index nd in most examples is low, around 1.5, and at most around 1.63, so the refractive index cannot be sufficiently improved. In addition, because the benzotriazole or phenyltriazine compounds mixed are low molecular weight compounds, there is a risk of bleed-out from the optical resin material. Furthermore, a polyfunctional (meth)acrylate resin, which is a curable resin, is assumed to be used, and it may be difficult to improve productivity or moldability.

[0009] On the other hand, Patent Document 2 discloses a resin composition containing a thermoplastic resin and an abnormally dispersible compound in a predetermined proportion, which has high abnormal dispersibility and is suitable for mass production and injection molding. In the examples of this document, a resin composition is prepared by melt-kneading a cyclic olefin polymer (a random copolymer of ethylene and tetracyclododecene) with a specific abnormally dispersible compound.

[0010] However, cyclic olefin polymers cannot sufficiently improve their refractive index, and generally, the Abbe number tends to be higher when the refractive index is low. Therefore, the Abbe number νd in the examples is also relatively high, ranging from 38.3 to 49.4. Furthermore, because the anomalous dispersibility compound is a low-molecular-weight compound, there is a risk of it bleeding out from the resin composition.

[0011] Patent Document 3 discloses a polycarbonate resin having specific structural units as a material that exhibits high anomalous dispersibility and a low Abbe number without the need to prepare a resin composition by adding anomalous dispersibility compounds (low molecular weight compounds) to the resin itself. The examples in this document describe that a molded article obtained by injection molding of a polycarbonate resin having specific structural units exhibited a low Abbe number and high anomalous dispersibility.

[0012] However, the examples in this document only state that the θgF value is 0.600 or higher, and do not provide specific numerical values.

[0013] In particular, Patent Document 3 states that conventional resins containing a fluorene skeleton cannot sufficiently reduce the Abbe number and have low anomalous dispersibility. It also states that in Comparative Examples 1 to 4 of the patent document, the resins containing a 9,9-bisarylfluorene skeleton had an Abbe number νD of 24.2 to 25.8, 0.500 < θgF < 0.600, and a refractive index nD of 1.62 to 1.63.

[0014] Although various optical resin materials are known, from the perspective of broadening the range of material selection in the design of optical components, there is a need for resin materials and their raw materials (or monomers) that possess superior properties.

[0015] Although patent documents 4 and 5 disclose carboxylic acids having a 9,9-bisarylfluorene skeleton, in both documents only specific dicarboxylic acids are prepared in the examples, and their specific properties are not measured. Furthermore, in neither document is a resin prepared using the dicarboxylic acid as a raw material, and its optical and thermal properties remain unknown.

[0016] Therefore, the object of the present invention is to provide a compound (or a salt thereof) that exhibits a high refractive index and high heat resistance, a resin using the compound (or a salt thereof) as a raw material (reactant), and methods for producing them and their uses. [Means for solving the problem]

[0017] As a result of diligent research to achieve the above objectives, the inventors of the present invention discovered that a compound (or a salt thereof) having a specific structure exhibits a high refractive index and high heat resistance, making it useful as a raw material for resin materials, and thus completed the present invention.

[0018] In other words, the present invention may encompass the following embodiments, etc.

[0019] Embodiment [1]: A compound represented by the following formula (1) or a salt thereof.

[0020] [Chemical formula]

[0021] [In the formula, R 1 represents a substituent, k1 represents an integer from 0 to 8, Z 1a and Z 1b each independently represent a substituted or unsubstituted arene ring, Z 2a and Z 2b each independently represent a substituted or unsubstituted arene ring, A 1a and A 1b each independently represent an alkylene group, m1a and m1b each independently represent an integer of 0 or more, R 2a and R 2b each independently represent a substituted or unsubstituted divalent hydrocarbon group, R 3a and R 3b each independently represent a hydroxyl group, a group [-OR h3 (wherein R h3 represents a hydrocarbon group) or a halogen atom.].

[0022] Aspect [2]: In the above formula (1), R 1 is a halogen atom, a hydrocarbon group, a group [-OR h1 (wherein R h1 represents a hydrocarbon group), an acyl group, a nitro group, a cyano group or a substituted amino group, k1 is an integer from 0 to 4, Z 1a and Z 1b the arene rings of are each independently a monocyclic or fused polycyclic arene ring, Z 2a and Z 2b the arene rings of are each independently a monocyclic or fused polycyclic arene ring, m1a and m1b are each independently an integer from 0 to 10, R 2a and R 2b The compound according to Aspect [1] or a salt thereof, wherein the divalent hydrocarbon groups of are each independently an alkylene group.

[0023] Embodiment [3]: The compound or salt thereof according to Embodiment [1] or [2], in crystalline form.

[0024] Embodiment [4]: ​​A method for producing a compound represented by formula (1) or a salt thereof as described in any of Embodiments [1] to [3] by reacting a compound represented by formula (2) or a salt thereof with a compound represented by formula (3a) and a compound represented by formula (3b).

[0025] [ka]

[0026] [where, X 1a and X 1b And, X 2a and X 2b These are groups that can form carbon-carbon bonds with each other through coupling reactions. R 1 , k1, Z 1a and Z 1b , Z 2a and Z 2b , A 1a and A 1b , m1a and m1b, R 2a and R 2b , R 3a and R 3b These are the same as in formula (1) above.

[0027] Embodiment [5]: A resin comprising at least one constituent unit represented by the following formula (A-1).

[0028] [ka]

[0029] [In the formula, R 1 represents a substituent, and k1 represents an integer from 0 to 8. Z 1a and Z 1b These independently represent substituted or unsubstituted arene rings. Z2a and Z 2b These independently represent substituted or unsubstituted arene rings. A 1a and A 1b m1a and m1b independently represent an alkylene group, and m1a and m1b independently represent an integer greater than or equal to 0. R 2a and R 2b [This independently represents a substituted or unsubstituted divalent hydrocarbon group.]

[0030] Embodiment [6]: The resin is a thermoplastic resin comprising at least dicarboxylic acid units (A) derived from a dicarboxylic acid component as a polymerization component, The resin according to embodiment [5], wherein the dicarboxylic acid unit (A) includes at least a constituent unit represented by formula (A-1) as a first dicarboxylic acid unit (A1).

[0031] Embodiment [7]: The resin according to Embodiment [6], wherein the dicarboxylic acid unit (A) further comprises at least a second dicarboxylic acid unit (A2) represented by the following formula (A-2).

[0032] [ka]

[0033] (In the formula, Z 3 (The symbol indicates a substituted or unsubstituted arene ring.)

[0034] Embodiment [8]: In the above formula (A-2), Z 3 The resin according to [7], wherein the arene ring is a fused polycyclic arene ring.

[0035] Embodiment [9]: The resin according to Embodiment [7] or [8], wherein the ratio of the first dicarboxylic acid unit (A1) to the second dicarboxylic acid unit (A2) is the former / latter (molar ratio) = 10 / 90 to 90 / 10.

[0036] Embodiment

[10] : The resin according to any one of Embodiments [5] to [9], wherein the resin is a polyester resin further comprising at least diol units (B) derived from a diol component as a polymerization component.

[0037] Embodiment

[11] : The resin according to Embodiment

[10] , wherein the diol unit (B) comprises at least one diol unit selected from a first diol unit (B1) represented by the following formula (B-1) and a second diol unit (B2) represented by the following formula (B-2).

[0038] [ka]

[0039] (In the formula, R 4 represents a substituent, and k4 represents an integer from 0 to 8. Z 4a and Z 4b These independently represent substituted or unsubstituted arene rings. A 2a and A 2b (Each represents a linear or branched alkylene group independently, and m2a and m2b independently represent 0 or an integer greater than or equal to 1.)

[0040] [ka]

[0041] (In the formula, A 3 (where m3 represents a linear or branched alkylene group, and m3 represents an integer of 1 or more).

[0042] Embodiment

[12] : In the above formula (B-1), R 4 k4 is a halogen atom, hydrocarbon group, alkoxy group, acyl group, nitro group, cyano group, or substituted amino group, and k4 is an integer from 0 to 4. Z 4a and Z 4b The arene rings are independently monocyclic or fused polycyclic arene rings. The resin according to embodiment

[11] in which m2a and m2b are independently 0 to 10.

[0043] Embodiment

[13] : The resin according to Embodiment

[11] or

[12] , wherein the ratio of the first diol unit (B1) to the second diol unit (B2) is the former / latter (molar ratio) = 50 / 50 to 99 / 1.

[0044] Embodiment

[14] : The dicarboxylic acid unit (A) further comprises at least a second dicarboxylic acid unit (A2) represented by formula (A-2) as described in any of Embodiments [7] to [9], The resin according to any one of the embodiments

[11] to

[13] , wherein the diol unit (B) comprises at least the first diol unit (B1).

[0045] Embodiment

[15] : The resin according to any of Embodiments [5] to

[14] , wherein the Abbe number νd is 17 to 23 and the partial dispersion ratio θgF is 0.67 or more.

[0046] Embodiment

[16] : A method for producing a resin according to any of Embodiments [5] to

[15] using a compound or salt thereof according to any of Embodiments [1] to [3] as a raw material.

[0047] Embodiment

[17] : A molded article containing the resin described in any of Embodiments [5] to

[15] .

[0048] Embodiment

[18] : The molded article according to Embodiment

[17] , which is an optical component.

[0049] Embodiment

[19] : The molded body according to embodiment

[17] or

[18] , which is an optical lens.

[0050] Furthermore, the present invention may achieve (or solve) the following secondary objectives.

[0051] In other words, another object of the present invention is to provide a compound (or a salt thereof) that can prepare a resin that satisfies in a good balance between high refractive index and high heat resistance and low birefringence (low absolute value of birefringence), which is an optical property that is a trade-off with high refractive index, as well as a resin made from the compound (or a salt thereof), and methods for producing them and their uses.

[0052] Another object of the present invention is to provide a compound (or a salt thereof) that can prepare a resin having a fluorene skeleton that exhibits high anomalous dispersion characteristics (high partial dispersion ratio θgF value), a resin made from the compound (or a salt thereof), and methods for producing them and their uses.

[0053] In this specification and in the claims, “dicarboxylic acid unit” and “constituent unit derived from a dicarboxylic acid component” mean a unit (or divalent group) obtained by removing the OH (hydroxyl group) from each of the two carboxyl groups of the corresponding dicarboxylic acid, and “dicarboxylic acid component” (including compounds exemplified as dicarboxylic acid components) may be used synonymously with the corresponding “dicarboxylic acid unit.” Similarly, “diol unit” and “constituent unit derived from a diol component” mean a unit (or divalent group) obtained by removing the hydrogen atom from each of the two hydroxyl groups of the corresponding diol component, and “diol component” (including compounds exemplified as diol components) may be used synonymously with the corresponding “diol unit.”

[0054] Furthermore, in this specification and in the claims, the term "dicarboxylic acid component" is used to mean dicarboxylic acid in addition to its ester-forming derivatives. Examples of ester-forming derivatives include alkyl esters, acid halides such as acid chlorides, and acid anhydrides. Examples of alkyl esters include lower alkyl esters, such as methyl esters, ethyl esters, and t-butyl esters. 1-4 Examples include alkyl esters. The ester-forming derivative may also be a monoester (half-ester) or a diester.

[0055] In this specification and the claims, the number of carbon atoms in a substituent is defined as C1, C6, C 10 These are sometimes used to indicate this. For example, an alkyl group with 1 carbon atom is indicated as "C1 alkyl", and an aryl group with 6 to 10 carbon atoms is indicated as "C 6-10 It is indicated by "Ariel". [Effects of the Invention]

[0056] The compound (or salt thereof) of the present invention has a high refractive index and high heat resistance. Therefore, it can be effectively used as a resin raw material with a high refractive index and high heat resistance. Furthermore, resins made from the compound (or salt thereof) of the present invention can balance high refractive index and high heat resistance with low birefringence (low absolute value of birefringence), which is an optical property that is a trade-off with high refractive index. Moreover, even if the resin has a fluorene skeleton, it can exhibit high anomalous dispersion characteristics (high partial dispersion ratio θgF value). [Modes for carrying out the invention]

[0057] [Compound represented by formula (1)] The present invention encompasses compounds (dicarboxylic acid compounds) (or salts thereof) represented by the following formula (1) and their derivatives. In this specification and in the claims, the compound represented by formula (1) may be simply referred to as "compound (1)".

[0058] [ka]

[0059] [In the formula, R 1 represents a substituent, and k1 represents an integer from 0 to 8. Z 1a and Z 1b These independently represent substituted or unsubstituted arene rings. Z 2a and Z 2b These independently represent substituted or unsubstituted arene rings. A 1a and A 1bm1a and m1b independently represent an alkylene group, and m1a and m1b independently represent an integer greater than or equal to 0. R 2a and R 2b These independently represent substituted or unsubstituted divalent hydrocarbon groups. R 3a and R 3b The hydroxyl group and the group [-OR h3 ](where R h3 [This indicates a hydrocarbon group or a halogen atom.]

[0060] In the above equation (1), R 1 The substituent represented by may be an inert, nonreactive group (or nonpolymerizable group) that is inert to the reaction, for example, a halogen atom, a hydrocarbon group, or a group [-OR h1 ](where R h1 Examples include hydrocarbon groups, acyl groups, nitro groups, cyano groups, or substituted amino groups (mono or disubstituted amino groups).

[0061] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0062] Examples of hydrocarbon groups include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups.

[0063] Examples of alkyl groups (linear or branched alkyl groups) include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl groups. 1-10 Examples include alkyl groups, preferably C 1-6 Alkyl alkyl groups, more preferably C 1-4 It is an alkyl group.

[0064] Examples of cycloalkyl groups include cyclopentyl groups, cyclohexyl groups, and other C groups. 5-10 Examples include cycloalkyl groups.

[0065] Examples of the aryl group include C aryl groups such as a phenyl group, an alkylphenyl group, a biphenylyl group, and a naphthyl group. 6-12 Examples of the alkylphenyl group include mono- to tri-C alkyl-phenyl groups such as a methylphenyl group (or tolyl group) and a dimethylphenyl group (or xylyl group). 1-4

[0066] Examples of the aralkyl group include C aryl-C alkyl groups such as a benzyl group and a phenethyl group. 6-10 aryl-C 1-4 alkyl groups.

[0067] In the group [-OR h1 , examples of the hydrocarbon group R h1 include the same groups as the above hydrocarbon groups such as an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Examples of the group [-OR h1 include groups corresponding to the examples of the hydrocarbon group R h1 , and include an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, etc. Examples of the alkoxy group (linear or branched alkoxy group) include C alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group. Examples of the cycloalkyloxy group include C cycloalkyloxy groups such as a cyclohexyloxy group. Examples of the aryloxy group include C aryloxy groups such as a phenoxy group. Examples of the aralkyloxy group include C aryl-C alkyl-oxy groups such as a benzyloxy group. 1-10 5-10 6-10 6-10 aryl-C 1-4 alkyl-oxy groups.

[0068] Examples of the acyl group include C acyl groups, and for example, include C alkyl-carbonyl groups such as an acetyl group. 1-12 1-6

[0069] ​​​​​​Examples of the mono- or di-substituted amino group include, for example, mono- or dialkylamino groups, mono- or bis(alkylcarbonyl)amino groups, and the like. Examples of the mono- or dialkylamino group include mono- or diC 1-4 alkylamino groups such as mono- or dimethylamino groups. Examples of the mono- or bis(alkylcarbonyl)amino group include mono- or bis(C 1-4 alkyl-carbonyl)amino groups such as mono- or diacetylamino groups.

[0070] Among these groups, typical R 1 include a halogen atom, a hydrocarbon group, a group [-OR h1 , a cyano group, and the like, preferably a halogen atom, a hydrocarbon group such as an alkyl group or an aryl group, a group [-OR h1 such as an alkoxy group or an aryloxy group.

[0071] The substitution number k1 may be, for example, an integer of about 0 to 6, preferably, stepwise, an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, 0 or 1, and particularly 0 is preferred. In addition, the substitution numbers of the group R 1 in the two benzene rings constituting the fluorene ring (the substitution numbers at the 1-4 positions and the substitution numbers at the 5-8 positions) may be different from each other, but are preferably the same.

[0072] In addition, when the substitution number k1 of the group R 1 is plural (2 or more), among the two benzene rings constituting the fluorene ring, the types of two or more groups R 1 substituting on one benzene ring may be the same or different; also, the types of the groups R 1 substituting on both benzene rings may be different, but are preferably the same. In addition, the bonding position (substitution position) of the group R 1 is not particularly limited as long as it is at the 1-8 positions of the fluorene ring, and examples include the 2-position, 7-position, 2,7-position, etc. of the fluorene ring, and the 2,7-position is preferred.

[0073] Z 1aand Z 1b Each independently represents a substituted or unsubstituted arene ring (an arene ring which may have substituents), and examples of the arene ring (aromatic hydrocarbon ring) include monocyclic arene rings such as benzene rings, and fused polycyclic arene rings (fused polycyclic aromatic hydrocarbon rings).

[0074] Examples of fused polycyclic arene rings include fused bicyclic arene rings, fused tricyclic arene rings, and other fused dicyclic to tetracyclic arene rings. Examples of fused bicyclic arene rings include naphthalene rings and indene rings. 10-16 Examples include arene rings. Examples of fused tricyclic arene rings include anthracene rings and phenanthrene rings. 14-20 Examples include arene rings. Preferred fused polycyclic arene rings include naphthalene rings and other fused polycyclic C rings. 10-14 It is an arene ring.

[0075] Z 1a and Z 1b A preferred arene ring in C is 6-14 C such as an arene ring, more preferably a benzene ring, naphthalene ring, etc. 6-10 It is an arene ring, and more specifically, a naphthalene ring. 1a and Z 1b In this process, the arene ring is preferably a fused polycyclic arene ring such as a naphthalene ring.

[0076] Z 1a and Z 1b The types of arene rings in the compound may be different from each other, but it is preferable that they be the same.

[0077] Z 1a and Z 1b In the arene ring, at position 9 of the fluorene ring, ring Z 2a ,Z 2b , and base [-O-(A 1a O) m1a -R 2a -C(=O)-R 3a ],[-O-(A 1b O)m1b -R 2b -C(=O)-R 3b The substitution position (bonding position) with ] is not particularly limited, but for example, a distant substitution position that is not adjacent to the bonding position with position 9 of the fluorene ring, preferably the most distant substitution position, is where the group [-O-(A 1a O) m1a -R 2a -C(=O)-R 3a ],[-O-(A 1b O) m1b -R 2b -C(=O)-R 3b It is preferable that ] is substituted (bonded); this group [-O-(A 1a O) m1a -R 2a -C(=O)-R 3a ],[-O-(A 1b O) m1b -R 2b -C(=O)-R 3b For the substitution position of ], ring Z is added to the adjacent substitution position (or ortho position). 2a ,Z 2b It is preferable that Z be substituted (joined). Specifically, Z 1a ,Z 1b In the case of a benzene ring, the bond position to the 9th position of the fluorene ring is the 1st position (or phenyl group) of the benzene ring, and the group [-O-(A 1a O) m1a -R 2a -C(=O)-R 3a ],[-O-(A 1b O) m1b -R 2b -C(=O)-R 3b It is preferable that ] is substituted (bonded); this group [-O-(A 1a O) m1a -R 2a -C(=O)-R 3a ],[-O-(A 1b O) m1b -R 2b -C(=O)-R 3b For the substitution position (position 4) of ], the ring Z is added to the adjacent substitution position (position 3). 2a ,Z 2b It is preferable that Z is substituted (joined). 1a ,Z1b In the case of a naphthalene ring, for example, the 2-position (or 2-naphthyl group) of the naphthalene ring, which is the bonding position with the 9-position of the fluorene ring, has a group [-O-(A] at the 6-position (in a 2,6 positional relationship). 1a O) m1a -R 2a -C(=O)-R 3a ],[-O-(A 1b O) m1b -R 2b -C(=O)-R 3b It is preferable that ] is substituted (bonded); this group [-O-(A 1a O) m1a -R 2a -C(=O)-R 3a ],[-O-(A 1b O) m1b -R 2b -C(=O)-R 3b For the substitution position (position 6) of ], the ring Z is added to the adjacent substitution position (position 5). 2a ,Z 2b It is preferable for substitution (combination) to occur.

[0078] Z 1a and Z 1b In this, the arene ring is an unsubstituted arene ring, i.e., the fluorene ring at position 9, ring Z 2a ,Z 2b , and base [-O-(A 1a O) m1a -R 2a -C(=O)-R 3a ],[-O-(A 1b O) m1b -R 2b -C(=O)-R 3b Substituents (hereinafter referred to as group [-R)) are located at positions other than the substitution position (bonding position) with ]. Z1 It may also be an arene ring that does not have a substituent (group [-R Z1 The arene ring may have a substituent [-R]. Z1 The group may be an inert, non-reactive group (or non-polymerizable group) that is inert to the reaction, for example, a halogen atom, a hydrocarbon group, or a group [-OR hZ1 ](where R hZ1 (represents a hydrocarbon group), group [-SRhZ1 ](where R hZ1 Examples include hydrocarbon groups, acyl groups, nitro groups, cyano groups, and substituted amino groups (mono or disubstituted amino groups).

[0079] Substituent [-R Z1 Examples of halogen atoms, acyl groups, and substituted amino groups (mono or disubstituted amino groups) in ] include R 1 Examples of halogen atoms, acyl groups, and substituted amino groups (mono- or disubstituted amino groups) are similar to those exemplified above.

[0080] Substituent [-R Z1 Examples of hydrocarbon groups in ] include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. 1 The same groups as those exemplified as hydrocarbon groups in the above can be exemplified. Note that substituents [-R Z1 The hydrocarbon group as ] may be any hydrocarbon group other than an aryl group.

[0081] Base [-OR hZ1 ], base [-SR hZ1 In ], hydrocarbon group R hZ1 For example, R 1 Examples of hydrocarbon groups include alkyl groups (linear or branched alkyl groups), cycloalkyl groups, aryl groups, and aralkyl groups, as well as groups similar to those exemplified in the above. hZ1 ], base [-SR hZ1 In ], hydrocarbon group R hZ1 The types may be the same or different from each other.

[0082] Base [-OR hZ1 For example, R 1 In the base [-OR h1 Examples include alkoxy groups (linear or branched alkoxy groups), cycloalkyloxy groups, aryloxy groups, and aralkyloxy groups, as exemplified above, and other similar groups.

[0083] Base [-SRhZ1 Examples of alkylthio groups include alkylthio groups, cycloalkylthio groups, arylthio groups, and aralkylthio groups. Examples of alkylthio groups include linear or branched C groups such as methylthio groups, ethylthio groups, propylthio groups, n-butylthio groups, and t-butylthio groups. 1-10 Examples include alkylthio groups. Cycloalkylthio groups include, for example, cyclohexylthio groups and other C groups. 5-10 Examples include cycloalkylthio groups. Examples of arylthio groups include phenylthio groups (thiophenoxy groups) and C 6-10 Examples of arylthio groups include the benzylthio group. 6-10 Aryl-C 1-4 Alkylthio groups are one example.

[0084] Typical substituents [-R Z1 ] includes halogen atoms, hydrocarbon groups, and groups [-OR hZ1 Examples include acyl groups, nitro groups, cyano groups, substituted amino groups, etc.; preferably hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, etc., and alkoxy groups [-OR hZ1 Examples include; more preferably linear or branched C such as a methyl group. 1-6 C such as alkyl groups and cyclohexyl groups 5-8 Cycloalkyl groups, phenyl groups, etc. 6-14 Linear or branched C such as aryl groups and methoxy groups 1-4 Examples include alkoxy groups. Substituents [-R Z1 Among these, alkyl groups are preferred, and in particular linear or branched C such as methyl groups. 1-4 Alkyl alkyl groups are preferred.

[0085] Z 1a ,Z 1b substituents [-R] in each arene ring Z1 The number of ] (number of permutations) is, depending on the type of arene ring, for example, an integer of about 0 to 5, preferably an integer of 0 to 3, an integer of 0 to 2, 0 or 1, and especially 0. 1aThe number of substitutions in Z 1b The number of substitutions in Z may be different from each other, but it is preferable that they be the same. 1a If the number of substitutions in is 2 or more, then 2 or more substituents [-R Z1 The types of ] may be the same or different from each other; Z 1b If the number of substitutions in is 2 or more, then 2 or more substituents [-R Z1 The types of ] may be the same or different from each other. Also, Z 1a substituents in [-R Z1 ] Types and Z 1b substituents in [-R Z1 The types of [items] may be different from each other, but it is preferable that they be the same.

[0086] Z 2a and Z 2b Each independently represents a substituted or unsubstituted arene ring (an arene ring which may have substituents), and examples of such arene rings include monocyclic arene rings such as benzene rings and polycyclic arene rings, and examples of polycyclic arene rings include fused polycyclic arene rings and ring-assembled arene rings.

[0087] Examples of fused polycyclic arene rings include Z 1a ,Z 1b Examples include fused polycyclic arene rings similar to those exemplified above, and preferred fused polycyclic arene rings such as naphthalene rings. 10-14 It is an arene ring.

[0088] Examples of ring-assembled arene rings include bialene rings such as biphenyl rings, phenylnaphthalene rings, and binaphthyl rings; and telarene rings such as terphenyl rings. Preferred ring-assembled arene rings include C such as biphenyl rings. 12-18 It is a Bialen ring.

[0089] In this specification and in the claims, "ring-assembled arene ring" means a ring in which two or more ring systems (arene ring systems) are directly connected by single or double bonds, and the number of bonds directly connecting the rings is one less than the number of ring systems. For example, as mentioned above, phenylnaphthalene rings and binaphthyl rings are classified as ring-assembled arene rings even though they have a fused polycyclic arene ring skeleton, and are clearly distinguished from "fused polycyclic arene rings" such as naphthalene rings (aring-assembled arene rings).

[0090] Z 2a and Z 2b A preferred arene ring in C is 6-14 Examples include arene rings, preferably monocyclic or fused polycyclic arene rings, and more preferably C such as benzene rings or naphthalene rings. 6-10 It is an arene ring. In particular, a condensed polycyclic arene ring such as a naphthalene ring is preferred because it is easy to improve the refractive index and heat resistance of compound (1) and the resin made from this compound (1) as a raw material. When a condensed polycyclic arene ring such as a naphthalene ring is used as a resin raw material, the resulting resin not only exhibits a high refractive index and high heat resistance, but also surprisingly low birefringence, and it seems that high refractive index, high heat resistance, and low birefringence can be satisfied in a highly balanced manner. Furthermore, even if it is a benzene ring instead of a condensed polycyclic arene ring such as a naphthalene ring, it is also preferred because it is surprisingly easy to improve the heat resistance of compound (1) and the resin made from this compound (1) as a raw material.

[0091] Z 2a and Z 2b The types of arene rings in the compound may be different from each other, but it is preferable that they be the same.

[0092] Z 2a and Z 2b In this case, the arene ring is an unsubstituted arene ring, i.e., ring Z 1a ,Z 1b Substituents (hereinafter referred to as group [-R)) are located at positions other than the substitution (bonding) position with the group. Z2 It may also be an arene ring that does not have a substituent (group [-R Z2The arene ring may have a substituent [-R]. Z2 The group may be an inert, non-reactive group (or non-polymerizable group) that is inert to the reaction, for example, a halogen atom, a hydrocarbon group, or a group [-OR hZ2 ](where R hZ2 (represents a hydrocarbon group), group [-SR hZ2 ](where R hZ2 Examples include hydrocarbon groups, acyl groups, nitro groups, cyano groups, and substituted amino groups (mono or disubstituted amino groups).

[0093] Substituent [-R Z2 Examples of halogen atoms, acyl groups, and substituted amino groups (mono or disubstituted amino groups) in ] include R 1 Examples of halogen atoms, acyl groups, and substituted amino groups (mono- or disubstituted amino groups) are similar to those exemplified above.

[0094] Substituent [-R Z2 Examples of hydrocarbon groups in ] include R 1 Examples of hydrocarbon groups include alkyl groups (linear or branched alkyl groups), cycloalkyl groups, aryl groups, and aralkyl groups, as exemplified above. Furthermore, substituents [-R Z2 The hydrocarbon group as ] may be any hydrocarbon group other than an aryl group.

[0095] Base [-OR hZ2 ], base [-SR hZ2 In ], hydrocarbon group R hZ2 For example, R 1 Examples of hydrocarbon groups include alkyl groups (linear or branched alkyl groups), cycloalkyl groups, aryl groups, and aralkyl groups, as well as groups similar to those exemplified in the above. hZ2 ], base [-SR hZ2 In ], hydrocarbon group R hZ2 The types may be the same or different from each other.

[0096] Base [-OR hZ2 For example, R1 In the base [-OR h1 Examples include alkoxy groups (linear or branched alkoxy groups), cycloalkyloxy groups, aryloxy groups, aralkyloxy groups, and similar groups, as exemplified above.

[0097] Base [-SR hZ2 For example, Z 1a ,Z 1b substituents [-R Z1 ] in base[-SR hZ1 Examples of similar groups include alkylthio groups, cycloalkylthio groups, arylthio groups, and aralkylthio groups, as exemplified above.

[0098] Typical substituents [-R Z2 ] includes halogen atoms, hydrocarbon groups, and groups [-OR hZ2 Examples include acyl groups, nitro groups, cyano groups, substituted amino groups, etc.; preferably hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, etc., and alkoxy groups [-OR hZ2 Examples include; more preferably linear or branched C such as a methyl group. 1-6 C such as alkyl groups and cyclohexyl groups 5-8 Cycloalkyl groups, phenyl groups, etc. 6-14 Linear or branched C such as aryl groups and methoxy groups 1-4 Examples include alkoxy groups. Substituents [-R Z2 Among these, alkyl groups are preferred, and in particular linear or branched C such as methyl groups. 1-4 Alkyl alkyl groups are preferred.

[0099] Z 2a ,Z 2b substituents [-R] in each arene ring Z2 The number of substitutions in ] depends on the type of arene ring, for example, an integer of about 0 to 5, preferably an integer of 0 to 3, an integer of 0 to 2, 0 or 1, and especially 0. 2a The number of substitutions in Z 2bThe number of substitutions in Z may be different from each other, but it is preferable that they be the same. 2a If the number of substitutions in is 2 or more, then 2 or more substituents [-R Z2 The types of ] may be the same or different from each other; Z 2b If the number of substitutions in is 2 or more, then 2 or more substituents [-R Z2 The types of ] may be the same or different from each other. Also, Z 2a substituents in [-R Z2 ] Types and Z 2b substituents in [-R Z2 The types of [items] may be different from each other, but it is preferable that they be the same.

[0100] A 1a , A 1b Examples of alkylene groups (linear or branched alkylene groups) represented by this symbol include ethylene, propylene (1,2-propanediyl), trimethylene, 1,2-butanediyl, and tetramethylene groups. 2-6 Examples include alkylene groups, preferably C 2-4 C such as an alkylene group, more preferably an ethylene group, a propylene group, etc. 2-3 Alkylene groups, particularly ethylene groups, are preferred.

[0101] Alkylene oxy group [-(A 1a O)-], [-(A 1b The number of repetitions (number of added moles) m1a and m1b of O)-] can be 0 or greater, and may be selected from integers of approximately 0 to 15, and are preferably, in order from which refractive index, heat resistance and productivity can be easily improved, integers from 0 to 10, integers from 0 to 8, integers from 0 to 6, integers from 0 to 4, integers from 0 to 2, 0 or 1, with 0 being particularly preferred.

[0102] Furthermore, the "number of repetitions (number of added moles)" m1a and m1b may be the average value (arithmetic mean), that is, the average number of added moles as an aggregate (molecular aggregate) of compound (1), and may be selected from a range of approximately 0 to 15, and from the standpoint of easily improving refractive index, heat resistance and productivity, the following steps are preferred: 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, 0 to 1, with 0 being particularly preferred.

[0103] Furthermore, m1a and m1b may be the same or different from each other. If m1a is 2 or more, then 2 or more alkylene oxy groups [-(A 1a The types of O)-] may be different from each other, but are preferably the same; if m1b is 2 or more, 2 or more alkylene oxy groups [-(A 1b The types of O)-] may be different from each other, but it is preferable that they be the same. Note that A 1a and A 1b The types may be different from each other, but it is preferable that they be the same.

[0104] R 2a and R 2b Examples of divalent hydrocarbon groups in this context include divalent aliphatic hydrocarbon groups and divalent aromatic hydrocarbon groups.

[0105] The divalent aliphatic hydrocarbon group may be formed from an aliphatic hydrocarbon skeleton, may be saturated or unsaturated, and may contain a linear (linear or branched) structure or a cyclic structure (alicyclic skeleton).

[0106] Examples of divalent saturated aliphatic hydrocarbon groups include linear saturated aliphatic hydrocarbon groups and alicyclic saturated hydrocarbon groups. Examples of linear saturated aliphatic hydrocarbon groups include linear or branched alkylene groups (including alkylidene groups), specifically methylene groups, ethylene groups, ethylidene groups, trimethylene groups, propylene groups, propylenene groups, tetramethylene groups, pentamethylene groups, hexamethylene groups, etc. 1-10 Examples include alkylene groups, preferably C 1-8 Alkylene group, more preferably C1-4 It may also be an alkylene group. Examples of alicyclic saturated hydrocarbon groups include cycloalkylene groups, specifically cyclohexylene groups, etc. 5-10 Examples include cycloalkylene groups. These alicyclic saturated hydrocarbon groups are alkyl groups, such as methyl groups. 1-6 It may also be an alicyclic saturated hydrocarbon group having an alkyl group, etc.

[0107] Examples of divalent unsaturated aliphatic hydrocarbon groups include chain-like unsaturated aliphatic hydrocarbon groups and alicyclic unsaturated hydrocarbon groups. Examples of chain-like unsaturated aliphatic hydrocarbon groups include alkenylene groups, specifically vinylene groups and propene-1,3-diyl groups. 2-6 Examples include alkenylene groups. Alicyclic unsaturated hydrocarbon groups include, for example, cycloalkenylene groups, specifically cyclohexene-1,4-diyl groups, etc. 5-10 Examples include cycloalkenylene groups. These alicyclic unsaturated hydrocarbon groups are alkyl groups, such as methyl groups. 1-6 It may also be an alicyclic unsaturated hydrocarbon group having an alkyl group, etc.

[0108] Divalent aliphatic hydrocarbon groups include divalent hydrocarbon groups formed by combining two or more of these chain- or cyclic saturated or unsaturated aliphatic hydrocarbon groups, such as alkylene-cycloalkylene groups.

[0109] Of these divalent aliphatic hydrocarbon groups, saturated aliphatic hydrocarbon groups are preferred, and chain-like saturated aliphatic hydrocarbon groups are more preferred, C 1-6 Alkylene groups are even more preferred. The chain-like saturated aliphatic hydrocarbon group may be linear or branched, with linear being preferred.

[0110] The divalent aromatic hydrocarbon group only needs to contain at least an aromatic hydrocarbon skeleton (arene ring skeleton), and may also contain an aliphatic hydrocarbon skeleton such as the aliphatic hydrocarbon group mentioned above. Typical divalent aromatic hydrocarbon groups include arylene groups, such as monocyclic arylene groups, condensed polycyclic arylene groups, and ring-assembled arylene groups. These arylene groups may contain alkyl groups, such as methyl groups. 1-6 It may also be an arylene group having an alkyl group or the like.

[0111] Examples of monocyclic arylene groups include phenylene groups which may have alkyl groups, specifically phenylene groups such as 1,4-phenylene groups, methylphenylene groups, dimethylphenylene groups, and other mono- or tri-C groups. 1-4 Examples include alkylphenylene groups.

[0112] Examples of condensed polycyclic arylene groups include C such as naphthylene groups. 10-14 Arylene group, mono or tri C 1-4 Alkyl-C 10-14 Examples include the arylene group.

[0113] Examples of ring-assembled arylene groups include ring-assembled arylene groups in which two to four arene rings are bonded, such as biphenyl-diyl groups, binaphthyl-diyl groups, phenylnaphthalene-diyl groups, and terphenyl-diyl groups. Preferred ring-assembled arylene groups are ring-assembled arylene groups in which two or three arene rings are bonded, and among these, ring-assembled arylene groups in which two arene rings are bonded, such as biphenyl-diyl groups and C 6-10 Aryl C 6-10 Arene-diyl group, mono or triC 1-4 Alkyl-C 6-10 Aryl C 6-10 An example of an arene-diyl group is a biphenyl-diyl group, such as a biphenyl-4,4'-diyl group or a biphenyl-4,2'-diyl group.

[0114] Of these arylene groups, monocyclic arylene groups and ring-aggregated arylene groups are preferred.

[0115] The divalent aromatic hydrocarbon group includes at least one or more of the aforementioned arylene groups (arylene groups which may have alkyl groups), and also includes divalent hydrocarbon groups bonded in combination with one or more of the aforementioned divalent aliphatic hydrocarbon groups, preferably alkylene groups, such as alkylene-arylene groups and diarylalkane-diyl groups.

[0116] Examples of alkylene-arylene groups include methylene-phenylene groups and methylene-biphenyl-diyl groups. 1-4 Alkylene-C 6-14 Examples include the arylene group. Examples of the methylene-phenylene group include the methylene-1,4-phenylene group, and examples of the methylene-biphenyl-diyl group include the methylene-biphenyl-4,2'-diyl group. Note that among the alkylene-arylene groups, the alkylene group is the group [-C(=O)-R 3a ],[-C(=O)-R 3b The alkylene group may be located on the side of the group [-O-(A 1a O)m 1a -],[-O-(A 1b O)m 1b It is preferable to connect them on the -] side.

[0117] Examples of diarylalkane-diyl groups include diphenylmethane-diyl groups and other diC groups. 6-10 Aryl C 1-10 Examples include alkane-diyl groups.

[0118] Of these divalent aromatic hydrocarbon groups, arylene groups and alkylene-arylene groups are preferred, and phenylene groups, mono- or di-C groups are more preferred. 1-4 C such as alkylphenylene group 6-12 Allirene group, C 1-4 Alkylene-C 6-14Arylene group, especially C 6-10 Allirene group, C 1-3 Alkylene-C 6-12 Arylene groups are preferred.

[0119] Note, R 2a and R 2b The divalent hydrocarbon group in may have one or more substituents, and the substituents may be non-reactive groups (or non-polymerizable groups) that are inert to the reaction, such as nitro groups, cyano groups, and substituted amino groups (mono or disubstituted amino groups). Examples of substituted amino groups (mono or disubstituted amino groups) include R 1 Examples of substituted amino groups (mono- or disubstituted amino groups) similar to those exemplified above can be given.

[0120] R 2a ,R 2b The number of substituents that each divalent hydrocarbon group may have is, depending on the type of divalent hydrocarbon group, for example, an integer of about 0 to 5, preferably in the following order: an integer of 0 to 3, an integer of 0 to 2, 0 or 1, 0 (i.e., unsubstituted). 2a The number of substitutions in R 2b The number of substitutions in R may be different from each other, but it is preferable that they be the same. 2a If the number of substitutions in is two or more, the types of the two or more substituents may be the same or different from each other; R 2b If the number of substitutions in is two or more, the types of the two or more substituents may be the same or different from each other. Also, R 2a The type of substituent in R 2b The types of substituents in the compound may be different from each other, but it is preferable that they be the same.

[0121] Preferred R 2a and R 2bThe group is an unsubstituted divalent hydrocarbon group such as an alkylene group, an arylene group, or an alkylene-arylene group, and more preferably a divalent hydrocarbon group containing at least an aliphatic hydrocarbon skeleton such as an alkylene group, an arylene group, or an alkylene-arylene group, among which a divalent hydrocarbon group containing a saturated aliphatic hydrocarbon skeleton such as an alkylene group is preferred, and an alkylene group (including an alkylidene group) is particularly preferred. In addition, a preferred alkylene group (including an alkylidene group) is C 1-8 It is an alkylene group, and in terms of heat resistance, C 2-6 Alkylene groups having 2 or more carbon atoms, such as alkylene groups, are more preferable, and from the viewpoint of heat resistance and productivity, C 3-5 Alkylene groups having 3 or more carbon atoms, such as alkylene groups, are even more preferred, and C groups such as trimethylene groups are also preferred. 3-4 Alkylene groups are particularly preferred. The alkylene groups may be linear or branched, with linear being preferred. Such R 2a and R 2b Therefore, when used as a resin raw material, it tends to be possible to prepare resins that easily achieve a good balance between high refractive index, high heat resistance, and low birefringence, and exhibit high anomalous dispersion characteristics (high partial dispersion ratio θgF value).

[0122] R 3a and R 3b is a hydroxyl group, group [-OR h3 ](where R h3 (This may represent a hydrocarbon group) or a halogen atom.

[0123] Base [-OR h3 ] hydrocarbon group R h3 Examples include alkyl groups (linear or branched alkyl groups), cycloalkyl groups, aryl groups, and aralkyl groups. 1 Examples of hydrocarbon groups similar to those exemplified in the above are also possible. Preferred hydrocarbon group R h3 C is an alkyl group, and among them lower alkyl groups such as methyl, ethyl, and t-butyl groups. 1-4 Alkyl alkyl groups are even more preferred.

[0124] Base [-OR h3 Examples of alkoxy groups include alkoxy groups (linear or branched alkoxy groups), cycloalkyloxy groups, aryloxy groups, and aralkyloxy groups. Specifically, R 1 In the base [-OR h1 Examples of preferred groups include those similar to the groups exemplified as ]. h3 ] refers to the preferred hydrocarbon group R h3 Corresponding to this, alkoxy groups are preferred, such as methoxy groups, ethoxy groups, t-butoxy groups, etc. 1-4 An alkoxy group is even more preferred.

[0125] R 3a and R 3b Examples of halogen atoms in this include R 1 Examples of atoms similar to the halogen atoms exemplified above can be used, with chlorine atoms and bromine atoms being preferred.

[0126] Note, R 3a and / or R 3b If is a hydroxyl group, the compound (1) may be in the form of a salt (a carboxylate salt). The salt form may be any salt with a metal or compound capable of forming a salt with a carboxyl group, for example, a metal salt, an ammonium salt (NH4 + Examples of metal salts include onium salts such as amine salts. Examples of metal salts include alkali metal salts such as lithium salts, sodium salts, and potassium salts, and alkaline earth metal salts such as calcium salts. Examples of amine salts include mono- or tetraalkylamine salts (mono- or tetraalkylammonium salts) such as dimethylamine salt (dimethylammonium salt), trimethylamine salt (trimethylammonium salt), and triethylamine salt (triethylammonium salt), and pyridine salts (pyridinium salt).

[0127] Also, R 3a and / or R 3bIf is a hydroxyl group, the compound (1) may be in the form of an amide derivative derived from a carboxylic acid, for example, an unsubstituted amide (carboxylic acid amide), a mono- or disubstituted amide, specifically a mono- or dialkylamide.

[0128] Preferred R 3a and R 3b is, base [-OR h3 ] is R 3a and R 3b The types may be different from each other, but it is preferable that they be the same.

[0129] Furthermore, if compound (1) has a substituted or unsubstituted amino group, it may form a salt with an acid, such as an organic acid or an inorganic acid.

[0130] Typical compounds (or salts thereof) represented by the above formula (1) include: R 1 However, halogen atoms, hydrocarbon groups, groups [-OR h1 ], acyl group, nitro group, cyano group or substituted amino group, and k1 is an integer from 0 to 4, Z 1a and Z 1b The arene rings are independently monocyclic or fused polycyclic arene rings. Z 1a and Z 1b substituents [-R Z1 ] independently, halogen atom, hydrocarbon group, group [-OR hZ1 ], base [-SR hZ1 ], acyl group, nitro group, cyano group or substituted amino group, and substituent [-R Z1 The number of ] is an independent integer between 0 and 3. Z 2a and Z 2b The arene rings are independently monocyclic or fused polycyclic arene rings. Z 2a and Z 2b substituents [-R Z2 ] independently constitute a halogen atom, hydrocarbon group, group [-OR hZ2 ], base [-SRhZ2 ], acyl group, nitro group, cyano group or substituted amino group, and substituent [-R Z2 The number of ] is an independent integer between 0 and 3. m1a and m1b are independent integers between 0 and 10. R 2a and R 2b The divalent hydrocarbon group is independently an alkylene group, an arylene group, or an alkylene-arylene group. R 2a and R 2b Examples of compounds (or salts thereof) in which the substituents that may be present are independently a nitro group, a cyano group, or a substituted amino group, and the number of substitutions is an integer from 0 to 3; Preferably, R 1 However, hydrocarbon groups such as alkyl groups and aryl groups, or groups such as alkoxy groups [-OR h1 ] and k1 is an integer between 0 and 2, Z 1a and Z 1b The arene ring is independently a benzene ring or a fused polycyclic C 10-14 It is an allene ring, Z 1a and Z 1b substituents [-R Z1 ] independently of hydrocarbon groups such as alkyl groups, or groups such as alkoxy groups [-OR hZ1 ] and substituent[-R Z1 The number of ] is an independent integer between 0 and 2. Z 2a and Z 2b The arene ring is independently a benzene ring or a fused polycyclic C 10-14 It is an allene ring, Z 2a and Z 2b substituents [-R Z2 ] independently of hydrocarbon groups such as alkyl groups, or groups such as alkoxy groups [-OR hZ2 ] and substituent[-R Z2 The number of ] is an independent integer between 0 and 2. A 1a and A 1b However, independently C2-6 It represents an alkylene group, and m1a and m1b are independent integers from 0 to 6. R 2a and R 2b The divalent hydrocarbon group is independently C 1-6 Alkylene groups such as alkylene groups R 2a and R 2b Examples include compounds (or salts thereof) in which the group is a divalent hydrocarbon group without substituents; More preferably, R 1 However, C 1-4 Alkyl or C 6-12 The aryl group, k1 is an integer between 0 and 2, Z 1a and Z 1b The arene ring is independently either a benzene ring or a naphthalene ring. Z 1a and Z 1b substituents [-R Z1 ] independently, C 1-4 It is an alkyl group and has a substituent [-R Z1 The number of ] is either 0 or 1 independently. Z 2a and Z 2b The arene ring is independently either a benzene ring or a naphthalene ring. Z 2a and Z 2b substituents [-R Z2 ] independently C 1-4 It is an alkyl group and has a substituent [-R Z2 The number of ] is either 0 or 1 independently. A 1a and A 1b However, independently C 2-4 It represents an alkylene group, and m1a and m1b are independent integers from 0 to 3. R 2a and R 2b However, independently C 2-5 C groups such as alkylene groups 1-5 It is an alkylene group, R 3a and R 3b However, independently of the hydroxyl group or group [-ORh3 Examples include compounds (or salts thereof) that are ]; Particularly preferred, R 1 However, C 1-4 Alkyl group, k1 is an integer of 0 or 2, Z 1a and Z 1b However, it is a naphthalene ring, Z 1a and Z 1b substituents [-R Z1 ] independently, C 1-4 It is an alkyl group and has a substituent [-R Z1 The number of ] is either 0 or 1 independently. Z 2a and Z 2b The arene ring is independently either a benzene ring or a naphthalene ring. Z 2a and Z 2b substituents [-R Z2 ] independently C 1-4 It is an alkyl group and has a substituent [-R Z2 The number of ] is either 0 or 1 independently. A 1a and A 1b However, independently C 2-3 It exhibits an alkylene group, and m1a and m1b are independently 0 or 1. R 2a and R 2b However, independently C 3-4 C groups such as alkylene groups 1-4 It is an alkylene group, R 3a and R 3b However, independently of the base [-OR h3 Examples of compounds include those that are [ ].

[0131] Examples of specific compounds (or salts thereof) represented by formula (1) include 9,9-bis(aryl-carboxyalkyloxy-aryl)fluorene, 9,9-bis(aryl-carboxyaryloxy-aryl)fluorene, and 9,9-bis(aryl-carboxyarylalkyloxy-aryl)fluorene.

[0132] Examples of 9,9-bis(aryl-carboxyalkyloxy-aryl)fluorene include 9,9-bis[3-phenyl-4-(3-carboxypropyloxy)-phenyl]fluorene, 9,9-bis[3-(2-naphthyl)-4-(3-carboxypropyloxy)-phenyl]fluorene, 9,9-bis[3-(1-naphthyl)-4-(3-carboxypropyloxy)-phenyl]fluorene, 9,9-bis[5-phenyl-6-(3-carboxypropyloxy)-2-naphthyl]fluorene, 9,9-bis[5-(2-naphthyl)-6-(3-carboxypropyloxy)-2-naphthyl]fluorene, and 9,9-bis[5-(1-naphthyl)-6-(3-carboxypropyloxy)-2-naphthyl]fluorene, etc. 6-10 Aryl-carboxyl C 1-6 Alkyloxy-C 6-10 Examples include aryl fluorenes and their derivatives, such as esters like alkyl esters, acid halides like acid chlorides, and salts like metal salts.

[0133] Examples of 9,9-bis(aryl-carboxyaryloxy-aryl)fluorene include 9,9-bis[3-phenyl-4-(4-carboxyphenyloxy)-phenyl]fluorene, 9,9-bis[3-(2-naphthyl)-4-(4-carboxyphenyloxy)-phenyl]fluorene, 9,9-bis[3-(1-naphthyl)-4-(4-carboxyphenyloxy)-phenyl]fluorene, 9,9-bis[5-phenyl-6-(4-carboxyphenyloxy)-2-naphthyl]fluorene, 9,9-bis[5-(2-naphthyl)-6-(4-carboxyphenyloxy)-2-naphthyl]fluorene, and 9,9-bis[5-(1-naphthyl)-6-(4-carboxyphenyloxy)-2-naphthyl]fluorene, etc. 6-10 Aryl-carboxyl C 6-10 Aryloxy-C 6-10Examples include aryl fluorenes and their derivatives, such as esters like alkyl esters, acid halides like acid chlorides, and salts like metal salts.

[0134] Examples of 9,9-bis(aryl-carboxyarylalkyloxy-aryl)fluorene include 9,9-bis(aryl-carboxyphenylalkyloxy-aryl)fluorene, 9,9-bis(aryl-carboxybiphenylalkyloxy-aryl)fluorene, and other 9,9-bis(C 6-10 Aryl-carboxyl C 6-12 Aryl C 1-6 Alkyloxy-C 6-10 Examples include aryl fluorenes and their derivatives, such as esters like alkyl esters, acid halides like acid chlorides, and salts like metal salts.

[0135] Examples of 9,9-bis(aryl-carboxyphenylalkyloxy-aryl)fluorene include 9,9-bis[3-phenyl-4-(4-carboxyphenylmethoxy)-phenyl]fluorene, 9,9-bis[3-(2-naphthyl)-4-(4-carboxyphenylmethoxy)-phenyl]fluorene, 9,9-bis[3-(1-naphthyl)-4-(4-carboxyphenylmethoxy)-phenyl]fluorene, 9,9-bis[5-phenyl-6-(4-carboxyphenylmethoxy)-2-naphthyl]fluorene, 9,9-bis[5-(2-naphthyl)-6-(4-carboxyphenylmethoxy)-2-naphthyl]fluorene, and 9,9-bis[5-(1-naphthyl)-6-(4-carboxyphenylmethoxy)-2-naphthyl]fluorene, etc. 6-10 Aryl-carboxyphenyl C 1-4 Alkyloxy-C 6-10 Examples include fluorene (aryl).

[0136] Examples of 9,9-bis(aryl-carboxybiphenylalkyloxy-aryl)fluorene include 9,9-bis[3-phenyl-4-(2'-carboxybiphenyl-4-yl-methoxy)-phenyl]fluorene, 9,9-bis[3-(2-naphthyl)-4-(2'-carboxybiphenyl-4-yl-methoxy)-phenyl]fluorene, and 9,9-bis[3-(1-naphthyl)-4-(2'-carboxybiphenyl-4-yl- Fluorene such as 9,9-bis[5-phenyl-6-(2'-carboxybiphenyl-4-yl-methoxy)-2-naphthyl]fluorene, 9,9-bis[5-(2-naphthyl)-6-(2'-carboxybiphenyl-4-yl-methoxy)-2-naphthyl]fluorene, 9,9-bis[5-(1-naphthyl)-6-(2'-carboxybiphenyl-4-yl-methoxy)-2-naphthyl]fluorene, etc. 6-10 Arylcarboxybiphenyl C 1-4 Alkyloxy-C 6-10 Examples include fluorene (aryl).

[0137] (Properties of the compound represented by formula (1)) Compound (1) (or its salt) may be in crystalline form.

[0138] Compound (1) (or its salt) has a high refractive index, and its refractive index nD may be, for example, about 1.63 to 1.7 at a temperature of 25°C and a wavelength of 589 nm, and preferably in the following increments: 1.64 to 1.69, 1.65 to 1.68, and 1.66 to 1.67.

[0139] In this specification and in the claims, the refractive index can be measured by the method described in the examples below.

[0140] Compound (1) (or its salt) has excellent heat resistance, and the 5% weight loss temperature may be, for example, around 200 to 450°C, preferably in stages, 250 to 430°C, 300 to 410°C, 320 to 350°C, and more preferably in stages, 330 to 430°C, 350 to 420°C, and 380 to 410°C. The 10% weight loss temperature may also be, for example, around 300 to 450°C, preferably in stages, 350 to 435°C, 380 to 430°C, 390 to 425°C, and 400 to 420°C.

[0141] In this specification and in the claims, the weight loss temperature is the temperature measured under a nitrogen atmosphere and a heating rate of 10°C / min, and can be measured by the method described in the examples below.

[0142] (Method for producing the compound represented by formula (1)) The method for producing the compound (1) (or a salt thereof) is not particularly limited, but it is preferable to include a coupling step in which the compound represented by formula (2) below (or a salt thereof) is coupled with the compounds represented by formulas (3a) and (3b) below.

[0143] In this specification and in the claims, the compound represented by formula (2) may also be simply referred to as "compound (2)," and similarly, the compound represented by formula (3a) may be referred to as "compound (3a)," and the compound represented by formula (3b) may be referred to as "compound (3b)." Furthermore, compound (3a) and compound (3b) may be referred to as "compound (3a)(3b)."

[0144] [ka]

[0145] [where, X 1a and X 1b And, X 2a and X 2b These are carbon-carbon bonds (Z) formed by a coupling reaction between them. 1a and Z 1b The arene ring and Z2a and Z 2b It shows a group that can form a direct bond with the arene ring, R 1 , k1, Z 1a and Z 1b , Z 2a and Z 2b , A 1a and A 1b , m1a and m1b, R 2a and R 2b , R 3a and R 3b [These are the same as formula (1) above, including preferred embodiments.]

[0146] Examples of coupling reactions (or cross-coupling reactions) include conventional coupling reactions such as the Suzuki-Miyaura coupling reaction, the Migita-Kosugi-Stille coupling reaction, the Negishi coupling reaction, and the Hiyama coupling reaction, which are catalyzed with palladium catalysts (or palladium(0) catalysts), and the Kumada-Tamao-Corriu coupling reaction, which are catalyzed with nickel catalysts (or nickel(0) catalysts). Of these coupling reactions, the Suzuki-Miyaura coupling reaction is preferred.

[0147] In equation (2) above, X 1a and X 1b Independently, these represent reactive groups capable of forming a carbon-carbon bond (or direct bond) by a coupling reaction; in formulas (3a) and (3b), X 2a The reactive group X 1a And, X 2b The reactive group X 1b Each of these groups exhibits a reactive group capable of forming a carbon-carbon bond through a coupling reaction. Reactive group X 1a and X 1b and X 2a and X 2b This can be appropriately selected depending on the type of coupling reaction. When synthesized by the Suzuki-Miyaura coupling reaction, one of the reactive groups, for example, group X 1a and X 1bExamples include boron-free groups (or leaving groups) such as halogen atoms or fluorinated alkanesulfonyloxy groups. Examples of halogen atoms include iodine atoms, bromine atoms, and chlorine atoms. Examples of fluorinated alkanesulfonyloxy groups include trifluoromethanesulfonyloxy groups (or groups [-OTf]) and other fluorinated C groups. 1-4 Examples include alkanesulfonyloxy groups. One of these reactive groups may be used alone or in combination of two or more. Of these reactive groups, a halogen atom is preferred, an iodine atom is more preferred, a bromine atom is more preferred, and a bromine atom is even more preferred.

[0148] The reactive group X in the Suzuki-Miyaura coupling reaction 1a and X 1b The other reactive group X that can be coupled with 2a and X 2b Examples of the other reactive group include boron-containing groups such as boronic acid groups (dihydroxyboryl group or group [-B(OH)2]) and boronic acid ester groups. Examples of boronic acid ester groups include dialkoxyboryl groups such as dimethoxyboryl group, diisopropoxyboryl group, and dibutoxyboryl group; and cyclic boronic acid ester groups such as pinacolateboryl group (or group [-Bpin]), 1,3,2-dioxaborinan-2-yl group, and 5,5-dimethyl-1,3,2-dioxaborinan-2-yl group. These other reactive groups may be used alone or in combination of two or more. Of the other reactive groups, the group [-B(OH)2] is preferred.

[0149] Note that base X 1a and X 1b And, base X 2a and X 2b This means that any pair of reactive groups that can be coupled with each other can be used, and group X 1a and X 1b The boron-containing group is a boronic acid group, and group X 2a and X 2b The group X may be a boron-free group (or leaving group) such as a halogen atom,1a and X 1b The group X is a boron-free group such as a halogen atom, and 2a and X 2b It is preferable that this is a boron-containing group such as a boronic acid group.

[0150] Compound (2) (or its salt) is a compound corresponding to a preferred embodiment of compound (1) (or its salt), for example, Z of formula (1). 2a ,Z 2b Instead, compounds in which halogen atoms such as bromine atoms are bonded (Z 1a ,Z 1b Z in the arene ring 2a ,Z 2b Examples include compounds in which a halogen atom is bonded to the bonding position of (2) (or salts thereof). Representative compounds (2) (or salts thereof) include, for example, 9,9-bis(halo-carboxyalkyloxy-aryl)fluorene, specifically 9,9-bis[3-bromo-4-(3-carboxypropyloxy)-phenyl]fluorene, 9,9-bis[5-bromo-6-(3-carboxypropyloxy)-2-naphthyl]fluorene, etc. 1-6 Alkyloxy-C 6-10 Examples include aryl fluorenes and their derivatives, such as esters like alkyl esters, acid halides like acid chlorides, and salts like metal salts.

[0151] Compounds (3a) and (3b) include compounds corresponding to preferred embodiments of compound (1) (or its salt), such as arylboronic acids like phenylboronic acid, 1-naphthylboronic acid, and 2-naphthylboronic acid, and C such as phenylboronic acid and 2-naphthylboronic acid. 6-10 Arylboronic acid is preferred.

[0152] It is preferable that compound (3a) and compound (3b) have the same chemical structure. Commercially available compounds (3a) and (3b) can be used.

[0153] The ratio of compound (2) (or its salt) to the total amount of compounds (3a) and (3b) may be, for example, the former / latter (molar ratio) = 1 / 2 to 1 / 10, and preferably, in stages, 1 / 2.1 to 1 / 5, 1 / 2.2 to 1 / 3, and 1 / 2.25 to 1 / 2.5.

[0154] The coupling reaction may be carried out in the presence of a catalyst. When synthesized by the Suzuki-Miyaura coupling reaction, the reaction may be carried out in the presence of a palladium catalyst, and examples of palladium catalysts include conventional coupling catalysts such as palladium(O) catalysts and palladium(II) catalysts.

[0155] Examples of palladium(O) catalysts include palladium(O)-phosphine complexes such as tetrakis(triphenylphosphine)palladium(O) [or Pd(PPh3)4] and bis(tri-t-butylphosphine)palladium(O) [or Pd(P(t-Bu)3)2].

[0156] Examples of palladium(II) catalysts include palladium(II)-phosphine complexes such as [1,2-bis(diphenylphosphino)ethane]palladium(II) dichloride [or PdCl2(dppe)], [1,3-bis(diphenylphosphino)propane]palladium(II) dichloride [or PdCl2(dppp)], [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride [or PdCl2(dppf)], bis(triphenylphosphine)palladium(II) dichloride [or PdCl2(PPh3)2], and bis(tri-o-tolylphosphine)palladium(II) dichloride [or PdCl2(P(o-tolyl)3)2]. When using a palladium(II) catalyst, the reaction is initiated by reduction to a zero-valent complex by reducing compounds in the reaction system, such as phosphine, amine, or organometallic reagents.

[0157] The palladium catalyst may also be prepared in the reaction system by adding a catalyst precursor such as tris(dibenzylideneacetone)dipalladium(0)chloroform complex [or Pd2(dba)3·CHCl3] or palladium(II) acetate to a ligand such as a phosphine such as triphenylphosphine or a carbene. The ratio of the catalyst precursor to the ligand may be, for example, about 1 / 2 to 1 / 10 (molar ratio), preferably 1 / 2.3 to 1 / 4, and more preferably 1 / 2.5 to 1 / 3.5.

[0158] These catalysts can be used individually or in combination of two or more. Of these catalysts, catalyst precursors such as palladium(II) acetate are particularly preferred due to their excellent operability (stability in air). The proportion of catalyst or catalyst precursor may be, for example, about 0.0001 to 0.1 moles of metal per mole of compound (2) (or its salt), preferably 0.001 to 0.05 moles, and more preferably 0.005 to 0.025 moles.

[0159] The Suzuki-Miyaura coupling reaction may be carried out in the presence of a base. Examples of bases include metal carbonates or bicarbonates, metal hydroxides, metal fluorides, metal phosphates, metal organic acid salts, and metal alkoxides.

[0160] Examples of metal carbonates or bicarbonates include alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate, alkali metal bicarbonates such as sodium bicarbonate, and thallium(I) carbonate.

[0161] Examples of metal hydroxides include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and cesium hydroxide, alkaline earth metal hydroxides such as barium hydroxide, and thallium(I) hydroxide.

[0162] Examples of metal fluorides include alkali metal fluorides such as potassium fluoride and cesium fluoride.

[0163] Examples of metal phosphates include alkali metal phosphates such as tripotassium phosphate.

[0164] Examples of metal organic salts include alkali metal acetates such as potassium acetate.

[0165] Examples of metal alkoxides include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide.

[0166] These bases can be used individually or in combination of two or more. Preferred bases include metal carbonates, with alkali metal carbonates such as sodium carbonate being even more preferred. The proportion of the base may be, for example, about 0.1 to 50 moles per mole of compound (2) (or its salt), and preferably in the following increments: 1 to 5 moles, 2 to 4 moles, and 2.5 to 3 moles.

[0167] The coupling reaction may be carried out with or without a phase transfer catalyst. Examples of phase transfer catalysts include tetrabutylammonium bromide (TBAB) and tetraalkylammonium halides such as trioctylmethylammonium chloride. These phase transfer catalysts can be used individually or in combination of two or more.

[0168] Coupling reactions may be carried out in the absence or presence of a solvent inert to the reaction. Examples of solvents include water; alcohols such as methanol and ethanol; ethers such as cyclic ethers and chain ethers; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone (MIBK); esters such as ethyl acetate; nitriles such as acetonitrile and benzonitrile; amides such as N,N-dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxides such as dimethyl sulfoxide; and hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

[0169] Examples of cyclic ethers include dioxane and tetrahydrofuran. Examples of linear ethers include dialkyl ethers such as diethyl ether and diisopropyl ether, and glycol ethers. Examples of glycol ethers include (poly)alkylene glycol monoalkyl ethers such as methyl cellosolve and methyl carbitol, and (poly)alkylene glycol dialkyl ethers such as dimethoxyethane.

[0170] Examples of aliphatic hydrocarbons include hexane and dodecane. Examples of alicyclic hydrocarbons include cyclohexane. Examples of aromatic hydrocarbons include toluene and xylene.

[0171] These solvents can be used individually or in combination of two or more. Of these solvents, a mixed solvent of water and ketones such as MIBK is preferred. The ratio of water to ketones such as MIBK may be, for example, about 5 / 95 to 50 / 50 (mass ratio), and preferably in stages, 10 / 90 to 40 / 60, 15 / 85 to 35 / 65, and 20 / 80 to 30 / 70. The proportion of the solvent is, for example, 100 to 1000 parts by mass, preferably 200 to 800 parts by mass, and more preferably 400 to 600 parts by mass, per 100 parts by mass of the total amount of compound (2) (or its salt) and compounds (3a)(3b).

[0172] The coupling reaction may be carried out under an inert gas atmosphere, such as nitrogen gas; a noble gas such as helium or argon; preferably under an inert gas atmosphere such as nitrogen gas; and may also be carried out under reduced pressure, atmospheric pressure, or pressurized pressure. The reaction temperature is, for example, 50 to 150°C, preferably 60 to 120°C, more preferably 70 to 100°C, and particularly 80 to 90°C, and the reaction may be carried out under reflux. The reaction time may be, for example, about 0.5 to 24 hours, preferably 3 to 6 hours.

[0173] After the reaction is complete, the reaction mixture may be separated and purified as needed by conventional separation and purification methods, such as neutralization, washing, extraction, filtration, dehydration, concentration, decantation, drying, crystallization, reprecipitation, column chromatography, adsorption, or a combination thereof.

[0174] (Method for producing the compound represented by formula (2)) The method for producing compound (2) (or its salt) is not particularly limited, and may be produced in accordance with the methods described in Japanese Patent Publication No. 2009-256332 and Japanese Patent Publication No. 2009-256333. Specifically, it can be produced by reacting (nucleophilic reaction or dehalogenation reaction) a compound represented by the following formula (4) with a compound represented by the following formula (5a) (or its salt) and a compound represented by the following formula (5b) (or its salt).

[0175] In this specification and in the claims, the compound represented by formula (4) may also be simply referred to as "compound (4)," and similarly, the compound represented by formula (5a) may be referred to as "compound (5a)," and the compound represented by formula (5b) may be referred to as "compound (5b)." Furthermore, compound (5a) and compound (5b) may be referred to as "compound (5a)(5b)."

[0176] [ka]

[0177] [where, X 3a and X 3b These independently represent halogen atoms, R 1 , k1, Z 1a and Z 1b , A 1a and A 1b , m1a and m1b, X 1a and X 1b , R 2a and R 2b , R 3a and R 3b These are the same as formulas (1) and (2) above, including preferred embodiments.

[0178] Examples of compound (4) include compounds corresponding to preferred embodiments of compound (1) (or its salt) and compound (2) (or its salt), and a representative example of compound (4) is X 3a and X 3b Examples include compounds in which the first element is a halogen atom such as a bromine atom, and m1a and m1b are 0, such as 9,9-bis(halo-hydroxy-aryl)fluorene, specifically 9,9-bis[3-bromo-4-hydroxy-phenyl]fluorene, 9,9-bis[5-bromo-6-hydroxy-2-naphthyl]fluorene, etc. 6-10 Examples include fluorene (aryl).

[0179] In equations (5a) and (5b) above, X 3a and X 3b Examples of halogen atoms include iodine, bromine, and chlorine atoms, with bromine being preferred.

[0180] Compounds (5a) and (5b) may be halogenated carboxylic acids or their derivatives, preferably compounds corresponding to preferred embodiments of compound (1) (or its salt) and compound (2) (or its salt), for example, haloalkanoic acids, specifically bromoalkanoic acids such as bromoacetic acid, 2-bromopropionic acid, 3-bromopropionic acid, 2-bromobutyric acid, 3-bromobutyric acid, 4-bromobutyric acid, chloroalkanoic acids (alkanoic acids in which a chlorine atom is bonded in place of a bromine atom) corresponding to these bromoalkanoic acids, and derivatives thereof, for example, esters such as alkyl esters, acid halides such as acid chlorides, salts such as metal salts, etc. Preferred compounds (5a) and (5b) (or their salts) are haloalkanoic acids such as bromoalkanoic acid and chloroalkanoic acid or derivatives thereof, and more preferably C 2-10 Bromoalkanoic acid, C 2-10 C such as chloroalkanoic acid 2-10 Haloalkanoic acid or esters thereof, more preferably C 3-6 Bromoalkanoic acid, C 3-6C such as chloroalkanoic acid 3-6 Haloalkanoates or their alkyl esters, in particular C, such as ethyl 4-bromobutyrate. 3-6 Bromoalkanoic acid or its C 1-4 Alkyl esters are preferred.

[0181] It is preferable that compound (5a) (or its salt) and compound (5b) (or its salt) have the same chemical structure. Commercially available compounds (5a) and (5b) can be used.

[0182] The ratio of compound (4) to the total amount of compounds (5a) and (5b) (or their salts) may be, for example, the former / latter (molar ratio) = 1 / 2 to 1 / 10, and preferably, in stages, 1 / 2.2 to 1 / 5, 1 / 2.4 to 1 / 3, and 1 / 2.5 to 1 / 2.7.

[0183] The reaction may usually be carried out in the presence of a basic compound (basic catalyst, base catalyst). Examples of basic compounds include inorganic bases and organic bases.

[0184] Examples of inorganic bases include metal hydroxides, metal hydrides, metal carbonates, and metal bicarbonates.

[0185] Examples of metal hydroxides include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, and alkaline earth metal hydroxides such as calcium hydroxide.

[0186] Examples of metal hydrides include alkali metal hydrides such as sodium hydride and potassium hydride, and alkaline earth metal hydrides.

[0187] Examples of metal carbonates include alkali metal carbonates such as lithium carbonate, potassium carbonate, and sodium carbonate, as well as alkaline earth metal carbonates.

[0188] Examples of metal bicarbonates include alkali metal bicarbonates such as potassium bicarbonate and sodium bicarbonate, and alkaline earth metal bicarbonates.

[0189] Examples of organic bases include amines, metal carboxylate salts, quaternary ammonium salts, and quaternary phosphonium salts.

[0190] Examples of amines include aliphatic amines, aromatic amines, and heterocyclic amines.

[0191] Examples of aliphatic amines include primary to tertiary aliphatic amines such as aliphatic tertiary amines, specifically trialkylamines such as triethylamine, diethylmethylamine, diisopropylethylamine, tri-n-propylamine, and tributylamine, tricycloalkylamines such as tricyclohexylamine, and methyldicyclohexylamine.

[0192] Examples of aromatic amines include primary to tertiary aromatic amines, such as aromatic tertiary amines like N,N-dimethylaniline.

[0193] Examples of heterocyclic amines include primary to tertiary heterocyclic amines, specifically, heterocyclic tertiary amines such as picoline, pyridine, pyrazine, pyrimidine, pyridazine, 1-methylimidazole, triethylenediamine, N,N-dimethylaminopyridine, and 1,8-diazabicyclo[5.4.0]unde-7-cene, and heterocyclic secondary amines such as piperidine.

[0194] Examples of carboxylate metal salts include alkali metal acetates such as sodium acetate, and alkaline earth metal acetates such as calcium acetate.

[0195] Examples of quaternary ammonium salts include tetraalkylammonium halides such as tetraethylammonium chloride, and benzyltrialkylammonium halides such as benzyltrimethylammonium chloride.

[0196] Examples of quaternary phosphonium salts include benzyltriphenylphosphonium chloride.

[0197] These basic compounds may be used individually or in combination of two or more. Of these, inorganic bases such as metal carbonates are preferred, and alkali metal carbonates such as potassium carbonate are even more preferred.

[0198] The amount of basic compound used may be adjusted depending on the reaction, for example, 0.1 to 10 moles per mole of hydroxyl group of compound (4), preferably in stages, 1 to 5 moles, 1.5 to 4 moles, and 2 to 3 moles.

[0199] The reaction between compound (4) and compounds (5a)(5b) (or their salts) may be carried out in the absence of a solvent or in the presence of a solvent. The solvent is not limited as long as it does not inhibit the reaction, but examples include organic solvents such as alcohols, amides, nitriles, sulfur compounds, ethers, and hydrocarbons; and inorganic solvents such as water.

[0200] Examples of alcohols include alkanols, specifically methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, etc. 1-6 Alkanols; alkylene glycol monoalkyl ethers, specifically C such as 2-methoxyethanol. 1-4 Alkoxy-C 2-4 Examples include alkanols, cycloalkanols such as cyclohexanol, and glycerin.

[0201] Examples of amides include N-methylformamide and N,N-dimethylformamide (DMF), which are N-mono or diC. 1-4Alkylformamides; N-methylacetamide, N,N-dimethylacetamide, and other N-mono or di-C formsamides. 1-4 Examples include alkylacetamides.

[0202] Examples of nitriles include acetonitrile and propionitrile.

[0203] Examples of sulfur compounds include sulfoxides such as dimethyl sulfoxide; and sulfones, specifically cyclic sulfones such as sulfolane.

[0204] Examples of ethers include dialkyl ethers such as diethyl ether; (poly)alkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether; and cyclic ethers such as tetrahydrofuran and 1,4-dioxane.

[0205] Examples of hydrocarbons include aliphatic hydrocarbons such as pentane, hexane, heptane, and cyclohexane; and aromatic hydrocarbons such as toluene and xylene.

[0206] These solvents may be used individually or in combination of two or more. Furthermore, amides such as DMF are preferred as solvents.

[0207] The proportion of the solvent is, for example, 10 to 1000 parts by mass, preferably 100 to 500 parts by mass, and more preferably 200 to 300 parts by mass, per 100 parts by mass of the total amount of compound (4) and compounds (5a)(5b) (or their salts).

[0208] The reaction may be carried out with stirring, in air or under an inert gas atmosphere, preferably nitrogen gas or a noble gas such as helium or argon, and under reduced pressure, atmospheric pressure or pressurized pressure. The reaction temperature may be, for example, around 0 to 250°C, preferably 30 to 150°C, more preferably 60 to 100°C, and particularly 70 to 90°C. The reaction may also be carried out under reflux of the solvent. The reaction time may be, for example, around 1 to 72 hours, preferably 2 to 6 hours.

[0209] After the reaction is complete, the reaction mixture may be separated and purified as needed by conventional separation and purification methods, such as neutralization, washing, extraction, filtration, dehydration, concentration, drying, crystallization, recrystallization, column chromatography, or a combination thereof.

[0210] (Method for producing the compound represented by formula (4)) The method for producing compound (4) is not particularly limited, and may be produced, for example, in accordance with the method described in Japanese Patent Application Publication No. 2009-256334, specifically a compound represented by the following formula (6) and a reactive group X 1a and X 1b It can be produced by reacting halogenating agents, etc., with halogen atoms as the basis for its production.

[0211] In this specification and in the claims, the compound represented by formula (6) may be simply referred to as "compound (6)".

[0212] [ka]

[0213] [In the formula, R 1 , k1, Z 1a and Z 1b , A 1a and A 1b m1a and m1b are the same as those in formulas (1), (2), and (4), respectively, including preferred embodiments.

[0214] Examples of compound (6) include compounds corresponding to preferred embodiments of compound (1), compound (2), and compound (4), and a typical example of compound (6) is a compound in which m1a and m1b are 0, such as 9,9-bis(hydroxyaryl)fluorene, specifically 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)fluorene, etc. 6-10 Examples include fluorene (aryl).

[0215] Reactive group X 1a and X 1b Examples of halogenating agents corresponding to halogen atoms include elemental halogens such as bromine (Br2).

[0216] The ratio of compound (6) to halogenating agent may be, for example, the former / latter (molar ratio) = approximately 1 / 0.9 to 1 / 20, and preferably, in stages, 1 / 1 to 1 / 10, 1 / 1.5 to 1 / 3, and 1 / 2 to 1 / 2.1.

[0217] A catalyst (or additive) may be used to accelerate the reaction. An example of such a catalyst is a reactive group X. 1a and X 1b When the atom is bromine, examples include Lewis acids such as iron chloride and zinc chloride, halogens (other than bromine) such as iodine (I2), heavy metals such as iron and nickel, oxidizing agents such as hydrogen peroxide and periodic acid, and mineral acids such as sulfuric acid, hydrochloric acid, and hydrobromic acid.

[0218] The reaction may be carried out in the presence of a solvent. The solvent can be any solvent that can dissolve (or disperse) compound (6) and does not react with halogenating agents such as bromine, such as ethers, halogenated solvents, and ketones.

[0219] Examples of ethers include dialkyl ethers such as diethyl ether and diisopropyl ether, and cyclic ethers such as tetrahydrofuran and dioxane.

[0220] Examples of halogenated solvents include halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride.

[0221] Examples of ketones include acetone, methyl ethyl ketone, and dialkyl ketones such as methyl isobutyl ketone.

[0222] These solvents may be used individually or in combination of two or more. Of these solvents, halogenated hydrocarbons such as chloroform are preferred.

[0223] The method of mixing the solvent is not particularly limited. For example, it may be mixed with compound (4) beforehand, or mixed with compound (4) and a halogenating agent such as bromine beforehand, or a halogenating agent such as bromine may be dissolved in part or all of the solvent and then mixed with compound (4).

[0224] The reaction may be carried out with stirring, in air or under an inert gas atmosphere, preferably nitrogen gas or a noble gas such as helium or argon, and under reduced pressure, atmospheric pressure, or pressurized pressure. The reaction temperature is, for example, -20°C to 100°C, preferably -10°C to 50°C, more preferably 0°C to 30°C, and particularly 10 to 25°C. If the reaction generates heat, the heat generated may be removed as needed during the reaction. The reaction time is, for example, 1 minute to 48 hours, preferably 30 minutes to 12 hours, and more preferably 1 to 6 hours.

[0225] The reaction products may be separated and purified by conventional methods, such as washing, filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination thereof. In this method, the process usually proceeds quantitatively, and the target product can be easily recovered from the reaction products (reaction system) with high purity by operations such as liquid-liquid separation or filtration after decomposing any remaining bromine as needed. Further purification by distillation or recrystallization may be performed to increase purity.

[0226] [resin] The present invention includes resins that use the above compound (1) (or a salt thereof) or a derivative thereof as a raw material (precursor component or intermediate), for example, resins that include at least a constituent unit represented by the following formula (A-1).

[0227] [ka]

[0228] [In the formula, R 1 represents a substituent, and k1 represents an integer from 0 to 8. Z 1a and Z 1b These independently represent substituted or unsubstituted arene rings. Z 2a and Z 2b These independently represent substituted or unsubstituted arene rings. A 1a and A 1b m1a and m1b independently represent an alkylene group, and m1a and m1b independently represent an integer greater than or equal to 0. R 2a and R 2b These independently represent substituted or unsubstituted divalent hydrocarbon groups. All of these are the same as formula (1) above, including preferred embodiments.

[0229] The resin of the present invention may be a curable resin (thermo-curable or photo-curable resin) or a thermoplastic resin.

[0230] The curable resin (thermally or photocurable resin) can be any resin made from compound (1) (or a salt thereof) as a raw material. Examples include epoxy resins such as glycidyl ester type epoxy resins obtained by reaction with epihalohydrins (or cured products of curable compositions containing this epoxy resin); (meth)acrylic resins obtained by reaction with hydroxyalkyl (meth)acrylates (or cured products of curable compositions containing this (meth)acrylic resin); and reaction products (cured products or three-dimensional crosslinked products) of compound (1) (or a salt thereof) with polyol components, polyamine components and / or polyisocyanate components.

[0231] The thermoplastic resin may contain at least a dicarboxylic acid component as a polymerization component (monomer component), and this dicarboxylic acid component may contain at least the aforementioned compound (1) (or a salt thereof). For example, it may be a polyester resin that further contains a diol component in addition to the dicarboxylic acid component as a polymerization component, or it may be a polyamide resin that contains a diamine component or the like.

[0232] The polyester resin can be any resin that contains at least ester bonds as linking groups in the main chain [groups formed by polymerization reactions that connect adjacent structural units (structural units derived from polymerization components) (divalent groups)], and it is sufficient if the resin contains, for example, 30 to 100 mol% of ester bonds, preferably in stages of 50 mol% or more, 70 mol% or more, and 90 mol% or more, relative to the total number of linking groups. Note that the ester bonds as linking groups also include carbonate ester bonds. Typical polyester resins include polyester resins and polyester carbonate resins.

[0233] Of these resins, thermoplastic resins are preferred from the viewpoint of moldability and optical properties, polyester resins are more preferred from the viewpoint of water resistance and dimensional stability, and polyester resins are particularly preferred.

[0234] (Dicarboxylic acid unit (A)) The resin (thermoplastic resin) contains at least a dicarboxylic acid unit (A) corresponding to the dicarboxylic acid component as a polymerization component, and this dicarboxylic acid unit (A) contains at least the constituent unit represented by the formula (A-1) [first dicarboxylic acid unit (A1)].

[0235] First dicarboxylic acid unit (A1) The first dicarboxylic acid unit (A1) represented by formula (A-1) is a dicarboxylic acid unit corresponding to compound (1) (or its salt) [also called the first dicarboxylic acid unit (A1)] as a polymerization component (dicarboxylic acid component), and the specific embodiment of the first dicarboxylic acid unit (A1) is the same as that of compound (1) (or its salt), including preferred embodiments. That is, in formula (A-1), R 1 , k1, Z 1a and Z 1b , Z 2a and Z 2b , A 1a and A 1b , m1a and m1b, R 2a and R 2b Each corresponds to formula (1) and is similar, including preferred embodiments. A typical first dicarboxylic acid unit (A1) is the dicarboxylic acid unit corresponding to the typical compound (1) mentioned above.

[0236] The first dicarboxylic acid unit (A1) may be used alone or in combination of two or more types. The preferred first dicarboxylic acid unit (A1) is a constituent unit derived from 9,9-bis(aryl-carboxyalkyloxy-aryl)fluorene; more preferably, 9,9-bis[3-phenyl-4-(3-carboxypropyloxy)-phenyl]fluorene, 9,9-bis[3-(2-naphthyl)-4-(3-carboxypropyloxy)-phenyl]fluorene, 9,9-bis[3-(1-naphthyl)-4-(3-carboxypropyloxy)-phenyl]fluorene, 9,9-bis[5-phenyl-6-(3-carboxypropyloxy)-2-naphthyl]fluorene, 9,9-bis[5-(2-naphthyl)-6-(3-carboxypropyloxy)-2-naphthyl]fluorene, etc. 6-10 Aryl-carboxyl C 1-6 Alkyloxy-C 6-10 It is a constituent unit derived from aryl)fluorene; in particular, 9,9-bis[5-phenyl-6-(3-carboxypropyloxy)-2-naphthyl]fluorene, 9,9-bis[5-(2-naphthyl)-6-(3-carboxypropyloxy)-2-naphthyl]fluorene, etc. 6-10 Aryl-carboxyl C 2-5 A constituent unit derived from alkyloxy-naphthyl)fluorene is preferred.

[0237] The proportion of the first dicarboxylic acid unit (A1) in these preferred embodiments, in particular, 9,9-bis(C 6-10 Aryl-carboxyl C 1-6 Alkyloxy-C 6-10 The proportion of constituent units derived from aryl)fluorene is, for example, about 10 to 100 mol%, preferably in stages, 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, and substantially 100 mol%, relative to the total first dicarboxylic acid unit (A1), and it is preferable that the first dicarboxylic acid unit (A1) consists only of the first dicarboxylic acid unit (A1) of the above preferred embodiment.

[0238] The proportion of the first dicarboxylic acid unit (A1) may be, for example, about 5 to 100 mol% of the total dicarboxylic acid unit (A), and preferably in stages, 10 to 90 mol%, 20 to 80 mol%, 30 to 70 mol%, 40 to 60 mol%, and 45 to 55 mol%. In terms of easily improving the anomalous dispersion characteristics (partial dispersion ratio θgF value), the proportion of the first dicarboxylic acid unit (A1) may be, for example, about 10 to 50 mol% of the total dicarboxylic acid unit (A), and preferably in stages, 15 to 45 mol%, 20 to 40 mol%, and 25 to 35 mol%. If the proportion of the first dicarboxylic acid unit (A1) is too low, it may become difficult to sufficiently improve the refractive index and heat resistance of the resin, the birefringence of the resin may increase, and the anomalous dispersion characteristics (partial dispersion ratio θgF value) of the resin may decrease. If the proportion of the first dicarboxylic acid unit (A1) is too high, the abnormal dispersion properties (partial dispersion ratio θgF value) of the resin may decrease.

[0239] Second dicarboxylic acid unit (A2) The dicarboxylic acid unit (A) may further include, in addition to the first dicarboxylic acid unit (A1), at least a second dicarboxylic acid unit (A2) represented by the following formula (A-2). Combining the first dicarboxylic acid unit (A1) and the second dicarboxylic acid unit (A2) makes it easier to reduce birefringence while improving the refractive index and heat resistance of the resin. It also tends to improve the anomalous dispersion characteristics (partial dispersion ratio θgF value) of the resin.

[0240] [ka]

[0241] (In the formula, Z 3 (The symbol indicates a substituted or unsubstituted arene ring.)

[0242] In the above equation (A-2), Z 3Examples of arene rings include monocyclic arene rings such as benzene rings and polycyclic arene rings. Examples of polycyclic arene rings include fused polycyclic arene rings and ring-assembled arene rings.

[0243] As an example of a fused polycyclic arene ring, in the term of formula (1) above, Z 1a ,Z 1b Examples include fused polycyclic arene rings similar to those exemplified, preferably fused polycyclic C such as a naphthalene ring. 10-14 It is an arene ring.

[0244] As an allene ring set, for example, in the term of equation (1) above, Z 2a ,Z 2b Examples include ring-assembled arene rings similar to those exemplified, preferably C such as a biphenyl ring. 12-18 It is a Bialen ring.

[0245] Z 3 Typical arene rings in this context include benzene rings, naphthalene rings, biphenyl rings, and other C11 rings. 6-14 Examples include arene rings, preferably monocyclic or fused polycyclic arene rings, and more preferably C such as benzene rings or naphthalene rings. 6-10 These are arene rings, particularly naphthalene rings.

[0246] Z 3 In the arene ring, the substitution positions (bonding positions) of the two carbonyl groups on either side of formula (A-2) may be adjacent to each other, preferably at distant positions that are not adjacent, and more preferably at the furthest positions. Specifically, Z 3 When the arene ring is a naphthalene ring, the other carbonyl group may be substituted at the 5th to 8th position relative to the substitution position of the other carbonyl group at position 1 or 2, preferably at position 6 (2,6) relative to position 2.

[0247] Z 3In the above, the arene ring is an unsubstituted arene ring, that is, a substituent other than the two carbonyl groups on both sides of formula (A-2) (hereinafter referred to as the group [-R Z3 It may also be an arene ring that does not have a substituent (group [-R Z3 The arene ring may have a substituent [-R]. Z3 The group may be an inert, non-reactive group (or non-polymerizable group) that is inert to the reaction, for example, a halogen atom, a hydrocarbon group, or a group [-OR hZ3 ](where R hZ3 (represents a hydrocarbon group), group [-SR hZ3 ](where R hZ3 Examples include hydrocarbon groups, acyl groups, nitro groups, cyano groups, and substituted amino groups (mono or disubstituted amino groups).

[0248] Substituent [-R Z3 In the term (1) above, R is an example of a halogen atom, acyl group, or substituted amino group (mono or disubstituted amino group). 1 Examples of halogen atoms, acyl groups, and substituted amino groups (mono- or disubstituted amino groups) are similar to those exemplified above.

[0249] Substituent [-R Z3 As for the hydrocarbon group in ], for example, in the term of formula (1) above, R 1 Examples of hydrocarbon groups include alkyl groups (linear or branched alkyl groups), cycloalkyl groups, aryl groups, and aralkyl groups, as well as other similar groups.

[0250] Base [-OR hZ3 ], base [-SR hZ3 In ], hydrocarbon group R hZ3 For example, in the term of equation (1) above, R 1 Examples of hydrocarbon groups include alkyl groups (linear or branched alkyl groups), cycloalkyl groups, aryl groups, and aralkyl groups, as well as groups similar to those exemplified in the above. hZ3 ], base [-SR hZ3 In ], hydrocarbon group RhZ3 The types may be the same or different from each other.

[0251] Base [-OR hZ3 For example, in the term of formula (1) above, R 1 (Base [-OR h1 Examples include alkoxy groups (linear or branched alkoxy groups), cycloalkyloxy groups, aryloxy groups, aralkyloxy groups, and similar groups, as exemplified by ]).

[0252] Base [-SR hZ3 For example, in the term of equation (1) above, Z 1a ,Z 1b substituents [-R Z1 ](Base [-SR hZ1 Examples of similar groups include alkylthio groups, cycloalkylthio groups, arylthio groups, and aralkylthio groups, as exemplified above.

[0253] Typical substituents [-R Z3 ] includes halogen atoms, hydrocarbon groups, and groups [-OR hZ3 Examples include acyl groups, nitro groups, cyano groups, substituted amino groups, etc.; preferably hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, etc., and alkoxy groups [-OR hZ3 Examples include; more preferably linear or branched C such as a methyl group. 1-6 C such as alkyl groups and cyclohexyl groups 5-8 Cycloalkyl groups, phenyl groups, etc. 6-14 Linear or branched C such as aryl groups and methoxy groups 1-4 Examples include alkoxy groups. Substituents [-R Z3 Among these, alkyl groups are preferred, and in particular linear or branched C such as methyl groups. 1-4 Alkyl alkyl groups are preferred.

[0254] Z 3 substituents in [-R Z3The number of substitutions in ] depends on the type of arene ring, for example, an integer of about 0 to 5, preferably in stages below, an integer of 0 to 3, an integer of 0 to 2, 0 or 1, 0. 3 If the number of substitutions in is 2 or more, then 2 or more substituents [-R Z3 The types of ] may be the same or different from each other.

[0255] Typical second dicarboxylic acid units (A2) include, for example, constituent units derived from the second dicarboxylic acid component (A2) of monocyclic aromatic dicarboxylic acids and polycyclic aromatic dicarboxylic acids. Examples of monocyclic aromatic dicarboxylic acids include benzene dicarboxylic acids such as phthalic acid, terephthalic acid, and isophthalic acid; alkylbenzene dicarboxylic acids, specifically C4-methylisophthalic acid. 1-4 Examples include alkylbenzene dicarboxylic acids.

[0256] Examples of polycyclic aromatic dicarboxylic acids include condensed polycyclic aromatic dicarboxylic acids (condensed polycyclic arene dicarboxylic acids), specifically naphthalenedicarboxylic acid, anthracene dicarboxylic acid, phenantradiocarboxylic acid, and other condensed polycyclic C 10-24 Allene-dicarboxylic acids, etc.; biaryldicarboxylic acids, specifically 2,2'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-dicarboxy-1,1'-binaphthyl, etc. 6-10 Examples include aryl dicarboxylic acids.

[0257] Examples of the aforementioned naphthalenedicarboxylic acids 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.

[0258] The second dicarboxylic acid unit (A2) may be alone or in combination of two or more. A preferred second dicarboxylic acid unit (A2) is C 10-14Examples include structural units corresponding to condensed polycyclic arenedicarboxylic acids, such as condensed polycyclic arenedicarboxylic acids, and preferably structural units corresponding to naphthalenedicarboxylic acids, such as 2,6-naphthalenedicarboxylic acid.

[0259] The proportion of the second dicarboxylic acid units (A2) in these preferred embodiments, particularly the proportion of constituent units derived from naphthalenedicarboxylic acid, is, for example, about 10 to 100 mol%, preferably in stages, 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, and substantially 100 mol%, relative to the total second dicarboxylic acid units (A2), and it is preferable that the second dicarboxylic acid units (A2) consist only of the second dicarboxylic acid units (A2) of the above preferred embodiments.

[0260] The ratio of the first dicarboxylic acid unit (A1) to the second dicarboxylic acid unit (A2) (also called A1 / A2) may be, for example, around 10 / 90 to 90 / 10, and preferably in stages as follows: 20 / 80 to 80 / 20, 30 / 70 to 70 / 30, 40 / 60 to 60 / 40, and 45 / 55 to 55 / 45. In terms of easily improving the anomalous dispersion characteristics (partial dispersion ratio θgF value), the A1 / A2 (molar ratio) may be, for example, around 10 / 90 to 50 / 50, and preferably in stages as follows: 15 / 85 to 45 / 55, 20 / 80 to 40 / 60, and 25 / 75 to 35 / 65. If the proportion of the second dicarboxylic acid unit (A2) is too small, the anomalous dispersion characteristics (partial dispersion ratio θgF value) of the resin may decrease. If the proportion of the second dicarboxylic acid unit (A2) is too high, it may become difficult to sufficiently improve the refractive index and heat resistance of the resin, the birefringence of the resin may increase, and the anomalous dispersion characteristics of the resin (partial dispersion ratio θgF value) may decrease.

[0261] Third dicarboxylic acid unit (A3) Furthermore, the dicarboxylic acid unit (A) may or may not include a third dicarboxylic acid unit (A3) that is different from the first dicarboxylic acid unit (A1) and the second dicarboxylic acid unit (A2) [not belonging to the categories of the first and second dicarboxylic acid units (A1) and (A2)], as needed.

[0262] Examples of the third dicarboxylic acid unit (A3) include constituent units derived from third dicarboxylic acid components (A3), such as aliphatic dicarboxylic acid components, alicyclic dicarboxylic acid components, and aromatic dicarboxylic acid components.

[0263] Examples of aliphatic dicarboxylic acid components include alkanedicarboxylic acids (linear or branched alkanedicarboxylic acids), specifically succinic acid, adipic acid, suberic acid, sebacic acid, decanedicarboxylic acid, etc. 2-12 Alkane-dicarboxylic acids, etc.; unsaturated aliphatic dicarboxylic acids (linear or branched unsaturated aliphatic dicarboxylic acids), specifically, maleic acid, fumaric acid, itaconic acid, etc. 2-10 Examples include alkene-dicarboxylic acids and their ester-forming derivatives.

[0264] Examples of alicyclic dicarboxylic acid components include cycloalkanedicarboxylic acids, specifically 1,4-cyclohexanedicarboxylic acid and other C13 5-10 Cycloalkane-dicarboxylic acids, etc.; crosslinked cyclic cycloalkane-dicarboxylic acids, specifically decalin-dicarboxylic acid, norbornane-dicarboxylic acid, adamantane-dicarboxylic acid, tricyclodecane-dicarboxylic acid, etc. or tricycloalkane-dicarboxylic acids, etc.; cycloalkene-dicarboxylic acids, specifically cyclohexene-dicarboxylic acid, etc. 5-10 Examples include cycloalkene-dicarboxylic acids; crosslinked cyclic cycloalkenedicarboxylic acids, specifically bi or tricycloalkenedicarboxylic acids such as norbornenedicarboxylic acid; and ester-forming derivatives thereof.

[0265] Aromatic dicarboxylic acid components [excluding dicarboxylic acid components corresponding to the first and second dicarboxylic acid units (A1) and (A2)] include, for example, bis(carboxyalkoxy)biaryls, specifically bis(carboxyC) such as 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl. 1-4 Alkoxy)bi C 6-10Aryls, etc.; bis[(carboxyalkoxy)-aryl]alkanes, specifically bis[(carboxyC)[(carboxymethyl)methane, etc.] 1-4 Alkoxy)-C 6-10 Ariel)C 1-6 Alkanes, etc.; diarylalkane dicarboxylic acids, specifically diC such as 4,4'-diphenylmethanedicarboxylic acid. 6-10 Aryl C 1-6 Alkane-dicarboxylic acids, etc.; diarylketone dicarboxylic acids, specifically di(C) such as 4,4'-diphenylketone dicarboxylic acid. 6-10 Aryl)ketone-dicarboxylic acids, etc.; diaryl ether dicarboxylic acids, specifically, di(C) such as 4,4'-diphenyl ether dicarboxylic acid. 6-10 aryl) ether-dicarboxylic acids, etc.; diaryl sulfone dicarboxylic acids, specifically, di(C) such as 4,4'-diphenyl sulfone dicarboxylic acid. 6-10 Examples include aryl)sulfone-dicarboxylic acids and their ester-forming derivatives.

[0266] The third dicarboxylic acid unit (A3) may be present alone or in combination of two or more types.

[0267] The proportion of the third dicarboxylic acid unit (A3) is, for example, less than 50 mol%, preferably 30 mol% or less, and more preferably 10 mol% or less, relative to the total dicarboxylic acid unit (A), and it is preferable that the third dicarboxylic acid unit (A3) is substantially absent. If the third dicarboxylic acid unit (A3) is present, the proportion may be, for example, about 0.1 to 5 mol%.

[0268] The ratio of the total amount of the first dicarboxylic acid unit (A1) and the second dicarboxylic acid unit (A2) may be selected from a range of, for example, 10 mol% or more, specifically 30 to 100 mol%, relative to the total amount of dicarboxylic acid units (A), preferably in stages of 50 mol% or more, 70 mol% or more, 90 mol% or more, and substantially 100 mol%, and it is preferable that the dicarboxylic acid units (A) consist only of the first dicarboxylic acid unit (A1) and the second dicarboxylic acid unit (A2).

[0269] The proportion of dicarboxylic acid units (A) [total amount of the first to third dicarboxylic acid units (A1) to (A3)] may be, for example, 10 mol% or more, specifically around 20 to 50 mol%, relative to the total constituent units of the resin (thermoplastic resin) (total amount of units derived from all monomer components constituting the resin), and preferably in stages as follows: 30 to 50 mol%, 40 to 50 mol%, 45 to 50 mol%, and substantially 50 mol%.

[0270] (Diol unit (B)) The resin (thermoplastic resin) is preferably a polyester resin that contains, in addition to dicarboxylic acid units (A), at least diol units (B) derived from a diol component as a polymerization component.

[0271] Typical diol units (B) include, for example, the first diol unit (B1) and the second diol unit (B2) described later, and these diol units may be included individually or in combination of two or more types.

[0272] The diol unit (B) preferably includes at least one diol unit selected from a first diol unit (B1) and a second diol unit (B2), more preferably includes at least the first diol unit (B1), and particularly preferably includes at least both the first diol unit (B1) and the second diol unit (B2).

[0273] The first diol unit (B1) The first diol unit (B1) is represented by the following formula (B-1). When the first diol unit (B1) is combined with the first dicarboxylic acid unit (A1), preferably with the first dicarboxylic acid unit (A1) and the second dicarboxylic acid unit (A2), it is possible to improve the refractive index and heat resistance of the resin while reducing birefringence, and despite containing a fluorene skeleton, the anomalous dispersion characteristics (partial dispersion ratio θgF value) of the resin tend to improve as well.

[0274] [ka]

[0275] (In the formula, R 4 represents a substituent, and k4 represents an integer from 0 to 8. Z 4a and Z 4b These independently represent substituted or unsubstituted arene rings. A 2a and A 2b (where m2a and m2b independently represent linear or branched alkylene groups, and m2a and m2b independently represent 0 or an integer greater than or equal to 1).

[0276] In the above formula (B-1), substituent R 4 These may be non-reactive groups (or non-polymerizable groups) that are inert to the reaction, such as halogen atoms, hydrocarbon groups, or groups [-OR h4 ](where R h4 (represents a hydrocarbon group), group [-SR h4 ](where R h4 Examples include hydrocarbon groups, acyl groups, nitro groups, cyano groups, and substituted amino groups (mono or disubstituted amino groups).

[0277] R 4 Examples of halogen atoms, acyl groups, and substituted amino groups (mono or disubstituted amino groups) in formula (1) above include, 1 Examples of halogen atoms, acyl groups, and substituted amino groups (mono- or disubstituted amino groups) are similar to those exemplified above.

[0278] R 4 As for the hydrocarbon group in the above formula (1), for example, R 1 Examples of hydrocarbon groups include alkyl groups (linear or branched alkyl groups), cycloalkyl groups, aryl groups, and aralkyl groups, as exemplified above, and other similar groups.

[0279] Base [-OR h4 ], base [-SR h4 In ], hydrocarbon group R h4 For example, in the term of equation (1) above, R 1 Examples of hydrocarbon groups include alkyl groups (linear or branched alkyl groups), cycloalkyl groups, aryl groups, aralkyl groups, and similar groups. h4 ], base [-SR h4 In ], hydrocarbon group R h4 The types may be the same or different from each other.

[0280] Base [-OR h4 For example, in the term of formula (1) above, R 1 (Base [-OR h1 Examples include alkoxy groups (linear or branched alkoxy groups), cycloalkyloxy groups, aryloxy groups, aralkyloxy groups, and similar groups, as exemplified by ]).

[0281] Base [-SR h4 For example, in the term of equation (1) above, Z 1a ,Z 1b substituents [-R Z1 ](Base [-SR hZ1 Examples of similar groups include alkylthio groups, cycloalkylthio groups, arylthio groups, and aralkylthio groups, as exemplified above.

[0282] Typical R 4 Examples include halogen atoms, hydrocarbon groups, and groups [-OR h4Examples include acyl groups, nitro groups, cyano groups, substituted amino groups, etc.; preferably hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, etc., and alkoxy groups [-OR h4 Examples include; more preferably linear or branched C such as a methyl group. 1-6 C such as alkyl groups and cyclohexyl groups 5-8 Cycloalkyl groups, phenyl groups, etc. 6-14 Linear or branched C such as aryl groups and methoxy groups 1-4 An example is an alkoxy group. 4 Among these, alkyl groups are preferred, and in particular linear or branched C groups such as methyl groups are preferred. 1-4 Alkyl alkyl groups are preferred.

[0283] R 4 For example, the number of substitutions k4 is R 1 The number of substitutions k1 can be a number in the same range as exemplified, preferably an integer from 0 to 2, more preferably 0 or 2, and particularly preferably 0. Note that the R in the two benzene rings constituting the fluorene ring 4 The number of each permutation (the number of permutations at positions 1-4 and the number of permutations at positions 5-8) may be different from each other, but it is preferable that they be the same.

[0284] Note, R 4 If the number of substitutions k4 is multiple (2 or more), then two or more groups R substituted on one of the two benzene rings constituting the fluorene ring. 4 The types may be the same or different; and the groups R substituted on both benzene rings may also be different. 4 The types may be different, but they are preferably the same. 4 The bonding position (substitution position) is not particularly limited as long as it is between positions 1 and 8 of the fluorene ring. Examples include positions 2, 7, and 2,7 of the fluorene ring, with position 2,7 being preferred.

[0285] Z 4a and Z 4bExamples of arene rings include monocyclic arene rings such as benzene rings and polycyclic arene rings. Examples of polycyclic arene rings include fused polycyclic arene rings and ring-assembled arene rings.

[0286] As an example of a fused polycyclic arene ring, in the term of formula (1) above, Z 1a ,Z 1b Examples include fused polycyclic arene rings similar to those exemplified above, and preferred fused polycyclic arene rings such as naphthalene rings. 10-14 It is an arene ring.

[0287] As an allene ring set, for example, in the term of equation (1) above, Z 2a ,Z 2b Examples include ring-assembled arene rings similar to those exemplified, and preferred ring-assembled arene rings include C such as biphenyl rings. 12-18 It is a Bialen ring.

[0288] Z 4a and Z 4b Typical arene rings in this context include benzene rings, naphthalene rings, biphenyl rings, and other C11 rings. 6-14 Examples include arene rings, preferably monocyclic or fused polycyclic arene rings, and more preferably C such as benzene rings or naphthalene rings. 6-10 This refers to an arene ring, particularly a benzene ring.

[0289] Z 4a and Z 4b The types of arene rings in the compound may be different from each other, but it is preferable that they be the same.

[0290] Z 4a and Z 4b In the arene ring, the 9th position of the fluorene ring, and the group [-O-(A 2a O) m2a -],[-O-(A 2b O) m2bThe substitution position (bonding position) with the group [-O-(A 2a O) m2a -],[-O-(A 2b O) m2b It is preferable that -] is substituted (joined). Specifically, Z 4a ,Z 4b In the case of a benzene ring, relative to the 1st position (or phenyl group) of the benzene ring as the bonding position with the 9th position of the fluorene ring, the group [-O-(A 2a O) m2a -],[-O-(A 2b O) m2b -] is preferred to be substituted (joined). Also, Z 4a ,Z 4b In the case of a naphthalene ring, for example, with respect to the 1st or 2nd position (1-naphthyl group or 2-naphthyl group) of the naphthalene ring as the bonding position with the 9th position of the fluorene ring, a group [-O-(A] is attached to any position from 5 to 8, preferably at the 5th or 6th position (in a 1,5 or 2,6 positional relationship). 2a O) m2a -],[-O-(A 2b O) m2b -] is preferred to be substituted (joined). 4a ,Z 4b In the case of a biphenyl ring, for example, the 3-position (3-biphenyl group) of the biphenyl ring, which is the bonding position with the 9-position of the fluorene ring, has a group [-O-(A] at the 6-position (in a 3,6 positional relationship). 2a O) m2a -],[-O-(A 2b O) m2b It is preferable for -] to be substituted (joined).

[0291] Z 4a and Z 4b The arene ring in is an unsubstituted arene ring, i.e., the 9th position of the fluorene ring, and the group [-O-(A 2a O) m2a -],[-O-(A 2b O) m2bSubstituents (hereinafter referred to as group [-R)) are located at positions other than the substitution position (bonding position) with the group [-R Z4 It may also be an arene ring that does not have a substituent (group [-R Z4 It may also be an arene ring in which a substituent [-R] is substituted (bonded). Z4 The group may be an inert, non-reactive group (or non-polymerizable group) that is inert to the reaction, for example, a halogen atom, a hydrocarbon group, or a group [-OR hZ4 ](where R hZ4 (represents a hydrocarbon group), group [-SR hZ4 ](where R hZ4 Examples include hydrocarbon groups, acyl groups, nitro groups, cyano groups, and substituted amino groups (mono or disubstituted amino groups).

[0292] Substituent [-R Z4 In the term (1) above, R is an example of a halogen atom, acyl group, or substituted amino group (mono or disubstituted amino group). 1 Examples of halogen atoms, acyl groups, and substituted amino groups (mono- or disubstituted amino groups) are similar to those exemplified above.

[0293] Substituent [-R Z4 As for the hydrocarbon group in ], for example, in the term of formula (1) above, R 1 Examples of hydrocarbon groups include alkyl groups (linear or branched alkyl groups), cycloalkyl groups, aryl groups, and aralkyl groups, as well as other similar groups.

[0294] Base [-OR hZ4 ], base [-SR hZ4 In ], hydrocarbon group R hZ4 For example, in the term of equation (1) above, R 1 Examples of hydrocarbon groups include alkyl groups (linear or branched alkyl groups), cycloalkyl groups, aryl groups, aralkyl groups, and similar groups. hZ4 ], base [-SR hZ4 In ], hydrocarbon group R hZ4The types may be the same or different from each other.

[0295] Base [-OR hZ4 For example, in the term of formula (1) above, R 1 (Base [-OR h1 Examples include alkoxy groups (linear or branched alkoxy groups), cycloalkyloxy groups, aryloxy groups, aralkyloxy groups, and similar groups, as exemplified by ]).

[0296] Base [-SR hZ4 For example, in the term of equation (1) above, Z 1a ,Z 1b substituents [-R Z1 ](Base [-SR hZ1 Examples of similar groups include alkylthio groups, cycloalkylthio groups, arylthio groups, and aralkylthio groups, as exemplified above.

[0297] Typical substituents [-R Z4 ] includes halogen atoms, hydrocarbon groups, and groups [-OR hZ4 Examples include acyl groups, nitro groups, cyano groups, substituted amino groups, etc.; preferably hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, etc., and alkoxy groups [-OR hZ4 Examples include; more preferably linear or branched C such as a methyl group. 1-6 C such as alkyl groups and cyclohexyl groups 5-8 Cycloalkyl groups, phenyl groups, etc. 6-14 Linear or branched C such as aryl groups and methoxy groups 1-4 Examples include alkoxy groups. Substituents [-R Z4 Among these, alkyl groups are preferred, and in particular linear or branched C such as methyl groups. 1-4 Alkyl alkyl groups are preferred.

[0298] Z 4a ,Z 4b substituents [-R] in each arene ring Z4The number of substitutions in ] depends on the type of arene ring, for example, an integer of about 0 to 5, preferably in stages below, an integer of 0 to 3, an integer of 0 to 2, 0 or 1, 0. 4a The number of substitutions in Z 4b The number of substitutions in Z may be different from each other, but it is preferable that they be the same. 4a If the number of substitutions in is 2 or more, then 2 or more substituents [-R Z4 The types of ] may be the same or different from each other; Z 4b If the number of substitutions in is 2 or more, then 2 or more substituents [-R Z4 The types of ] may be the same or different from each other. Also, Z 4a substituents in [-R Z4 ] Types and Z 4b substituents in [-R Z4 The types of [items] may be different from each other, but it is preferable that they be the same.

[0299] A 2a and A 2b An alkylene group represented by (linear or branched alkylene group) is, for example, in the term of formula (1) above, A 1a , A 1b Examples include groups similar to the alkylene group exemplified above, and typically C 2-6 Alkylene group, preferably C 2-4 C such as an alkylene group, more preferably an ethylene group, a propylene group, etc. 2-3 An alkylene group, particularly preferably an ethylene group.

[0300] Alkylene oxy group [-(A 2a O)-],[-(A 2bThe number of repeats (number of moles added) of O)-] m2a and m2b may be 0 or 1 or more, and may be selected from an integer range of about 0 to 15, preferably in the following increments: an integer from 0 to 10, an integer from 0 to 6, an integer from 0 to 4, an integer from 0 to 2, 0 or 1, and especially 1. It is preferable that m2a and m2b are each 1 or more, as this easily improves polymerization reactivity. Also, m2a and m2b may be the average value (arithmetic mean, arithmetic mean) or the average number of moles added, and m2a and m2b may be selected from a range of about 0 to 15, preferably in the following increments: 0 to 10, 0 to 6, 0 to 4, 0 to 2, 0 to 1, and especially 1. If m2a and m2b are too large, the heat resistance and refractive index may decrease. Also, m2a and m2b may be the same or different from each other. When m2a is 2 or more, 2 or more alkylene oxy groups [-(A 2a The types of O)-] may be different from each other, but are preferably the same, and if m2b is 2 or more, 2 or more alkylene oxy groups [-(A 2b The types of O)-] may be different from each other, but it is preferable that they be the same. Also, A 2a and A 2b The types may be the same or different from each other.

[0301] Examples of the first diol component (B1) corresponding to a typical first diol unit (B1) include 9,9-bis(hydroxyaryl)fluorenes in formula (B-1) where m2a and m2b are 0, and 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes in which m2a and m2b are 1 or more, for example, about 1 to 10.

[0302] In this specification and in the claims, unless otherwise specified, "(poly)alkoxy" is used to mean both alkoxy groups and polyalkoxy groups.

[0303] 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.

[0304] Examples of 9,9-bis(hydroxyphenyl)fluorene include 9,9-bis(4-hydroxyphenyl)fluorene.

[0305] Examples of 9,9-bis(alkyl-hydroxyphenyl)fluorene include 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, and other 9,9-bis[(mono or di)C 1-4 Examples include alkyl-hydroxyphenyl fluorene.

[0306] Examples of 9,9-bis(aryl-hydroxyphenyl)fluorene include 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene and other 9,9-bis(C 6-10 Examples include aryl-hydroxyphenyl ()fluorene.

[0307] 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.

[0308] 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.

[0309] Examples of 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxypropoxy)phenyl]fluorene, and other 9,9-bis[hydroxy(mono or deca)C 2-4 Examples include alkoxyphenyl fluorene.

[0310] Examples of 9,9-bis[alkyl-hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene, 9,9-bis[4-(2-hydroxypropoxy)-3,methylphenyl]fluorene, and other 9,9-bis[(mono or di)C 1-4 Alkyl-hydroxy(mono or deca)C 2-4 Examples include alkoxyphenyl fluorene.

[0311] Examples of 9,9-bis[aryl-hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxypropoxy)-3-phenylphenyl)fluorene, and other 9,9-bis[C 6-10 Aryl-hydroxy(mono or deca)C 2-4 Examples include alkoxyphenyl fluorene.

[0312] Examples of 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorene include 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, 9,9-bis[5-(2-hydroxyethoxy)-1-naphthyl]fluorene, 9,9-bis[6-(2-hydroxypropoxy)-2-naphthyl]fluorene, etc. 2-4 Examples include alkoxy-naphthyl fluorene.

[0313] The first diol unit (B1) may be present alone or in combination of two or more types. A preferred first diol unit (B1) is 9,9-bis[hydroxy(mono or penta)C 2-4 Alkoxy C 6-10 The constituent units are derived from 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes such as aryl[fluorene]fluorene; more preferably 9,9-bis[hydroxyC 2-4 Alkoxy C 6-10 Constituent units derived from aryl[fluorene]; particularly preferably 9,9-bis[hydroxy[C]fluorene such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene 2-3 It is a constituent unit derived from alkoxyphenyl fluorene.

[0314] The proportion of the first diol unit (B1) in these preferred embodiments, in particular, 9,9-bis[hydroxyC 2-4 Alkoxy C 6-10 The proportion of constituent units derived from 9,9-bis[hydroxyalkoxyaryl]fluorene, such as aryl[fluorene]fluorene, is, for example, about 10 to 100 mol%, preferably in stages, 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, and substantially 100 mol%, relative to the total first diol unit (B1), and it is preferable that the first diol unit (B1) consists only of the first diol unit (B1) of the above preferred embodiment.

[0315] The proportion of the first diol unit (B1) may be, for example, about 10 to 100 mol% of the total diol unit (B), and preferably in stages, 30 to 100 mol%, 50 to 99 mol%, 70 to 95 mol%, 75 to 92 mol%, and 80 to 90 mol%. If the proportion of the first diol unit (B1) is too low, it may be difficult to sufficiently improve the refractive index and heat resistance of the resin. If the proportion of the first diol unit (B1) is too high, it may be difficult to sufficiently improve the molecular weight of the resin or the mechanical properties may deteriorate.

[0316] Second diol unit (B2) The second diol unit (B2) is represented by the following formula (B-2). When the second diol unit (B2) is included, the polymerization reaction proceeds efficiently and it is easy to prepare a high molecular weight, and the mechanical properties (flexibility or toughness) of the resin can be improved, and the moldability and handleability can also be improved.

[0317] [Chemical formula]

[0318] (In the formula, A 3 represents a linear or branched alkylene group, and m3 represents an integer of 1 or more).

[0319] A 3 Examples of the alkylene group (linear or branched alkylene group) represented by include ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, 1,3-butanediyl group, tetramethylene group, 1,5-pentanediyl group, 1,6-hexanediyl group, 1,8-octanediyl group, 1,10-decanediyl group, etc. C 2-12 alkylene groups and the like. Preferred alkylene group A 3 is, in the following stages, a C 2-8 alkylene group, a C 2-6 alkylene group, a C 2-4 alkylene group, and more preferably a C such as an ethylene group or a propylene group 2-3 alkylene group, and particularly preferably an ethylene group.

[0320] The repeating number (number of added moles) m3 of the alkyleneoxy group [-(A 3 O)-] may be selected, for example, from an integer of about 1 to 15, preferably, in the following stages, an integer of 1 to 10, an integer of 1 to 6, an integer of 1 to 4, an integer of 1 to 2, and particularly, 1. Also, m3 may be an average value (arithmetic average value, additive average value) or an average number of added moles, and may be selected, for example, from a range of about 1 to 15, preferably, in the following stages, 1 to 10, 1 to 6, 1 to 4, 1 to 2, and particularly, 1. If m3 is too large, there is a risk that the heat resistance and refractive index will decrease. When m3 is 2 or more, two or more alkyleneoxy groups [-(A3 The types of O)-] may be different from each other, but the same is preferred.

[0321] Examples of the second diol component (B2) corresponding to the second diol unit (B2) include alkane diols (or alkylene glycols), polyalkane diols (or polyalkylene glycols), and the like.

[0322] Examples of alkylene glycols (linear or branched alkylene glycols) include compounds in which m3 is 1 in the above formula (B-2) and A 3 corresponds to the exemplified alkylene groups, specifically, 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, 1,10-decanediol, and other C 2-12 alkylene glycols, etc. Preferred embodiments are the same corresponding to the alkylene group A 3 is the same.

[0323] Examples of polyalkylene glycols (linear or branched polyalkylene glycols) include compounds in which m3 is 2 or more, preferably 2 to 10, more preferably 2 to 6, and still more preferably 2 to 4 in the above formula (B-2), and A 3 corresponds to the exemplified alkylene groups, specifically, diethylene glycol, dipropylene glycol, triethylene glycol, and other di- to deca- C 2-12 alkylene glycols, etc. Preferably, di- to hexa- C 2-6 alkylene glycols, and more preferably di- to tetra- C 2-4 alkylene glycols are included.

[0324] The second diol unit (B2) may be included alone or in combination of two or more. Preferred second diol units (B2) are from the viewpoint of being easy to maintain high heat resistance, C2-6 It is a constituent unit derived from alkylene glycol, such as alkylene glycol; more preferably C 2-4 Constituent units derived from alkylene glycol; more preferably C such as ethylene glycol or propylene glycol. 2-3 Constituent units derived from alkylene glycol; particularly preferably, constituent units derived from ethylene glycol.

[0325] The proportion of the second diol unit (B2) in these preferred embodiments, in particular, C 2-4 The proportion of constituent units derived from alkylene glycols, such as alkylene glycols, is, for example, about 10 to 100 mol%, preferably in stages, 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, and substantially 100 mol%, relative to the entire second diol unit (B2), and it is preferable that the second diol unit (B2) consists only of the second diol unit (B2) of the above preferred embodiment.

[0326] The ratio of the first diol unit (B1) to the second diol unit (B2) (also called B1 / B2) may be approximately 10 / 90 to 100 / 0 in molar ratio, and preferably in the following increments: 30 / 70 to 100 / 0, 50 / 50 to 99 / 1, 70 / 30 to 95 / 5, 75 / 25 to 92 / 8, and 80 / 20 to 90 / 10. If the proportion of the second diol unit (B2) is too low, the molecular weight of the resin may not be sufficiently improved, or the mechanical properties may deteriorate. If the proportion of the second diol unit (B2) is too high, it may be difficult to sufficiently improve the refractive index and heat resistance of the resin.

[0327] The third diol unit (B3) Furthermore, the diol unit (B) may or may not include a third diol unit (B3) that is different from the first diol unit (B1) and the second diol unit (B2) [and does not belong to the categories of the first and second diol units (B1) and (B2)], as needed.

[0328] Examples of the third diol unit (B3) include aromatic diols, alicyclic diols, and constituent units derived from third diol components (B3), such as alkylene oxide (or alkylene carbonate, haloalkanol) adducts of these diol components.

[0329] Examples of aromatic diols [excluding the first diol component (B1)] 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.

[0330] Examples of alicyclic diols include cycloalkane diols such as cyclohexanediol; bis(hydroxyalkyl)cycloalkanes such as cyclohexanedimethanol; and hydrogenations of the above aromatic diols such as hydrogenations of bisphenol A.

[0331] Examples of alkylene oxide (or corresponding alkylene carbonate, haloalkanol) adducts of these diol components include, for example, C 2-4 C such as alkylene oxide adducts, preferably ethylene oxide adducts, propylene oxide adducts, etc. 2-3 Examples include alkylene oxide adducts, and the number of moles added is not particularly limited. Specifically, examples include adducts in which approximately 2 to 10 moles of ethylene oxide are added to 1 mole of bisphenol A.

[0332] The third diol unit (B3) may be present alone or in combination of two or more types.

[0333] The proportion of the third diol unit (B3) is, for example, less than 50 mol%, preferably 30 mol% or less, and more preferably 10 mol% or less, relative to the total diol unit (B), and it is preferable that it substantially does not contain the third diol unit (B3). If the third diol unit (B3) is included, the proportion may be, for example, about 0.1 to 5 mol%.

[0334] The ratio of the total amount of the first diol unit (B1) and the second diol unit (B2) can be selected from a range of, for example, 10 mol% or more, specifically 30 to 100 mol%, relative to the total amount of diol units (B). Preferred ranges are, in stages, 50 mol% or more, 70 mol% or more, 90 mol% or more, and substantially 100 mol%, and it is preferable that the diol units (B) consist only of the first diol unit (B1) and the second diol unit (B2).

[0335] Furthermore, the proportion of diol units (B) [total amount of the first to third diol units (B1) to (B3)] may be, for example, 10 mol% or more, specifically around 20 to 50 mol%, relative to the total constituent units of the resin (thermoplastic resin) (total amount of units derived from all monomer components constituting the resin), and preferably in stages as follows: 30 to 50 mol%, 40 to 50 mol%, 45 to 50 mol%, and substantially 50 mol%.

[0336] (Carbonate units (C)) If the resin (thermoplastic resin) is a polyester resin containing diol units (B), it does not necessarily have to contain them, but if necessary, it may also contain carbonate units (C) to form a polyester carbonate resin.

[0337] In this specification and in the claims, "carbonate unit" means a constituent unit derived from a carbonate bond-forming component capable of forming a carbonate bond [-OC(=O)-O-] through reaction 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 bonded adjacent to the carbonate unit (carbonyl group).

[0338] Therefore, the carbonate bond-forming component (C) can be any compound capable of forming a carbonate bond through reaction with the diol component, such as phosgenes like phosgene and triphosgene, and diesters of carbonates like diphenyl carbonate.

[0339] These carbonate bond-forming components (C) can be used individually or in combination of two or more. Of these carbonate bond-forming components (C), diphenyl carbonate and other diesters are preferred from the viewpoint of safety and other factors.

[0340] The ratio of the total amount of dicarboxylic acid units (A) and carbonate units (C) in the resin (thermoplastic resin) to the amount of diol units (B) is preferably approximately equimolar, with a molar ratio of 1 / 0.8 to 1 / 1.2, more preferably 1 / 0.9 to 1 / 1.1. The ratio of dicarboxylic acid units (A) to carbonate units (C) (also called A / C) may be approximately 99 / 1 to 1 / 99, for example, selected from the range of 90 / 10 to 10 / 90, and preferably progressively 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 decrease.

[0341] The proportion of carbonate units (C) may be, for example, 30 mol% or less relative to the total constituent units of the resin (thermoplastic resin) (the total amount of units derived from all monomer components that make up the resin), and preferably, in stages, 0 to 20 mol%, 0 to 10 mol%, 0 to 5 mol%, and may also be around 1 to 3 mol%.

[0342] (Other constituent units (D)) The resin (thermoplastic resin) does not necessarily have to contain other constituent units (D) different from the dicarboxylic acid unit (A), diol unit (B), and carbonate unit (C), but may contain them as needed, to the extent that it does not impair the effects of the present invention.

[0343] Other constituent units (D) include, for example, constituent units derived from hydroxycarboxylic acid components, corresponding lactone components, and polyfunctional polymer components having three or more polymerizable groups (carboxyl groups and / or hydroxyl groups). Other constituent units (D) may be included individually or in combination of two or more types.

[0344] Examples of hydroxycarboxylic acid components include aromatic hydroxycarboxylic acids such as hydroxybenzoic acid; aliphatic hydroxycarboxylic acids (hydroxyalkanoic acids) such as lactic acid, 3-hydroxybutyric acid, and 6-hydroxyhexanoic acid; and ester-forming derivatives thereof. Examples of lactone components include lactones corresponding to hydroxyalkanoic acids such as ε-caprolactone.

[0345] The resin (thermoplastic resin) may be a crystalline polymer, but in applications such as optical lenses and other optical components, it is preferable that it is a non-liquid crystal polymer that does not contain units derived from aromatic hydroxycarboxylic acids such as hydroxybenzoic acid, and is particularly preferable that it be an amorphous polymer, as it is easier to reduce birefringence.

[0346] 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; and trivalent or higher polyhydric alcohols such as glycerin and pentaerythritol.

[0347] The proportion of such other constituent units (D) is, for example, 50 mol% or less, preferably in stages, 0 to 30 mol%, 0 to 10 mol%, and 0.01 to 5 mol%, relative to the total constituent units (the total amount of units derived from all monomer components constituting the resin, i.e., the total amount of dicarboxylic acid units (A), diol units (B), carbonate units (C), and other constituent units (D)), and it is preferable that the other constituent units (D) are substantially absent.

[0348] Preferred embodiments of the resin (thermoplastic resin) of the present invention include: The dicarboxylic acid unit (A) contains at least the first dicarboxylic acid unit (A1), The diol unit (B) is a polyester resin containing at least the first diol unit (B1); More preferably, The dicarboxylic acid unit (A) comprises at least a first dicarboxylic acid unit (A1) and a second dicarboxylic acid unit (A2), The diol unit (B) is a polyester resin containing at least a first diol unit (B1); Particularly preferred The dicarboxylic acid unit (A) comprises at least a first dicarboxylic acid unit (A1) and a second dicarboxylic acid unit (A2), The diol unit (B) is a polyester resin containing at least a first diol unit (B1) and a second diol unit (B2).

[0349] (Method of manufacturing resin) The method for producing the resin of the present invention is not particularly limited as long as it uses compound (1) as a raw material, and may be a conventional method depending on the type of resin and other polymerization components (copolymer components). If the resin is a thermoplastic resin, the polymerization components may be mixed and polymerized (or polycondensed), and typical examples include melt polymerization, solution polymerization, and interfacial polymerization.

[0350] For example, in the case of polyester resins such as polyester resins, they can be produced by reacting a dicarboxylic acid component (A) corresponding to the aforementioned dicarboxylic acid unit (A), a diol component (B) corresponding to the aforementioned diol unit (B), and, if necessary, a carbonate bond-forming component (C). These can be prepared by conventional methods, specifically by transesterification, melt polymerization methods such as direct polymerization, solution polymerization, or interfacial polymerization.

[0351] Depending on the polymerization method, the reaction may be carried out in or without a solvent. However, if solvent remains in the resulting thermoplastic resin, it may corrode the mold during molding. Also, depending on the polymerization method, if by-products such as salts remain, it can cause turbidity in the thermoplastic resin (or its molded product), which may result in defects, especially in applications requiring high transparency, such as optical components. Therefore, from the viewpoint of improving moldability (productivity) and transparency, a melt polymerization method (or melt polymer) that can effectively suppress the residue or inclusion of solvents and salts is preferred.

[0352] The charging ratio of dicarboxylic acid component (A) to diol component (B) is usually, for example, 1 / 1.2 to 1 / 0.8, preferably 1 / 1.1 to 1 / 0.9, but it is not necessarily limited to this range, and at least one component selected from dicarboxylic acid component (A) and diol component (B) may be used in excess of the planned introduction ratio. For example, a second diol component (B2), such as ethylene glycol, which can be distilled from the reaction system, may be used in excess of the ratio introduced into the polyester resin (or the introduction ratio).

[0353] Furthermore, when using the carbonate bond-forming component (C), the ratio of the total amount of the dicarboxylic acid component (A) and the carbonate bond-forming component (C) to the amount of the diol component (B) used is, for example, former / latter (molar ratio) = 1 / 1.2 to 1 / 0.8, preferably 1 / 1.1 to 1 / 0.9. Note that the carbonate bond-forming component (C) may be used in slightly excess of the planned introduction ratio, taking into account volatilization and decomposition in the reaction. For example, the carbonate bond-forming component (C) may be used in excess of 0.1 to 5 mol%, preferably 2 to 3 mol%, relative to the total amount of dicarboxylic acid units (A) and carbonate units (C) (total amount to be introduced into the resin).

[0354] The reaction may be carried out in the presence of a catalyst. Conventional esterification catalysts, such as metal catalysts, can be used as catalysts. 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; group 12 metals of the periodic table such as zinc and cadmium; group 13 metals of the periodic table such as aluminum; group 14 metals of the periodic table such as germanium and lead; and group 15 metals 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, for example, germanium compounds such as germanium dioxide, germanium hydroxide, germanium oxalate, germanium tetraethoxide, and germanium-n-butoxide; antimony compounds such as antimony trioxide, antimony acetate, and antimony ethylene glycolate; 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.

[0355] These catalysts can be used individually 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, and titanium(IV) tetrabutoxide are preferred. The amount of catalyst used is, for example, 0.01 × 10⁻¹⁶ per mole of dicarboxylic acid component (A). -4 ~100×10 -4 moles, preferably 0.1 × 10⁻⁶ -4 ~40×10 -4 It is a mole.

[0356] Furthermore, the reaction may be carried out in the presence of stabilizers such as heat stabilizers or antioxidants, if necessary. Heat stabilizers are commonly used, and examples include phosphorus compounds such as trimethyl phosphate (or trimethyl phosphate), triethyl phosphate, tributyl phosphate (or tributyl phosphate), triphenyl phosphate, dibutyl phosphate (or dibutyl phosphate), phosphorous acid, trimethyl phosphate, and triethyl phosphate. Of these, trimethyl phosphate is commonly used. The amount of heat stabilizer used is, for example, 0.01 × 10⁻¹⁶ per mole of dicarboxylic acid component (A). -4 ~100×10 -4 moles, preferably 0.1 × 10⁻⁶ -4 ~40×10 -4 It is a mole.

[0357] The reaction may be carried out in an atmosphere of an inert gas, such as nitrogen gas; or a noble gas such as helium or argon. The reaction may also be carried out under reduced pressure, for example, 1 × 10⁻⁶. 2 ~1 × 10 4 The reaction can also be carried out at around Pa. The transesterification reaction may be carried out under an inert gas atmosphere such as nitrogen gas, and the polycondensation reaction may be carried out under reduced pressure. The reaction temperature can be selected according to the polymerization method; for example, the reaction temperature in the melt polymerization method is, for example, 150 to 320°C, preferably 200 to 310°C, and more preferably 250 to 300°C.

[0358] After the reaction is complete, the resulting resin may be separated and purified by conventional methods, such as washing, extraction, concentration, reprecipitation, centrifugation, filtration, column chromatography, adsorption, or a combination thereof.

[0359] (Properties of resin) The resin of the present invention has excellent heat resistance, and its glass transition temperature (Tg) may be, for example, around 130 to 200°C, and preferably in stages, 150 to 195°C, 160 to 190°C, 165 to 185°C, and 170 to 180°C. If the Tg is too low, the heat resistance will decrease, making it prone to discoloration (or staining) during manufacturing and / or use, or prone to deformation in high-temperature environments after being molded into a predetermined shape, which may prevent its use in applications requiring high thermal stability.

[0360] The resin of the present invention also has excellent optical properties and possesses a high refractive index.

[0361] The refractive index nd of the resin may be, for example, about 1.65 to 1.7 at a temperature of 20°C and a wavelength of 587.6 nm, and preferably in the following increments: 1.663 to 1.69, 1.665 to 1.685, and 1.67 to 1.68.

[0362] The refractive index nC of the resin may be, for example, around 1.64 to 1.69 at a temperature of 20°C and a wavelength of 656.3 nm, and preferably in the following increments: 1.65 to 1.68, 1.655 to 1.675, and 1.66 to 1.67.

[0363] The refractive index ne of the resin may be, for example, about 1.66 to 1.71 at a temperature of 20°C and a wavelength of 546.1 nm, and preferably in the following increments: 1.67 to 1.7, 1.675 to 1.695, and 1.68 to 1.69.

[0364] The refractive index nF of the resin may be, for example, around 1.67 to 1.72 at a temperature of 20°C and a wavelength of 486.1 nm, and preferably in the following increments: 1.68 to 1.715, 1.69 to 1.71, and 1.695 to 1.705.

[0365] The refractive index ng of the resin may be, for example, about 1.69 to 1.75 at a temperature of 20°C and a wavelength of 435.8 nm, and preferably in the following increments: 1.7 to 1.74, 1.71 to 1.735, and 1.72 to 1.73.

[0366] The refractive index nh of the resin may be, for example, about 1.7 to 1.76 at a temperature of 20°C and a wavelength of 404.7 nm, and preferably in the following increments: 1.715 to 1.75, 1.725 to 1.745, and 1.73 to 1.74.

[0367] Furthermore, resins exhibit low birefringence even at relatively high refractive indices. The birefringence of a resin may also be evaluated by the birefringence (3x birefringence) of a stretched film obtained by uniaxially stretching a film formed from the resin alone at a stretching temperature of glass transition temperature Tg + 10°C, a stretching speed of 25 mm / min, and a stretching ratio of 3x. The absolute value of the birefringence (3x birefringence) of the stretched film can be, for example, 0 to 75 × 10⁻¹⁰ at a measurement temperature of 25°C and a wavelength of 600 nm. -4 It may be within a range of degree, preferably in stages as follows: 60 × 10 -4 Below, 50 x 10 -4 Below, 40 x 10 -4 Below, 30 x 10 -4 Below, 25 x 10 -4 Below, 20 x 10 -4 The following applies; for example, the lower limit of the absolute value range for the birefringence (triple birefringence) is 1 × 10⁻⁶. -4 The above 5 x 10 -4 The above is 10 x 10 -4 The above is 15 x 10 -4 That's all.

[0368] Furthermore, the Abbe number νd of the resin may be, for example, around 15 to 25 at a temperature of 20°C, and preferably in the following increments: 17 to 23, 17.5 to 21, 18 to 20, and 18.5 to 19.5. If the Abbe number is too high, the refractive index may decrease. In the present invention, even with a relatively low Abbe number, it is easy to exhibit large anomalous dispersion characteristics (θgF value or ΔθgF value), and the selection of optical materials can be effectively increased, making it particularly suitable for use as an optical lens.

[0369] The resin of the present invention exhibits greater anomalous dispersion characteristics compared to conventional resins, even when containing a fluorene skeleton. The partial dispersion ratio θgF value of the thermoplastic resin may be, for example, 0.66 or higher at a temperature of 20°C, specifically around 0.665 to 0.71, and preferably in the following increments: 0.67 to 0.7, 0.675 to 0.695, and 0.68 to 0.69.

[0370] Furthermore, the difference in θgF (ΔθgF value) for reference dispersion glasses with the same Abbe number may be, for example, 0.04 or more, specifically around 0.05 to 0.1, and preferably in the following increments: 0.055 to 0.095, 0.06 to 0.09, 0.065 to 0.085, and 0.07 to 0.08.

[0371] If the partial dispersion ratio θgF or ΔθgF is too low, chromatic aberration may not be effectively reduced or corrected.

[0372] The weight-average molecular weight (Mw) of the resin can be measured by gel permeation chromatography (GPC), and in terms of polystyrene equivalent, it may be, for example, around 10,000 to 300,000, and preferably in the following increments: 20,000 to 100,000, 25,000 to 70,000, 30,000 to 50,000, and 35,000 to 40,000. If the weight-average molecular weight (Mw) is too low, moldability (productivity) may decrease, or the range of applications may be limited.

[0373] In this specification and in the claims, the glass transition temperature Tg, refractive indices (nd, nC, ne, nF, ng, ng), birefringence (3x birefringence), Abbe number νd, partial dispersion ratio θgF value, ΔθgF value, and weight-average molecular weight Mw can be measured by the methods described in the examples below.

[0374] While the resin may be crystalline (crystalline polymer), it is preferable that it be amorphous (amorphous polymer), especially for applications such as optical lenses and other optical components, because it is easier to reduce birefringence.

[0375] (Molded body containing resin) The present invention also includes molded articles containing the aforementioned resin.

[0376] The molded article only needs to contain at least the aforementioned resin, and may optionally contain other resins different from the aforementioned resin (the resin of the present invention), such as conventional curable resins or thermoplastic resins, either alone or in combination of two or more, or it may not contain any resins at all. The proportion of the aforementioned resin (the resin of the present invention) in the molded article may be, for example, about 10 to 100% by mass, preferably in stages of 30% or more by mass, 50% or more by mass, 70% or more by mass, 90% or more by mass, and substantially 100% by mass. Alternatively, the proportion of the aforementioned resin (the resin of the present invention) in the molded article may be, for example, about 1 to 90% by mass or 60 to 80% by mass.

[0377] 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 regulators, leveling agents, defoaming agents, surface modifiers, hydrolysis inhibitors, carbon materials, stabilizers, and stress reducers. Examples of stabilizers include antioxidants, ultraviolet absorbers, and thermal stabilizers. Examples of stress reducers include silicone oil, silicone rubber, various plastic powders, and various engineering plastic powders. These additives may be used individually or in combination of two or more. The total proportion of these additives is, for example, 50 parts by mass or less, preferably in stages, 30 parts by mass or less, 0 to 10 parts by mass, or about 0.1 to 5 parts by mass, per 100 parts by mass of the resin.

[0378] The method for manufacturing the molded article is not particularly limited, and it can be molded using conventional molding methods depending on the type of resin. For example, in the case of a thermoplastic resin, it can be manufactured using injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, pressure molding, casting molding, etc.

[0379] Furthermore, the shape of the molded body is not particularly limited and can include, for example, one-dimensional structures such as linear, fibrous, or thread-like structures; two-dimensional structures such as film-like, sheet-like, or plate-like structures; lens-like structures such as concave or convex lens-like structures; and three-dimensional structures such as rod-like or hollow (tubular) structures.

[0380] Because the molded product possesses a good balance of excellent optical properties and heat resistance, it can be effectively used as an optical component, particularly as an optical lens, such as an optical film (optical sheet) or optical lens.

[0381] The film can be manufactured by forming (or molding) the resin using conventional film-forming methods, such as casting (solvent casting), melt extrusion, or calendering.

[0382] The average thickness of the film can be selected from a range of approximately 1 to 1000 μm depending on the application, for example, 1 to 200 μm, preferably 5 to 150 μm, and more preferably 10 to 120 μm.

[0383] The film may be unstretched or stretched, and even if it is stretched, it can maintain low birefringence. Such a stretched film may be either uniaxially oriented or biaxially oriented.

[0384] The stretching ratio is, for example, 1.1 to 10 times, preferably 1.2 to 8 times, and more preferably 1.5 to 6 times, in each direction for uniaxial or biaxial stretching. In the case of biaxial stretching, equal stretching, for example, 1.5 to 5 times in both the longitudinal and transverse directions, is also possible, as is eccentric stretching, for example, 1.1 to 4 times in the longitudinal direction and 2 to 6 times in the transverse direction. In the case of uniaxial stretching, longitudinal stretching, for example, 2.5 to 8 times in the longitudinal direction, is also possible, as is transverse stretching, for example, 1.2 to 5 times in the transverse direction.

[0385] 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.

[0386] Such stretched films can be obtained by subjecting a film (or unstretched film) after film formation to a stretching treatment. There are no particular restrictions on the stretching method; in the case of uniaxial stretching, either wet stretching or dry stretching may be used, and in the case of biaxial stretching, either the tenter method (flat method) or the tube method may be used, but the tenter method is preferred because it is superior in terms of uniformity of stretched thickness. [Examples]

[0387] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. The evaluation items and details of the raw materials are shown below.

[0388] [Evaluation Method] ( 1 (H-NMR) The sample was dissolved in a deuterated solvent such as deuterated chloroform, using tetramethylsilane as an internal standard, and then analyzed using a nuclear magnetic resonance spectrometer (BRUKER "AVANCE III HD"). 1 The 1H-NMR spectrum was measured.

[0389] (LC purity) Using a Shimadzu LC-2010A HT HPLC (High Performance Liquid Chromatography) instrument and a Tosoh ODS-80TM column, samples were dissolved in acetonitrile and measured to calculate HPLC purity [area %].

[0390] (5% weight loss temperature, 10% weight loss temperature) Thermogravimetric analysis - Using a differential thermal analyzer (TG-DTA) (TG / DTA6200, manufactured by SII Nanotechnology Co., Ltd.), the temperatures at which the sample mass decreased by 5% and 10% were measured under a nitrogen atmosphere and a heating rate of 10°C / min.

[0391] (Glass transition temperature Tg) Measurements were taken using a differential scanning calorimeter (EXSTAR6000 DSC6220 ASD-2, manufactured by SII Nanotechnology Co., Ltd.) under a nitrogen atmosphere at a heating rate of 10°C / min.

[0392] (molecular weight) The sample was dissolved in chloroform, and the weight-average molecular weight (Mw) in terms of standard polystyrene was determined using gel permeation chromatography (HLC-8320GPC, manufactured by Tosoh Corporation).

[0393] (Refractive index) The refractive indices of the dicarboxylic acids or their derivatives obtained in Examples 1 and 2 were measured using a refractometer ("RX-7000i" manufactured by Atago Co., Ltd.) at a temperature of 25°C and a wavelength of 589 nm (D line). The refractive index was calculated by dissolving the sample in dimethyl sulfoxide to prepare several solutions with different concentrations (10% by mass, 30% by mass), measuring the refractive index of the resulting solutions, and then extrapolating the concentration to 100% by mass in a calibration curve (approximate straight line).

[0394] The refractive index of the resin sample was measured as follows: A test specimen with a thickness of approximately 1 mm was formed by hot pressing the sample at 200-240°C. This test specimen was measured using a Carnu precision refractometer "KPR-2000" [manufactured by Shimadzu Devices Mfg. Ltd.] at a measurement temperature of 20°C, using a contact fluid with a refractive index of 1.60 as the contact fluid for the test specimen, and measuring the refractive index nd at a wavelength of 587.6 nm (d line). Similarly, the refractive indices nC, ne, nF, ng, and nh were measured in the same manner as for the refractive index nd, except that the measurement wavelengths were changed to 656.3 nm (C line), 546.1 nm (e line), 486.1 nm (F line), 435.8 nm (g line), and 404.7 nm (h line).

[0395] (Abbe number νd) The Abbe number νd was calculated from the refractive indices nF, nd, and nC using the following formula.

[0396] (Abbe number νd) = (nd-1) / (nF-nC).

[0397] (Partial dispersion ratio θgF) The value of the partial dispersion ratio θgF was calculated from the refractive indices ng, nF, and nC using the following formula.

[0398] (Partial dispersion ratio θgF)=(ng-nF) / (nF-nC).

[0399] Furthermore, the ΔθgF value was calculated using the method described below. Specifically, when two types of optical glasses that do not exhibit anomalous dispersion, K7(νd,θgF)=(60.5,0.547) and F2(νd,θgF)=(36.3,0.583), are plotted on a graph with the Abbe number νd on the horizontal axis and the partial dispersion ratio θgF on the vertical axis, the straight line connecting the coordinates of these two reference dispersion glasses is expressed by the following equation.

[0400] (Partial dispersion ratio θgF)=-0.00149×(Abbe number νd)+0.637

[0401] The Abbe number νd of the obtained resin was substituted into this formula to obtain the θgF value of the reference dispersion glass, and the ΔθgF value was calculated by subtracting this from the measured θgF value of the resin.

[0402] (Birefringence (3x stretching)) A film with a thickness of 200 to 600 μm was formed by hot pressing the sample at 200 to 240°C. This film was cut into strips of 10 mm x 50 mm and uniaxially stretched at 25 mm / min under the glass transition temperature Tg + 10°C to obtain test specimens. The retardation of the obtained test specimens was measured using a phase difference film / optical material inspection device (RETS-100, manufactured by Otsuka Electronics Co., Ltd.) at a measurement temperature of 25°C and a measurement wavelength of 600 nm, using the parallel nicol rotation method. The birefringence (or 3x birefringence) was calculated by dividing the value by the thickness of the measurement area.

[0403] [Raw materials] BNF:9,9-Bis(6-hydroxy-2-naphthyl)fluorene (Dicarboxylic acid component) 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 Japanese Patent Publication No. 2005-89422, except that methyl acrylate [37.9 g (0.44 mol)] is used instead of t-butyl acrylate. DMN: 2,6-Bis(methoxycarbonyl)naphthalene (Diol component) BPEF:9,9-Bis[4-(2-hydroxyethoxy)phenyl]fluorene EG: Ethylene glycol

[0404] [Synthesis Example 1] Bromination of BNF

[0405] [ka]

[0406] Under a nitrogen atmosphere, 360 g (0.80 mol) of BNF and 8.0 kg of chloroform were added to a 10 L reaction vessel, and a mixed solution of 258 g (1.61 mol) of bromine and 3.9 kg of chloroform was added dropwise. The mixture was stirred at room temperature (15-20°C) for 3 hours, and the disappearance of the starting material (BNF) was confirmed. The resulting reaction mixture was washed twice with 900 g of saturated sodium sulfite aqueous solution, and then washed three times with 900 g of distilled water. The resulting organic layer was concentrated to remove chloroform, and the precipitated crystals were filtered off. The mixture was then rinsed with 800 g of isopropyl alcohol (IPA) to obtain 419 g of the target product, 9,9-bis(5-bromo-6-hydroxy-2-naphthyl)fluorene (hereinafter also referred to as BNF-Br) (yield 86%, LC purity 99%). 1 The results of the H-NMR spectrum are shown below.

[0407] 1 H-NMR (CDCl3, 300MHz): δ(ppm)=5.8(s,2H), 7.2(d,2H), 7.2-7.5(m,12H), 7.8(d,2H), 7.9(d,2H).

[0408] [Synthesis Example 2] Ethylation of BNF-Br compound by butyrate

[0409] [ka]

[0410] Under a nitrogen atmosphere, 216 g (355 mmol) of BNF-Br, 180 g (923 mmol) of ethyl 4-bromobutyrate, and 1 L of N,N-dimethylformamide (DMF) were added to a reaction vessel. Then, 245 g (1.77 mol) of potassium carbonate was added, and the temperature was raised to 80°C. After stirring at 80°C for 3 hours to confirm the formation of the target product, the mixture was cooled to 50°C, and 1.2 L of methyl isobutyl ketone (MIBK) was added. After repeating the washing operation with 2.0 L of deionized water three times, the mixture was heated to 80°C to remove the organic solvent by distillation, and 317 g (LC purity 99% or higher) of the target product, 9,9-bis[5-bromo-6-(3-ethoxycarbonylpropyloxy)-2-naphthyl]fluorene (hereinafter also referred to as dibromo-BNF ethyl butyrate), was obtained as a reddish-brown viscous solid. 1 The results of the H-NMR spectrum are shown below.

[0411] 1 H-NMR (CDCl3, 300MHz): δ(ppm)=1.2-1.3(m,6H), 2.1-2.2(m,4H), 2.6(t,4H) , 4.1-4.2(m,8H), 7.1-7.2(d,2H), 7.3-7.6(m,12H), 7.8(d,2H), 8.1(d,2H).

[0412] [Example 1] Synthesis of dinaphthyl BNF ethyl butyrate

[0413] [ka]

[0414] In a 3 L reaction vessel, 200 g (239 mmol) of ethyl dibromo-BNF butyrate, 95 g (552 mmol) of 2-naphthylboronic acid, 310 mL of 2 M Na2CO3 aqueous solution, and 1.08 kg of MIBK were added. After degassing and purging the system with nitrogen, 1.89 g (7.21 mmol) of triphenylphosphine and 540 mg (2.41 mmol) of palladium acetate were added, and the mixture was stirred under reflux at 85-88°C for 4 hours. After the reaction, the resulting reaction mixture was washed with deionized water, treated with activated carbon, and washed again with deionized water. The resulting organic layer was concentrated, 900 g of IPA was added over 14 minutes at 50°C, cooled to below 5°C, stirred for 1 hour, and the precipitated crystals were filtered off. The obtained crystals were rinsed three times with 100g of cold IPA at 5°C or below to obtain 197g of the target product, 9,9-bis[5-(2-naphthyl)-6-(3-ethoxycarbonylpropyloxy)-2-naphthyl]fluorene (hereinafter also called dinaphthyl BNF ethyl butyrate), as light brown crystals (yield 88.7%, LC purity 95.5%). 1 The results of the H-NMR spectrum are shown below.

[0415] 1 H-NMR (CDCl3, 300MHz): δ(ppm)=1.1(t,6H), 1.8-1.9(m,4H), 2.1-2.2(t,4H), 4.0(m,8H), 7.2-7.7(m,32H).

[0416] The resulting elemental dinaphthyl BNF ethyl butyrate had a refractive index nD (D line, 25°C) of 1.666, indicating high refraction. Furthermore, the 5% weight loss temperature of dinaphthyl BNF ethyl butyrate was 333.8°C, and the 10% weight loss temperature was 397.1°C, demonstrating high heat resistance.

[0417] [Example 2] Synthesis of ethyl diphenyl BNF butyrate

[0418] [ka]

[0419] In a 2 L reaction vessel, 104 g (124 mmol) of ethyl dibromo-BNF butyrate, 34.9 g (286 mmol) of phenylboronic acid, 160 mL of 2 M Na2CO3 aqueous solution, and 560 g of MIBK were added. After degassing and purging the system with nitrogen, 980 mg (3.74 mmol) of triphenylphosphine and 540 mg (2.41 mmol) of palladium acetate were added, and the mixture was stirred under reflux at 85-88°C for 4 hours. After the reaction, the resulting reaction mixture was washed with deionized water, treated with activated carbon, and washed again with deionized water. The resulting organic layer was concentrated, 310 g of methanol was added at 60°C, and the mixture was stirred at 60°C for 30 minutes. After cooling to 10°C and stirring for 1 hour, the resulting crystals were filtered to obtain 84.6 g of the target product, 9,9-bis[5-phenyl-6-(3-ethoxycarbonylpropyloxy)-2-naphthyl]fluorene (hereinafter also referred to as diphenyl BNF ethyl butyrate), as light brown crystals (yield 81.9%, LC purity: 99.5%). 1 The results of the H-NMR spectrum are shown below.

[0420] 1 H-NMR (CDCl3, 300MHz): δ(ppm)=1.2(t,6H), 1.9(m,4H), 2.2(t,4H), 4.0-4.1(m,8H), 6.7-6.8(d,2H), 7.1(d,2H), 7.1-7.8(m,24H).

[0421] The resulting ethyl diphenyl-BNF butyrate had a refractive index nD (D line, 25°C) of 1.647, indicating high refraction. Furthermore, the 5% weight loss temperature of ethyl diphenyl-BNF butyrate was 402°C, and the 10% weight loss temperature was 416°C, demonstrating high heat resistance.

[0422] [Example 3] In a reactor, 37 g (40 mmol) of dinaphthyl BNF ethyl butyrate and 23 g (92 mmol) of DMN were charged as dicarboxylic acid components, 49 g (112 mmol) of BPEF and 18 g (283 mmol) of EG were charged as diol components, and 7.8 mg (30 μmol) of manganese acetate tetrahydrate was charged as a catalyst for the transesterification reaction. Under a nitrogen atmosphere, the mixture was gradually heated to 250°C and stirred to carry out transesterification. After removing the alcohol component produced by the transesterification reaction, 36 mg (344 μmol) of germanium dioxide was added as a catalyst for the polycondensation reaction, and 11 mg (80 μmol) of trimethyl phosphate was added as a heat stabilizer. The mixture was gradually heated to 275°C and 130 Pa, and the pressure was reduced while removing EG during the polycondensation reaction. After the reaction was complete, the contents were removed from the reactor to obtain a polyester resin.

[0423] [Example 4] In the reactor, 52 g (56 mmol) of dinaphthyl BNF ethyl butyrate and 14 g (56 mmol) of DMN were charged as dicarboxylic acid components, 42 g (95 mmol) of BPEF and 15 g (241 mmol) of EG were charged as diol components, and 7.8 mg (30 μmol) of manganese acetate tetrahydrate was charged as a catalyst for the transesterification reaction. Under a nitrogen atmosphere, the mixture was gradually heated to 250°C and stirred to carry out transesterification. After removing the alcohol component produced by the transesterification reaction, 36 mg (344 μmol) of germanium dioxide was added as a catalyst for the polycondensation reaction, and 11 mg (80 μmol) of trimethyl phosphate was added as a heat stabilizer. The mixture was gradually heated to 275°C and 130 Pa, and the pressure was reduced while removing EG during the polycondensation reaction. After the reaction was complete, the contents were removed from the reactor to obtain polyester resin.

[0424] [Example 5] In a reactor, 32 g (39 mmol) of ethyl diphenyl BNF butyrate and 22 g (91 mmol) of DMN were added as dicarboxylic acid components, 49 g (111 mmol) of BPEF and 17 g (280 mmol) of EG were added as diol components, and 7.8 mg (30 μmol) of manganese acetate tetrahydrate was added as a catalyst for the transesterification reaction. The mixture was gradually heated to 250°C under a nitrogen atmosphere and stirred to carry out the transesterification. After removing the alcohol component produced by the transesterification reaction, 36 mg (344 μmol) of germanium dioxide was added as a catalyst for the polycondensation reaction, and 11 mg (80 μmol) of trimethyl phosphate was added as a heat stabilizer. The mixture was gradually heated to 275°C and 130 Pa, and the pressure was reduced while removing EG during the polycondensation reaction. After the reaction was complete, the contents were removed from the reactor to obtain a polyester resin.

[0425] [Example 6] In a reactor, 41 g (50 mmol) of ethyl diphenyl BNF butyrate and 15 g (61 mmol) of DMN were added as dicarboxylic acid components, 41 g (94 mmol) of BPEF and 15 g (238 mmol) of EG were added as diol components, and 7.8 mg (30 μmol) of manganese acetate tetrahydrate was added as a catalyst for the transesterification reaction. Under a nitrogen atmosphere, the mixture was gradually heated to 250°C and stirred to carry out transesterification. After removing the alcohol component produced by the transesterification reaction, 36 mg (344 μmol) of germanium dioxide was added as a catalyst for the polycondensation reaction, and 11 mg (80 μmol) of trimethyl phosphate was added as a heat stabilizer. The mixture was gradually heated to 275°C and 130 Pa, and the pressure was reduced while removing EG during the polycondensation reaction. After the reaction was complete, the contents were removed from the reactor to obtain a polyester resin.

[0426] [Comparative Example 1] In a reactor, 21 g (61 mmol) of FDP-m and 35 g (142 mmol) of DMN were added as dicarboxylic acid components, 76 g (173 mmol) of BPEF and 27 g (437 mmol) of EG were added as diol components, and 7.8 mg (30 μmol) of manganese acetate tetrahydrate was added as a catalyst for the transesterification reaction. Under a nitrogen atmosphere, the mixture was gradually heated to 250°C and stirred to carry out transesterification. After removing the alcohol component produced by the transesterification reaction, 36 mg (344 μmol) of germanium dioxide was added as a catalyst for the polycondensation reaction, and 11 mg (80 μmol) of trimethyl phosphate was added as a heat stabilizer. The mixture was gradually heated to 275°C and 130 Pa, and the pressure was reduced while removing EG during the polycondensation reaction. After the reaction was complete, the contents were removed from the reactor to obtain a polyester resin.

[0427] [Comparative Example 2] In a reactor, 33 g (98 mmol) of FDP-m and 24 g (99 mmol) of DMN were added as dicarboxylic acid components, 73 g (167 mmol) of BPEF and 26 g (423 mmol) of EG were added as diol components, and 7.8 mg (30 μmol) of manganese acetate tetrahydrate was added as a catalyst for the transesterification reaction. Under a nitrogen atmosphere, the mixture was gradually heated to 250°C and stirred to carry out transesterification. After removing the alcohol component produced by the transesterification reaction, 36 mg (344 μmol) of germanium dioxide was added as a catalyst for the polycondensation reaction, and 11 mg (80 μmol) of trimethyl phosphate was added as a heat stabilizer. The mixture was gradually heated to 275°C and 130 Pa, and the pressure was reduced while removing EG during the polycondensation reaction. After the reaction was complete, the contents were removed from the reactor to obtain a polyester resin.

[0428] The polymer composition ratio (the proportion (molar ratio) of constituent units derived from each polymerization component used in the preparation) was confirmed from the NMR spectra of each polyester resin obtained in the examples and comparative examples. The polymer composition ratio, charging ratio, and evaluation results of each physical property for each polyester resin are shown in the table below. Note that the numbers in parentheses in Table 1 indicate the charging ratio.

[0429] [Table 1]

[0430] [Table 2]

[0431] As is clear from the results in Tables 1 and 2, the examples showed higher glass transition temperatures (Tg) and refractive indices compared to the comparative examples. Furthermore, although the examples contained many aromatic ring skeletons (benzene ring skeletons) that tend to increase birefringence, in all examples the refractive index and Tg were improved without excessively increasing birefringence, and a good balance was achieved between low birefringence, high refractive index, and high heat resistance, which are in a trade-off relationship. In particular, Examples 3 and 4 showed surprisingly low birefringence compared to Examples 5 and 6, which used diphenyl BNF ethyl butyrate, and Comparative Examples 1 and 2, which used FDP-m, despite using dinaphthyl BNF ethyl butyrate, which has more aromatic ring skeletons (benzene ring skeletons). Among these, Example 4 best balanced low birefringence, high refractive index, and high heat resistance.

[0432] Furthermore, it was found that even resins with a fluorene skeleton can be prepared that exhibit high anomalous dispersion characteristics, with large partial dispersion ratios θgF and ΔθgF. Therefore, they can be effectively used in optical lenses, particularly optical lenses that reduce or correct chromatic aberration by combining multiple lenses. [Industrial applicability]

[0433] The dicarboxylic acid (or its salt) or derivative of the present invention exhibits high refractive index and heat resistance, and can therefore be effectively used as a resin raw material, an additive (or resin additive) such as a refractive index improver, a heat resistance improver, or a curing agent, or a resist material. Examples of curing agents include those for epoxy resins. Examples of resist materials include negative-type (curable-type) or positive-type resist materials. For example, negative-type (curable-type) resist materials can be used in the form of a crosslinking agent for alkali-available resins, and positive-type resist materials can be used as R 3a and R3b It may also be used in a form such as a branched alkoxy group, in combination with a photoacid generator.

[0434] The resin of the present invention exhibits excellent optical properties such as a high refractive index and low birefringence, as well as high heat resistance, making it suitable for a wide range of applications. For example, it can be used as a coating agent or coating film, specifically paints, inks, protective films for electronic equipment and liquid crystal components, etc.; adhesives and sealants; resin fillers; electrical and electronic materials or components (electrical and electronic equipment), specifically antistatic agents, carrier transport agents, light emitters, organic photoreceptors, thermal recording materials, photochromic materials, hologram recording materials, antistatic trays, conductive sheets, optical discs, inkjet printers, digital paper, color filters, organic EL elements, organic semiconductor lasers, dye-sensitized solar cells, sensors, EMI shielding films, etc.; and mechanical materials or mechanical parts (equipment), specifically automotive materials or parts, aerospace-related materials or parts, sliding members, etc.

[0435] Furthermore, the resin of the present invention can effectively utilize as an optical component because it can balance excellent optical properties such as a high refractive index and low birefringence with high heat resistance.

[0436] Typical optical components include optical films (optical sheets) such as liquid crystal films and organic EL films; optical lenses such as eyeglass lenses and camera lenses; prisms, holograms, and optical fibers.

[0437] Examples of optical films include polarizing films, polarizing elements and polarizer protective films that constitute polarizing films, phase difference films, alignment films, viewing angle expansion (compensation) films, diffuser films, prism sheets, light guide plates, brightness enhancement films, near-infrared absorption films, reflective films, anti-reflective (AR) films, anti-reflective (LR) films, anti-glare (AG) films, transparent conductive (ITO) films, anisotropic conductive (ACF) films, electromagnetic shielding (EMI) films, films for electrode substrates, films for color filter substrates, barrier films, color filter layers, black matrix layers, and adhesive 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 diodes (OLEDs), plasma displays (PDPs), field emission displays (FEDs), and electronic paper. Specific examples of such devices include televisions; personal computers (PCs) such as desktop PCs, notebook PCs, or tablet PCs; smartphones and mobile phones; car navigation systems; and devices or equipment equipped with flat panel displays (FPDs) such as touch panels.

[0438] Examples of optical lenses include eyeglass lenses, contact lenses, camera lenses, VTR zoom lenses, pickup lenses, Fresnel lenses, solar focusing lenses, objective lenses, and rod lens arrays.

[0439] In particular, because the resin of the present invention exhibits high anomalous dispersion characteristics, it may be suitably used in optical lenses such as camera lenses. Typical devices or equipment that incorporate such optical lenses include small devices 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).

Claims

1. A compound represented by the following formula (1) or a salt thereof, 【Chemistry 1】 [In the formula, R １ represents a substituent, and k1 represents an integer from 0 to 8. Z １ａ and Z １ｂ These independently represent substituted or unsubstituted arene rings. Z ２ａ and Z ２ｂ These independently represent substituted or unsubstituted arene rings. A １ａ and A １ｂ m1a and m1b independently represent an alkylene group, and m1a and m1b independently represent an integer greater than or equal to 0. R ２ａ and R ２ｂ each independently represents a substituted or unsubstituted divalent hydrocarbon group, R ３ａ and R ３ｂ The hydroxyl group and the group [-OR ｈ３ ] (wherein, R ｈ３ (This indicates a hydrocarbon group) or a halogen atom. In formula (1) above, R1 is a halogen atom, a hydrocarbon group, a group [-OR h1] (wherein R h1 represents a hydrocarbon group), an acyl group, a nitro group, a cyano group, or a substituted amino group, and k1 is an integer from 0 to 4. The arene rings of Z1a and Z1b are independently monocyclic or fused polycyclic arene rings. The arene rings of Z 2a and Z 2b are independently monocyclic or fused polycyclic arene rings. m1a and m1b are independent integers between 0 and 10. A compound or a salt thereof in which the divalent hydrocarbon groups R2a and R2b are independently alkylene groups.

2. A crystal of the compound or a salt thereof according to Claim 1.

3. A method for producing a compound represented by formula (1) or a salt thereof according to claim 1, by reacting a compound represented by formula (2) or a salt thereof with a compound represented by formula (3a) and a compound represented by formula (3b) below. 【Chemistry 2】 [In the formula, X １ａ and X １ｂ And, X ２ａ and X ２ｂ These are groups that can form carbon-carbon bonds with each other through coupling reactions. R １ ,k1,Z １ａ and Z １ｂ Z ２ａ and Z ２ｂ A １ａ and A １ｂ , m1a and m1b, R ２ａ and R ２ｂ , R ３ａ and R ３ｂ These are the same as in formula (1) above.

4. A resin containing at least one constituent unit represented by the following formula (A-1). 【Transformation 3】 [In the formula, R1, k1, Z １ａ and Z1b, Z ２ａ and Z2b, A １ａ and A1b, m1a and m1b, and R ２ａ and R ２ｂ Each of these is the same as formula (1) described in claim 1.

5. The resin is a thermoplastic resin containing at least dicarboxylic acid units (A) derived from a dicarboxylic acid component as a polymerization component, The resin according to claim 4, wherein the dicarboxylic acid unit (A) includes at least a constituent unit represented by formula (A-1) as the first dicarboxylic acid unit (A1).

6. The resin according to claim 5, wherein the dicarboxylic acid unit (A) further comprises at least a second dicarboxylic acid unit (A2) represented by the following formula (A-2). 【Chemistry 4】 (In the formula, Z ３ (This indicates a substituted or unsubstituted arene ring.)

7. In the above formula (A-2), Z ３ The resin according to claim 6, wherein the arene ring is a condensed polycyclic arene ring.

8. The resin according to claim 6 or 7, wherein the ratio of the first dicarboxylic acid unit (A1) to the second dicarboxylic acid unit (A2) is the former / latter (molar ratio) = 10 / 90 to 90 / 10.

9. The resin according to claim 5, wherein the resin further comprises a polyester resin containing at least diol units (B) derived from a diol component as a polymerization component.

10. The resin according to claim 9, wherein the diol unit (B) comprises at least one diol unit selected from a first diol unit (B1) represented by the following formula (B-1) and a second diol unit (B2) represented by the following formula (B-2). 【Transformation 5】 (In the formula, R ４ represents a substituent, and k4 represents an integer from 0 to 8. Z ４ａ and Z ４ｂ These independently represent substituted or unsubstituted arene rings. A ２ａ and A ２ｂ (Each independently represents a linear or branched alkylene group, and m2a and m2b independently represent 0 or an integer greater than or equal to 1.) 【Transformation 6】 (In the formula, A ３ (where m3 represents a linear or branched alkylene group, and m3 represents an integer of 1 or more.)

11. In the above formula (B-1), R ４ k4 is a halogen atom, hydrocarbon group, alkoxy group, acyl group, nitro group, cyano group, or substituted amino group, and k4 is an integer from 0 to 4. Z ４ａ and Z ４ｂ The arene rings are independently monocyclic or fused polycyclic arene rings. The resin according to claim 10, wherein m2a and m2b are independently 0 to 10.

12. The resin according to claim 10 or 11, wherein the ratio of the first diol unit (B1) to the second diol unit (B2) is the former / latter (molar ratio) = 50 / 50 to 99 / 1.

13. The dicarboxylic acid unit (A) further comprises at least a second dicarboxylic acid unit (A2) represented by formula (A-2) according to claim 6, The resin according to claim 10, wherein the diol unit (B) comprises at least the first diol unit (B1).

14. A resin according to any one selected from claims 4 to 7, 9 to 11, and 13, wherein the Abbe number νd is 17 to 23 and the partial dispersion ratio θgF is 0.67 or more.

15. A method for producing the resin described in claim 4, using the compound described in claim 1 or a salt thereof as a raw material.

16. A molded article comprising the resin described in any one selected from claims 4 to 7, 9 to 11, and 13.

17. The molded article according to claim 16, which is an optical component.

18. The molded article according to claim 16, which is an optical lens.

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