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

Abstract

To provide a compound or a salt thereof which has excellent heat resistance (or stability) and can be produced with high productivity, a resin using the compound or the salt thereof as a raw material (a reactive component), 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, R1 represents a substitutent, k1 represents an integer of 0 to 8, Z1a and Z1b each independently represent a substituted or unsubstituted arene ring, A1a and 1b each independently represent an alkylene group, m1a and m1b each independently represent an integer of 0 or more, R2a and R2b each independently represent an alkylene group having 3 or more carbon atoms, R3a and R3b each independently represent a hydroxyl group, a group [-ORh3] (wherein, Rh3 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] Compounds containing a 9,9-bisarylfluorene skeleton exhibit excellent properties such as refractive index and heat resistance, and are effectively utilized as raw materials for resins and other applications. Examples of compounds containing a 9,9-bisarylfluorene skeleton include polycarboxylic acids containing a 9,9-bisarylfluorene skeleton. However, with the rapid technological advancements of recent years, there is a demand for further improvements in heat resistance and refractive index.

[0003] Japanese Patent Publication No. 2009-256332 (Patent Document 1) describes a novel polycarboxylic acid having a fluorene skeleton that is excellent in properties such as heat resistance and can be used as a resin raw material. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2009-256332 [Overview of the project] [Problems that the invention aims to solve]

[0005] In Example 1 of Patent Document 1, it is described that 9,9-bis[6-(carboxymethoxy)-2-naphthyl]fluorene was prepared as a polycarboxylic acid having a fluorene skeleton, but specific properties such as heat resistance are not evaluated. Also, in Example 2 of Patent Document 1, it is described that 9,9-bis[6-(2-carboxyethoxy)-2-naphthyl]fluorene was prepared, but not only are specific properties not described, but also the yield and purity are not described.

[0006] Therefore, an object of the present invention is to provide a compound (or a salt thereof) having excellent heat resistance (or stability) and capable of being produced with high productivity (easily or efficiently), a resin using the compound (or a salt thereof) as a raw material (reaction component), and methods for producing and using them. [Means for Solving the Problems] <​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​1 is a halogen atom, hydrocarbon group, group [-OR h1 ](where R h1 k1 is an integer from 0 to 4, and is a hydrocarbon group, acyl group, nitro group, cyano group, or substituted amino group. Z 1a and Z 1b The arene rings are independently monocyclic or fused polycyclic arene rings. m1a and m1b are 0, R 2a and R 2b C 3-10 The compound or a salt thereof according to embodiment [1], wherein the compound is an alkylene group.

[0013] Embodiment [3]: In the above formula (1), R 1 It is a hydrocarbon group, and k1 is an integer from 0 to 2. Z 1a and Z 1b The arene ring is independently a benzene ring or C 10-14 It is a condensed polycyclic arene ring, m1a and m1b are 0, R 2a and R 2b Independent linear C 3-5 The compound or a salt thereof according to embodiment [1] or [2], wherein the compound is an alkylene group.

[0014] Embodiment [4]: ​​The compound or salt thereof according to any of Embodiments [1] to [3], wherein the 10% weight loss temperature is 200°C or higher.

[0015] Embodiment [5]: A compound or salt thereof according to any of Embodiments [1] to [4], in crystalline form.

[0016] Embodiment [6]: A method for producing a compound represented by formula (1) or a salt thereof according to any one of Embodiments [1] to [5], comprising a reaction step of reacting a compound represented by the following formula (2) with a compound represented by the following formula (3a) or a salt thereof and a compound represented by the following formula (3b) or a salt thereof.

[0017] [ka]

[0018] [where, X 1a and X 1b These independently represent halogen atoms, R 1 , k1, Z 1a and Z 1b , A 1a and A 1b , m1a and m1b, R 2a and R 2b , R 3a and R 3b This is the same as in equation (1) above.

[0019] Embodiment [7]: The method according to Embodiment [6], wherein in the reaction step, the reaction temperature is 90°C or less and the reaction time is 18 hours or less.

[0020] Embodiment [8]: The method according to Embodiment [6] or [7], wherein the yield of the compound represented by formula (1) or its salt obtained [based on the yield of the compound represented by formula (2)] is 80% or more, and the LC purity is 80 area% or more.

[0021] Embodiment [9]: A resin made from a compound or a salt thereof as described in any of Embodiments [1] to [5].

[0022] Embodiment

[10] : A molded article comprising a compound or salt thereof according to any of Embodiments [1] to [5], and / or a resin according to Embodiment [9].

[0023] Embodiment

[11] : The molded article according to Embodiment

[10] , which is an optical component.

[0024] Furthermore, the present invention may achieve (or solve) the following secondary objectives.

[0025] In other words, another object of the present invention is to provide compounds (or salts thereof) that exhibit a high refractive index, resins made from such compounds (or salts thereof), and methods for producing them and their uses.

[0026] Another object of the present invention is to provide a compound (or a salt thereof) capable of preparing a resin exhibiting high solvent solubility, a resin made from the compound (or a salt thereof), and methods for producing them and their uses.

[0027] 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 group", and an aryl group with 6 to 10 carbon atoms is indicated as "C 6-10 It is indicated by the "aryl group". [Effects of the Invention]

[0028] The compounds (or salts thereof) of the present invention exhibit excellent heat resistance (or stability) and can be manufactured with high productivity (easily or efficiently). Furthermore, the compounds (or salts thereof) of the present invention exhibit a high refractive index. In addition, the compounds (or salts thereof) of the present invention can also exhibit high solvent solubility. [Modes for carrying out the invention]

[0029] [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)".

[0030] [ka]

[0031] [In the formula, R 1 represents a substituent, and k1 represents an integer from 0 to 8. Z1a and Z 1b 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 alkylene groups with 3 or more carbon atoms. 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.

[0032] 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).

[0033] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0034] Examples of hydrocarbon groups include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups.

[0035] 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.

[0036] Examples of cycloalkyl groups include cyclopentyl groups, cyclohexyl groups, and other C groups.5-10 Examples include cycloalkyl groups.

[0037] Examples of aryl groups include phenyl groups, alkylphenyl groups, biphenylyl groups, naphthyl groups, etc. 6-12 Examples include aryl groups. Alkylphenyl groups include mono- or tri-C groups such as methylphenyl (or tolyl) and dimethylphenyl (or xylyl) groups. 1-4 Alkylphenyl groups are one example.

[0038] Examples of aralkyl groups include benzyl groups, phenethyl groups, and other C groups. 6-10 Aryl-C 1-4 Alkyl groups are examples.

[0039] The group [-OR h1 In ], hydrocarbon group R h1 Examples include groups similar to the hydrocarbon groups mentioned above, such as alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. h1 For example, the hydrocarbon group R h1 Examples of groups corresponding to the above include alkoxy groups, cycloalkyloxy groups, aryloxy groups, and aralkyloxy groups. Examples of alkoxy groups (linear or branched alkoxy groups) include methoxy groups, ethoxy groups, propoxy groups, n-butoxy groups, isobutoxy groups, and t-butoxy groups. 1-10 Examples include alkoxy groups. Cycloalkyloxy groups include, for example, cyclohexyloxy groups and other C groups. 5-10 Examples include cycloalkyloxy groups. Examples of aryloxy groups include phenoxy groups and other C groups. 6-10 Examples include aryloxy groups. Examples of aralkyloxy groups include the benzyloxy group and other C groups. 6-10 Aryl-C 1-4 Alkyloxy groups are one example.

[0040] As for the acyl group, C 1-12 Examples include acyl groups, such as acetyl groups and C1-6 Examples include alkyl-carbonyl groups.

[0041] Examples of mono- or disubstituted amino groups include mono- or dialkylamino groups and mono- or bis(alkylcarbonyl)amino groups. Examples of mono- or dialkylamino groups include mono- or diC groups such as mono- or dimethylamino groups. 1-4 Examples include alkylamino groups. Mono or bis(alkylcarbonyl)amino groups include mono or diacetylamino groups, etc. 1-4 Examples include alkyl-carbonyl amino groups.

[0042] Among these groups, a representative R 1 Examples include halogen atoms, hydrocarbon groups, and groups [-OR h1 Examples include cyano groups, preferably halogen atoms, hydrocarbon groups such as alkyl groups and aryl groups, alkoxy groups and aryloxy groups [-OR h1 ] are some examples.

[0043] The substitution number k1 may be an integer of, for example, 0 to 6, preferably an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, 0, or 1, with 0 being particularly preferred. Note that the group R in the two benzene rings constituting the fluorene ring. 1 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.

[0044] Note that the base R 1 If the number of substitutions k1 is multiple (2 or more), then two or more groups R substituted on one of the two benzene rings constituting the fluorene ring. 1 The types may be the same or different; and the groups R substituted on both benzene rings may also be different. 1 The types may be different, but they are preferably the same. 1The 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.

[0045] Z 1a and 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 polycyclic arene rings, and examples of polycyclic arene rings include condensed polycyclic arene rings (condensed polycyclic aromatic hydrocarbon rings) and ring-aggregated arene rings (ring-aggregated aromatic hydrocarbon rings).

[0046] 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.

[0047] 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.

[0048] In the present specification and claims, the "ring - assembled arene ring" means that two or more ring systems (arene ring systems) are directly connected by single bonds or double bonds, and the number of bonds connecting the rings is one less than the number of ring systems. For example, as described above, a phenylnaphthalene ring, a binaphthyl ring, etc. are classified as ring - assembled arene rings even if they have a condensed polycyclic arene ring skeleton, and are clearly distinguished from "condensed polycyclic arene rings" such as a naphthalene ring (non - ring - assembled arene ring).

[0049] Z 1a and Z 1b Preferred arene rings in include benzene rings, naphthalene rings, biphenyl rings, etc., C 6-14 arene rings, more preferably C 6-10 arene rings such as benzene rings and naphthalene rings, and particularly naphthalene rings. Z 1a and Z 1b The arene rings in seem to be preferably condensed polycyclic arene rings such as naphthalene rings.

[0050] Z 1a and Z 1b The types of arene rings in may be different from each other, but the same is preferred.

[0051] Z 1a and Z 1b In the arene rings of and Z, the substitution positions (bonding positions) of the 9 - position of the fluorene ring and the groups [-O-(A 1a O) m1a -R 2a -C(=O)-R 3a , [-O-(A 1b O) m1b -R 2b -C(=O)-R 3b are not particularly limited. However, with respect to the bonding position with the 9 - position of the fluorene ring, for example, at a non - adjacent and distant substitution position, preferably at the most distant substitution position, the groups [-O-(A 1a O) m1a -R 2a -C(=O)-R 3a , [-O-(A 1b O) m1b -R2b -C(=O)-R 3b It is preferable that ] be substituted (joined). Specifically, Z 1a ,Z 1b 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, for example, at the 2nd, 3rd, or 4th position, preferably the 3rd or 4th position, and more preferably the 4th position, a 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 (joined). Also, Z 1a ,Z 1b 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 1a O) m1a -R 2a -C(=O)-R 3a ],[-O-(A 1b O) m1b -R 2b -C(=O)-R 3b It is preferable that ] be substituted (joined). Also, Z 1a ,Z 1b In the case of a biphenyl ring, for example, the 3-position of the biphenyl ring (3-biphenylyl group) is bonded to the 9-position of the fluorene ring, and a group [-O-(A] is attached to the 6-position (in a 3,6 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 ] be substituted (joined).

[0052] Z 1a and Z 1bIn this, the arene ring is an unsubstituted arene ring, i.e., the 9th position of the fluorene 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 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 ](wherein, R hZ1 (represents a hydrocarbon group), group [-SR hZ1 ](wherein, R hZ1 Examples include hydrocarbon groups, acyl groups, nitro groups, cyano groups, and substituted amino groups (mono or disubstituted amino groups).

[0053] 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.

[0054] 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.

[0055] Base [-OR hZ1 ], base [-SR hZ1 In ], the hydrocarbon group RhZ1 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 ], the hydrocarbon group R hZ1 The types may be the same or different from each other.

[0056] 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.

[0057] Base [-SR hZ1 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.

[0058] 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 hZ1Examples include ]; more preferably 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 C such as aryl groups and methoxy groups 1-4 Examples include alkoxy groups. Substituents [-R Z1 Among these, hydrocarbon groups such as alkyl groups are preferred, and in particular, C groups such as methyl groups. 1-4 Alkyl alkyl groups are preferred.

[0059] 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 in stages below, an integer of 0 to 3, an integer of 0 to 2, 0 or 1, 0. 1a The 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 [ ] may be different from each other, but it is preferable that they be the same.

[0060] 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. 2-3Alkylene groups, particularly ethylene groups, are preferred.

[0061] 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.

[0062] 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.

[0063] In this invention, even if m1a and m1b are 0, heat resistance (or stability) can be effectively improved.

[0064] 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.

[0065] R 2a and R 2bThe C group can be any alkylene group (linear or branched alkylene group) with 3 or more carbon atoms, such as trimethylene, propylene, propyridene, tetramethylene, pentamethylene, hexamethylene, etc. 3-10 Examples include alkylene groups, preferably in the following steps, C 3-8 Alkylene group, C 3-6 Alkylene group, C 3-5 Alkylene group, C 3-4 It is a C3 alkylene group. Also, R 2a and R 2b The alkylene group may be linear or branched, but a linear alkylene group appears to be preferred. 2a and R 2b If the number of carbon atoms in the alkylene group is too large, the heat resistance and refractive index may decrease.

[0066] On the other hand, as specifically described in Patent Document 1, if the alkylene group has fewer than 3 carbon atoms, for example, R 2a and R 2b However, if it is a methylene group with 1 carbon atom, under high temperature conditions and / or alkaline conditions, the hydrogen at the α position of the carbonyl group is easily removed (the compound is easily decomposed), especially when m1a and m1b are 0 (R 2a and R 2b The methylene group of Z 1a and Z 1b (and when bonded via ether bonds), among them Z 1a and Z 1b When the ring is a condensed polycyclic arene ring such as a naphthalene ring, the heat resistance (stability) tends to decrease significantly. Also, R 2a and R 2b However, when the ethylene group has 2 carbon atoms, the reaction does not proceed easily, and productivity is significantly reduced. Therefore, in this invention, R 2a and R 2b This also includes methods to improve heat resistance (stability) and / or productivity by using an alkylene group with three or more carbon atoms.

[0067] R 3a and R3b is a hydroxyl group, group [-OR h3 ](wherein, R h3 (This may represent a hydrocarbon group) or a halogen atom.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] Note, R 3a and / or R 3bIf 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).

[0072] Also, R 3a and / or R 3b If 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.

[0073] Preferred R 3a and R 3b is a hydroxyl group or group [-OR h3 ] and more preferably a hydroxyl group. 3a and R 3b The types may be different from each other, but it is preferable that they be the same.

[0074] 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.

[0075] 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 constitutes a halogen atom, hydrocarbon group, and 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. m1a and m1b are 0, R 2a and R 2b C 3-10 Examples include compounds (or salts thereof) that have an alkylene group; Preferably, R 1 However, groups such as hydrocarbon groups or alkoxy groups [-OR h1 ], in particular hydrocarbon groups such as alkyl groups and aryl groups, where k1 is an integer from 0 to 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 forms a hydrocarbon group or an alkoxy group, etc. [-OR hZ1 ], in particular hydrocarbon groups such as alkyl groups and aryl groups, and substituents [-R Z1 The number of ] is an independent integer between 0 and 2. m1a and m1b are between 0 and 6. R 2a and R 2b Independently, linear C 3-5 C groups such as alkylene groups 3-5 Examples include compounds (or salts thereof) that have an alkylene group; More preferably, R1 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 a benzene ring or a naphthalene ring, particularly a naphthalene ring. Z 1a and Z 1b substituents [-R Z1 ] became independent, C 1-4 It is an alkyl group and has a substituent [-R Z1 The number of ] is independently either 0 or 1, m1a and m1b are 0, R 2a and R 2b Independently, linear C 3-4 C groups such as alkylene groups 3-4 It is an alkylene group, R 3a and R 3b The hydroxyl group or the group [-OR h3 ], in particular compounds (or salts thereof) that have a hydroxyl group, are examples.

[0076] Examples of specific compounds (or salts thereof) represented by formula (1) include 9,9-bis(carboxyC) 3-8 9,9-bis(carboxyC) such as alkyloxyaryl fluorene 3-10 Examples of alkyloxy-aryl)fluorenes and their derivatives include esters such as alkyl esters, acid halides such as acid chlorides, and salts such as metal salts. Examples of the compound (1) include 9,9-bis[4-(3-carboxypropyloxy)-phenyl]fluorene, 9,9-bis[6-(3-carboxypropyloxy)-2-naphthyl]fluorene, 9,9-bis[5-(3-carboxypropyloxy)-1-naphthyl]fluorene, etc. 3-6 Alkyloxy-aryl)fluorene, preferably in the following steps: 9,9-bis(carboxyC) 3-5 Alkyloxy-aryl)fluorene, 9,9-bis(carboxyC)3-4 Examples include alkyloxy-aryl)fluorene, 9,9-bis(carboxyC3alkyloxy-aryl)fluorene, and their derivatives, such as esters like alkyl esters, acid halides like acid chlorides, and salts like metal salts.

[0077] (Properties of the compound represented by formula (1)) Compound (1) (or its salt) may be in crystalline form.

[0078] Compound (1) (or its salt) has excellent heat resistance, and the 1% weight loss temperature may be, for example, around 50 to 150°C, preferably in stages as follows: 80 to 140°C, 90 to 130°C, and 100 to 120°C. The 5% weight loss temperature may be, for example, 130°C or higher, specifically around 150 to 250°C, preferably in stages as follows: 180 to 230°C, 190 to 220°C, and 195 to 215°C. The 10% weight loss temperature may be, for example, 200°C or higher, specifically around 250 to 350°C, preferably in stages as follows: 270 to 340°C, 280 to 330°C, 290 to 320°C, and 295 to 315°C.

[0079] 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.

[0080] Furthermore, compound (1) (or its salt) has a high refractive index, and its refractive index nD may be, for example, about 1.62 to 1.66 at a temperature of 25°C and a wavelength of 589 nm, and preferably in the following increments: 1.625 to 1.65, 1.63 to 1.645, and 1.635 to 1.64.

[0081] In this specification and in the claims, the refractive index can be measured by the method described in the examples below.

[0082] Compound (1) (or its salt) exhibits excellent solubility in solvents, and can satisfy a good balance of high heat resistance, high refractive index, and solubility. Compound (1) (or its salt) can relatively easily form a solution (or liquid composition), and such solvents include, for example, hydrocarbons, specifically aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and chloroform; alcohols such as methanol, ethanol, n-propanol, and benzyl alcohol; ethers, specifically dialkyl ethers such as diethyl ether and diisopropyl ether, cyclic ethers such as tetrahydrofuran and 1,4-dioxane, aromatic ethers such as anisole; and glycoglycers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME), ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. Examples include: ethers; ketones, specifically chain ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and 2-heptanone; cyclic ketones such as cyclohexanone and cyclopentanone; esters, specifically acetate esters such as ethyl acetate; lactate esters such as methyl lactate, ethyl lactate, and butyl lactate; lactones such as γ-butyrolactone; ether esters, specifically alkylene glycol monoalkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate (PGMEA); alkoxycarboxylic acid esters such as ethyl 3-ethoxypropionate; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone (NMP); and sulfoxides such as dimethyl sulfoxide.

[0083] These solvents may be used individually or in combination of two or more. Of these solvents, halogenated hydrocarbons, glycol ethers, ketones, esters such as lactic acid esters, ether esters, and amides are preferred; more preferably chlorinated hydrocarbons, glycol ethers such as alkylene glycol (mono or di)alkyl ethers, ketones such as cyclic ketones, ether esters such as alkylene glycol monoalkyl ether acetate, and amides; in particular, chlorinated aliphatic hydrocarbons such as chloroform, and C such as PGME are preferred. 2-4 Alkylene glycol mono C 1-4 C such as alkyl ethers, cyclopentanone, and cyclohexanone 4-8 Cyclic ketones, PGMEA, etc. 2-4 Alkylene glycol mono C 1-4 Alkyl ether acetates and cyclic amides such as NMP are preferred.

[0084] In a composition (solution or liquid composition) containing compound (1) (or a salt thereof) and a solvent, the proportion of compound (1) (or a salt thereof) is, for example, 1 to 50% by mass, preferably 3 to 40% by mass, more preferably 5 to 35% by mass, and particularly 10 to 25% by mass, relative to the entire composition. The composition (solution or liquid composition) containing compound (1) (or a salt thereof) and a solvent may be, for example, a reaction solution for solution polymerization.

[0085] In this specification and in the claims, solvent solubility can be measured by the method described in the examples below.

[0086] (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 reaction step of reacting (nucleophilic reaction or dehalogenation reaction) a compound represented by the following formula (2) with a compound represented by the following formula (3a) (or a salt thereof) and a compound represented by the following formula (3b) (or a salt thereof) [or a haloalkanoic acid (or a salt thereof) or a derivative thereof].

[0087] In this specification and in the claims, the compound represented by formula (2) may 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)."

[0088] [ka]

[0089] [In the formula, X 1a and X 1b These independently represent halogen atoms, R 1 , k1, Z 1a and Z 1b , 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.]

[0090] Compound (2) is a compound corresponding to a preferred embodiment of compound (1), for example, a compound having phenolic hydroxyl groups where m1a and m1b are 0, i.e., 9,9-bis(hydroxyC 6-12 Examples of 9,9-bis(hydroxyaryl)fluorenes include aryl)fluorenes, specifically 9,9-bis(hydroxyphenyl)fluorene, 9,9-bis(alkyl-hydroxyphenyl)fluorene, 9,9-bis(aryl-hydroxyphenyl)fluorene, and 9,9-bis(hydroxynaphthyl)fluorene.

[0091] Examples of 9,9-bis(hydroxyphenyl)fluorene include 9,9-bis[4-hydroxyphenyl]fluorene.

[0092] Examples of 9,9-bis(alkyl-hydroxyphenyl)fluorene include 9,9-bis[3-methyl-4-hydroxy-phenyl]fluorene, 9,9-bis[3,5-dimethyl-4-hydroxy-phenyl]fluorene, and other 9,9-bis(mono or diC) compounds. 1-4 Examples include alkyl-hydroxyphenyl (fluorene).

[0093] Examples of 9,9-bis(aryl-hydroxyphenyl)fluorene include 9,9-bis[3-phenyl-4-hydroxy-phenyl]fluorene and other 9,9-bis(C 6-10 Examples include aryl-hydroxyphenyl ()fluorene.

[0094] 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.

[0095] In equations (3a) and (3b) above, X 1a and X 1b Examples of halogen atoms include iodine, bromine, and chlorine atoms, with bromine being preferred.

[0096] Compound (3a)(3b) (or its salt) [or haloalkanoic acid (or its salt) or its derivative] may be a halogenated carboxylic acid (or its salt) or derivative having 4 or more carbon atoms, preferably a compound corresponding to a preferred embodiment of compound (1), for example, a haloalkanoic acid, specifically 2-bromobutyric acid, 3-bromobutyric acid, 4-bromobutyric acid, etc. 4-11 Bromoalkanoic acid, these C 4-11 C corresponding to bromoalkanoic acid 4-11 Examples include chloroalkanoic acids (alkanoic acids in which a chlorine atom is bonded in place of a bromine atom), and their derivatives, such as esters such as alkyl esters, acid halides such as acid chlorides, and salts such as metal salts. Preferred compounds (3a)(3b) are C 4-6Bromoalkanoic acid, C 4-6 C such as chloroalkanoic acid 4-6 Haloalkanoic acid or derivatives thereof, more preferably C 4-5 Bromoalkanoic acid, C 4-5 C such as chloroalkanoic acid 4-5 Haloalkanoic acid or esters thereof, more preferably linear C 4-5 Bromoalkanoic acid, linear C 4-5 Linear carbon such as chloroalkanoates 4-5 Haloalkanoates or their alkyl esters, in particular linear C2, such as ethyl 4-bromobutyrate. 4-5 Bromoalkanoic acid or its C 1-4 Alkyl esters are preferred. These compounds (3a)(3b) (or their salts) are relatively inexpensive, easy to handle (or safe), and can effectively improve productivity (or mass production).

[0097] It is preferable that compound (3a) (or its salt) and compound (3b) (or its salt) have the same chemical structure. Commercially available products can be used for compounds (3a) and (3b) (or their salts).

[0098] The ratio of compound (2) to the total amount of compounds (3a)(3b) (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.

[0099] The reaction between compound (2) and compounds (3a)(3b) (or their salts) 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.

[0100] Examples of inorganic bases include metal hydroxides, metal hydrides, metal carbonates, and metal bicarbonates.

[0101] 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.

[0102] Examples of metal hydrides include alkali metal hydrides such as sodium hydride and potassium hydride, and alkaline earth metal hydrides.

[0103] Examples of metal carbonates include alkali metal carbonates such as lithium carbonate, potassium carbonate, and sodium carbonate, as well as alkaline earth metal carbonates.

[0104] Examples of metal bicarbonates include alkali metal bicarbonates such as potassium bicarbonate and sodium bicarbonate, and alkaline earth metal bicarbonates.

[0105] Examples of organic bases include amines, metal carboxylate salts, quaternary ammonium salts, and quaternary phosphonium salts.

[0106] Examples of amines include aliphatic amines, aromatic amines, and heterocyclic amines.

[0107] 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.

[0108] Examples of aromatic amines include primary to tertiary aromatic amines, such as aromatic tertiary amines like N,N-dimethylaniline.

[0109] 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.

[0110] Examples of carboxylate metal salts include alkali metal acetates such as sodium acetate, and alkaline earth metal acetates such as calcium acetate.

[0111] Examples of quaternary ammonium salts include tetraalkylammonium halides such as tetraethylammonium chloride, and benzyltrialkylammonium halides such as benzyltrimethylammonium chloride.

[0112] Examples of quaternary phosphonium salts include benzyltriphenylphosphonium chloride.

[0113] 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. Compared to alkali metal hydroxides, alkali metal carbonates have relatively low alkalinity (basicity), offer excellent handling (or safety), and can effectively improve productivity (or mass production).

[0114] 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 (2), preferably in stages, 1 to 5 moles, 1.5 to 4 moles, and 2 to 3 moles.

[0115] The reaction between compound (2) and compounds (3a)(3b) (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.

[0116] 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.

[0117] Examples of amides include N-methylformamide and N,N-dimethylformamide (DMF), which are N-mono or diC. 1-4 Alkylformamides; N-methylacetamide, N,N-dimethylacetamide, and other N-mono or di-C formsamides. 1-4 Examples include alkylacetamides.

[0118] Examples of nitriles include acetonitrile and propionitrile.

[0119] Examples of sulfur compounds include sulfoxides such as dimethyl sulfoxide; and sulfones, specifically cyclic sulfones such as sulfolane.

[0120] 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.

[0121] Examples of hydrocarbons include aliphatic hydrocarbons such as pentane, hexane, heptane, and cyclohexane; and aromatic hydrocarbons such as toluene and xylene.

[0122] These solvents may be used individually or in combination of two or more. Furthermore, amides such as DMF are preferred as solvents.

[0123] 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 400 parts by mass, per 100 parts by mass of the total amount of compound (2) and compound (3a)(3b) (or their salts).

[0124] The reaction between compound (2) and compounds (3a)(3b) (or their salts) may be carried out with stirring, in air, or under an inert gas atmosphere, such as a noble gas such as nitrogen, helium, or argon, preferably under an inert gas atmosphere such as nitrogen. The reaction between compound (2) and compounds (3a)(3b) (or their salts) may be carried out under reduced pressure, atmospheric pressure, or pressurized pressure. The reaction temperature may be, for example, around 0 to 250°C, preferably in stages, 30 to 150°C, 50 to 120°C, 60 to 100°C, 70 to 90°C, and 75 to 85°C. In this invention, the reaction proceeds efficiently even at relatively low temperatures, for example, at 90°C or below, preferably 50 to 85°C, thus effectively improving productivity. The reaction may also be carried out while refluxing the solvent. The reaction time may be, for example, 0.5 to 72 hours, and preferably in stages, 48 ​​hours or less, 24 hours or less, 18 hours or less, 12 hours or less, 6 hours or less, and 1 to 3 hours. In this invention, the reaction proceeds efficiently even in a relatively short time, and productivity can be effectively improved.

[0125] 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.

[0126] (Hydrolysis process) Furthermore, in the reaction process, R 3a and R 3b is based on [-OR h3 When compound (1) is prepared, if necessary, the obtained R 3a and R 3b is based on [-OR h3 Compound (1), which is ], undergoes a hydrolysis (saponification) step by conventional methods, R 3a and R 3b Compound (1) (or a salt thereof) in which is a hydroxyl group may be prepared. In this way, after the reaction step, a hydrolysis (or saponification) step is performed, 3a and R 3b When compound (1) (or a salt thereof) in which is a hydroxyl group is prepared, the formation of by-products can be suppressed and productivity can be effectively improved. In addition, in the reaction step, compound (2) and R 3a and R 3b By reacting with compounds (3a)(3b) (or their salts) that have a hydroxyl group, R is directly (without hydrolysis) obtained. 3a and R 3b When attempting to prepare compound (1) (or a salt thereof) in which is a hydroxyl group, compound (2) and R are produced as byproducts. 3a and R 3b It appears that esters are easily formed with compounds (3a)(3b) (or their salts) that have a hydroxyl group, which tends to reduce purity and yield.

[0127] Hydrolysis (or saponification) may be carried out without separating and purifying the reaction mixture obtained after the reaction of compound (2) and compounds (3a) and (3b) described above, or after separating and purifying it. For example, the obtained reaction mixture may be washed with water, extracted with an organic solvent (extraction solvent), and the resulting extract (organic solvent layer) may be subjected to the hydrolysis (or saponification) reaction. Examples of extraction solvents include the organic solvents (reaction solvents) exemplified in the section on the reaction of compound (2) and compounds (3a) and (3b) (or their salts) described above, ketones, specifically chain ketones such as methyl isobutyl ketone (MIBK) (or dialkyl ketones).

[0128] Hydrolysis (or saponification) reactions usually occur in the presence of water. The proportion of water is R 3a and R 3b is based on [-OR h3 For 1 mole of compound (1) [or 1 mole of compound (2) used in the reaction between compound (2) and compounds (3a) and (3b) described above], the amount of water is, for example, 2 to 20 moles, preferably in stages, 3 to 15 moles, 4 to 10 moles, 5 to 7 moles, and 5.5 to 6.5 moles. The water may be added in the form of an aqueous solution of the basic compound described later.

[0129] The hydrolysis (or saponification) reaction may be carried out in the presence of a basic compound. Examples of basic compounds include those exemplified in the section on the reaction between compound (2) and compounds (3a)(3b) (or their salts) mentioned above. These basic compounds may be added in the form of an aqueous solution as needed. These basic compounds can be used alone or in combination of two or more. Preferred basic compounds are metal hydroxides, and more preferably alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Potassium hydroxide is particularly preferred because it has excellent solubility in organic solvents, does not easily cause heterogeneity in the reaction system, and allows the reaction to proceed efficiently. The proportion of basic compounds such as potassium hydroxide added during the hydrolysis (or saponification) reaction is R 3a and R 3b is based on [-OR h3For 1 mole of compound (1) [or 1 mole of compound (2) used in the reaction between compound (2) and compounds (3a) and (3b) as described above], the amount of potassium hydroxide used is, for example, 2 to 20 moles, preferably in stages, 3 to 15 moles, 4 to 10 moles, 5 to 9 moles, 6 to 8 moles, and 6.5 to 7.5 moles. When both sodium hydroxide and potassium hydroxide are used, the ratio may be, for example, the former / latter (molar ratio) = 10 / 90 to 70 / 30, preferably in stages, 20 / 80 to 50 / 50, 25 / 75 to 45 / 55, and 30 / 70 to 40 / 60. If the proportion of potassium hydroxide is too low, precipitation may occur as the reaction progresses, the reaction system may become heterogeneous, and the reaction may not proceed efficiently.

[0130] The hydrolysis (or saponification) reaction may be carried out with stirring, in air or under an inert gas atmosphere, such as nitrogen gas, helium, or argon, and preferably in air (atmosphere). The hydrolysis (or saponification) reaction may be carried out under reduced pressure, atmospheric pressure, or under increased pressure. The reaction temperature may be, for example, around 50 to 150°C, and preferably in stages, 80 to 140°C, 90 to 130°C, and 100 to 120°C. The reaction may also be carried out while refluxing the solvent. The reaction time may be, for example, around 1 to 24 hours, and preferably 6 to 18 hours.

[0131] 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, reprecipitation, column chromatography, or a combination thereof.

[0132] For example, the reaction mixture may be purified by adding an acid such as hydrochloric acid to precipitate it and filtering it, then dissolving the resulting filtrate with an ether such as THF or a ketone such as MIBK, washing it with water, and then purifying it by crystallization or reprecipitation. In crystallization or reprecipitation, the reaction mixture may be dissolved in an aromatic hydrocarbon such as toluene or xylene and mixed with an aliphatic hydrocarbon such as n-heptane as a poor solvent to crystallize or reprecipitation. Crystallization or reprecipitation may be carried out at room temperature or at low temperature (while cooling), for example, -10°C to 30°C, preferably -5°C to 20°C, more preferably 0 to 15°C, and particularly 5 to 10°C.

[0133] The production method of the present invention allows for the preparation of compound (1) (or its salt) in high yield and high purity, and offers excellent productivity. The yield of compound (1) (or its salt) may be, for example, about 70-100%, specifically about 75-98%, based on compound (2), and preferably in stages, 80% or more, 85% or more, and 90% or more. The yield is obtained in the reaction step R 3a and R 3b is based on [-OR h3 After preparing compound (1) which is ], the process is carried out through a hydrolysis (or saponification) step, R 3a and R 3b The yield may be the yield (total yield of the reaction and hydrolysis steps) when compound (1) (or a salt thereof) in which is a hydroxyl group is prepared.

[0134] The purity (LC purity) of compound (1) (or its salt) may be, for example, around 80 to 100 area%, and preferably, in stages, 85 area% or more, 90 area% or more, 95 area% or more, and 98 area% or more.

[0135] In this specification and in the claims, purity can be measured by the method described in the examples below.

[0136] [resin] The present invention includes resins that contain at least the above compound (1) (or a salt thereof) or a derivative thereof as a raw material (precursor component or intermediate) or polymerization component (or monomer component).

[0137] The resin of the present invention may be a curable resin (thermo-curable or photo-curable resin) or a thermoplastic resin.

[0138] 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.

[0139] 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.

[0140] 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.

[0141] 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.

[0142] [Molded body] The present invention also includes molded articles comprising at least the compound (1) (or a salt thereof) or a derivative thereof, and / or a resin (first resin) made from the compound (1). If the molded article comprises the compound (1) (or a salt thereof) or a derivative thereof, the compound (1) (or a salt thereof) or a derivative thereof may be blended as a resin additive to the second resin (it may also be a molded article of a resin composition comprising the compound (1) (or a salt thereof) or a derivative thereof and the second resin). The second resin may be a conventional resin, such as a (thermal or photo) curable resin or a thermoplastic resin.

[0143] 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.

[0144] The method for manufacturing the molded body is not particularly limited, and may be a conventional molding method according to the type of resin and the like. For example, when the first and / or second resin is a thermoplastic resin, an injection molding method, an injection compression molding method, an extrusion molding method, a transfer molding method, a blow molding method, a pressure molding method, a casting molding method, etc. can be used to manufacture the molded body.

[0145] Also, the shape of the molded body is not particularly limited, and examples include one-dimensional structures such as linear, fibrous, and thread-like, two-dimensional structures such as film-like, sheet-like, and plate-like, lens-like such as concave or convex lens-like, rod-like, three-dimensional structures such as hollow (tubular), etc.

[0146] Since the molded body has excellent optical properties and heat resistance in a balanced manner, it can be effectively used as optical members such as optical films (optical sheets) and optical lenses.

[0147] In addition, the film can be manufactured by forming (or molding) the resin using a conventional film-forming method, such as a casting method (solvent casting method), a melt extrusion method, a calender method, etc.

[0148] The average thickness of the film can be selected from the range of about 1 to 1000 μm according to the application, for example, 1 to 200 μm, preferably 5 to 150 μm, more preferably 10 to 120 μm.

[0149] The film may be an unstretched or stretched film, and even if it is a stretched film, low birefringence can be maintained. Such a stretched film may be either a uniaxially stretched film or a biaxially stretched film.

[0150] 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.

[0151] 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.

[0152] 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]

[0153] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. Details of the evaluation items are shown below.

[0154] [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.

[0155] (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 %].

[0156] (Refractive index) The refractive index was measured using a refractometer (ATAGO RX-7000i) at a temperature of 25°C and a wavelength of 589 nm (D-line). The refractive index was calculated by dissolving the sample in N-methyl-2-pyrrolidone (NMP), preparing multiple solutions with different concentrations, and measuring the refractive index of the resulting solutions. A calibration curve (approximate straight line) was then created, and the concentration was extrapolated to 100% by mass.

[0157] (weight loss temperature) Thermogravimetric analysis - Using a differential thermal analyzer (TG-DTA) (TG / DTA6200, manufactured by SII Nanotechnology Co., Ltd.), temperatures were measured in a nitrogen atmosphere under a heating rate of 10°C / min within a temperature range of 30 to 520°C. The temperatures were determined when the sample mass decreased by 1%, 5%, and 10%, respectively.

[0158] (Solvent solubility) The sample was added to a solvent to the specified concentration, its solubility was confirmed, and it was evaluated according to the following criteria.

[0159] ◎...Dissolved within 1 hour at room temperature (around 25℃) ○...Dissolved within 3 hours, but more than 1 hour, at room temperature (around 25°C). △...It did not dissolve within 3 hours at room temperature (around 25°C), but dissolved within 1 hour at 50°C. ×...It did not dissolve within 3 hours at room temperature (around 25°C) and did not dissolve within 1 hour at 50°C.

[0160] [Example 1]

[0161] [ka]

[0162] Under a nitrogen atmosphere, 22.5 g (50 mmol) of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF), 25.4 g (130 mmol, 2.6 equivalents (eq)) of ethyl 4-bromobutyrate, and 140 g of N,N-dimethylformamide (DMF) were added to a 1 L reaction vessel and stirred. Then, 34.6 g (250 mmol, 5.0 equivalents (eq)) of potassium carbonate was added, and the mixture was stirred at 80 °C for 2 hours. After confirming the disappearance of the starting material BNF, the mixture was cooled to about 40 °C, and 168 g of methyl isobutyl ketone (MIBK) was added. 280 g of ion-exchanged water was added to the resulting mixture to remove the aqueous layer, and the operation of extracting (recovering) the organic layer was repeated twice.

[0163] 10 g (120 mmol, 2.4 equivalents (eq)) of a 48% by mass aqueous sodium hydroxide solution and 15.2 g (230 mmol, 4.6 equivalents (eq)) of potassium hydroxide (solid, purity 85% by mass) were added to the obtained organic layer, and the mixture was refluxed at 110 °C under an air atmosphere for 12 hours. After completion of the reaction, tetrahydrofuran (THF) and MIBK were added, and then 31.6 g (130 mmol) of 15% by mass hydrochloric acid was added to adjust the pH to 1. Then, the precipitated crystals were collected by filtration. The obtained crystals were dissolved in THF and MIBK. Ion-exchanged water was added to the obtained solution for washing with water, and the operation of recovering the organic layer was repeated three times. After concentrating the obtained organic layer to remove the organic solvent, 45 g of toluene was added and heated to dissolve, making a uniform solution. The obtained solution was slowly dropped into n-heptane cooled to 5 - 10 °C for crystallization and isolation, and 28.8 g (yield 93%, LC purity 98 area%) of 9,9-bis[6-(3-carboxypropyloxy)-2-naphthyl]fluorene (hereinafter also referred to as BNF dibutylcarboxylic acid), the target product, could be obtained in a high yield and high purity.

[0164] The 1 results of the 1H-NMR spectrum of the obtained BNF dibutylcarboxylic acid are shown below.

[0165] 1H-NMR (CDCl3, 300MHz): δ(ppm)=2.1(m,4H), 2.5-2.6(t,4H), 4.1(t,4H), 7.0(m,4H), 7.2-7.3(m,14H), 7.3-7.4(m,2H).

[0166] The elemental refractive index nD (D line, 25°C) of the obtained BNF-dibutylcarboxylic acid was 1.6386, indicating high refraction. Furthermore, the 1% weight loss temperature of BNF-dibutylcarboxylic acid was 109°C, the 5% weight loss temperature was 206°C, and the 10% weight loss temperature was 307°C, demonstrating high heat resistance.

[0167] The results of the solvent solubility test of BNF dibutylcarboxylic acid are shown in Table 1 below. In Table 1, "PGMEA" means propylene glycol monomethyl ether acetate, "PGME" means propylene glycol monomethyl ether, and "NMP" means N-methyl-2-pyrrolidone.

[0168] [Table 1]

[0169] As is clear from the results in Table 1, BNF dibutylcarboxylic acid exhibited excellent solvent solubility. Its solubility in PGMEA, cyclohexanone, cyclopentanone, PGME, NMP, and chloroform was particularly excellent, making it suitable as a high refractive index negative-type resist material.

[0170] Furthermore, solutions with a result of △ in Table 1 showed precipitation after being stored at room temperature (around 25°C) for several days.

[0171] [Comparative Example 1] 9,9-bis[6-(carboxymethoxy)-2-naphthyl]fluorene, represented by the following formula, was prepared in accordance with Example 1 of Japanese Patent Publication No. 2009-256332. Decomposition was observed under high temperature and alkaline conditions, indicating low heat resistance.

[0172] [ka]

[0173] [Comparative Example 2] In Comparative Example 2, we attempted to prepare 9,9-bis[6-(2-carboxyethoxy)-2-naphthyl]fluorene, represented by the following formula, in the same manner as in Example 1, except that bromopropionic acid was used instead of ethyl bromobutyrate, and the reaction temperature was changed to 110°C and the reaction time to 72 hours. After the reaction was completed (after 72 hours), the conversion rate was checked by HPLC and found to be 0%, indicating extremely low reactivity, and almost all of the starting material was recovered (most of the starting material was unreacted). In Comparative Example 2, unlike in Example 1, the reaction did not proceed, which was presumed to be due to the difference in the charge distribution between the bromopropionic acid skeleton and the bromobutyric acid skeleton.

[0174] [ka] [Industrial applicability]

[0175] 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, or as an additive (or resin additive) such as a refractive index improver, heat resistance improver, or curing agent. Examples of curing agents include those for epoxy resins. It can also be effectively used as a resist material, such as a negative (curable) or positive resist material. For example, in a negative (curable) resist material, it can be used in the form of a crosslinking agent for alkali-available resins, and in a positive resist material, R 3a and R 3b It may also be used in a form such as a branched alkoxy group, in combination with a photoacid generator.

[0176] The resin of the present invention exhibits high heat resistance and can be used in a variety of applications, such as coating agents or coating films, specifically paints, inks, protective films for electronic devices and liquid crystal components; adhesives and sealants; resin fillers; electrical and electronic materials or electrical and electronic 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.

[0177] Furthermore, the resin of the present invention exhibits excellent optical properties such as high refractive index as well as high heat resistance, making it effectively usable as an optical component.

[0178] 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.

[0179] 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.

[0180] 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.

[0181] Typical devices or equipment that incorporate 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 dashcams and backup cameras (rear cameras).

Claims

1. A method for producing 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. 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 exhibit a C3-10 alkylene group. R ３ａ and R ３ｂ each independently represents a hydroxyl group or an alkoxy group.] A method comprising a reaction step of reacting a compound represented by the following formula (2) with a compound represented by the following formula (3a) and a compound represented by the following formula (3b). 【Chemistry 2】 [In the formula, X1a and X1b independently represent halogen atoms.] In formulas (3a) and (3b), R 3a and R 3b represent alkoxy groups. R1, k1, Z1a and Z1b, A1a and A1b, m1a and m1b, R2a and R2b are the same as in formula (1) above.

2. In the above formula (1), R １ is a halogen atom, hydrocarbon group, group [-OR ｈ１ ] (wherein, R ｈ１ k1 is an integer from 0 to 4, and is an acyl group, nitro group, cyano group, or substituted amino group, where k1 is an integer from 0 to 4. Z １ａ and Z １ｂ The arene rings are independently monocyclic or fused polycyclic arene rings. A method for producing the compound or a salt thereof according to claim 1, wherein m1a and m1b are 0.

3. In the above formula (1), R １ is a hydrocarbon group, and k1 is an integer from 0 to 2. Z １ａ and Z １ｂ The arene ring is independently a benzene ring or C １０－１４ It is a condensed polycyclic arene ring, m1a and m1b are 0, R ２ａ and R ２ｂ Independent linear C ３－５ A method for producing the compound according to claim 1 or 2, which is an alkylene group, or a salt thereof.

4. A method for producing the compound or a salt thereof according to claim 1 or 2, wherein the 10% weight loss temperature is 200°C or higher.

5. A method for producing the compound or a salt thereof according to claim 1 or 2, wherein the reaction step involves a reaction temperature of 90°C or less and a reaction time of 18 hours or less.

6. The process further comprises a hydrolysis step of hydrolyzing the compound represented by formula (1) obtained in the reaction step, wherein R 3a and R 3b are alkoxy groups, A method for producing the compound according to claim 1 or 2 or a salt thereof, wherein R 3a and R 3b in formula (1) are hydroxyl groups.

7. A method for producing the compound or salt of the compound represented by formula (1) or the salt thereof according to claim 1 or 2, wherein the yield of the obtained compound or salt of the compound or salt of the compound represented by formula (1) is 80% or more and the LC purity is 80 area% or more.

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