Fluorene compound, and method for producing the same and use thereof

Abstract

To provide a method capable of easily or efficiently producing a fluorene compound having a 9,9-bisarylfluorene skeleton and having two amino groups at 1- to 8-positions of the fluorene skeleton, a novel fluorene compound for use in the method (a reaction intermediate or a precursor), and a use of the fluorene compound obtained by the method.SOLUTION: For example, there are provided a method for producing a fluorene compound having two amino groups at 1- to 8-positions or a salt thereof, the method including a hydrolysis step of hydrolyzing a fluorene compound having two imino groups at 1- to 8-positions as shown in the following reaction formula.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to fluorene compounds having specific chemical structures, as well as methods for producing and using the same. [Background technology]

[0002] Compounds having a 9,9-bisarylfluorene skeleton (a cardo skeleton or a cardo structure) have various excellent properties, such as optical properties, and are used as resin raw materials (or polymerization components), etc. For example, it is known that diamine compounds having a 9,9-bisarylfluorene skeleton can be used as resin raw materials for polyamides, polyimides, etc.

[0003] Japanese Patent Laid-Open Publication No. 62-149650 (Patent Document 1) discloses a method for producing aromatic bisanilines, and in the examples it is described that fluorenone and 2-fluoroaniline are reacted by a predetermined method to produce 9,9-bis(4-aminophenyl)fluorene.

[0004] Furthermore, Japanese Patent Application Laid-Open Publication No. 2011-84502 (Patent Document 2) discloses a method for producing 9,9-bis(3-fluoro-4-aminophenyl)fluorene by reacting fluorenone with 2-fluoroaniline in a predetermined manner, and describes that the resulting diamine compound is effective as a resin raw material for polyamides and polyimides.

[0005] Furthermore, in Figure 3 of Hasegawa Masatoshi, "Low Thermal Expansion and Low Water Absorption Polyimide for Flexible Circuit Boards," Journal of the Japan Institute of Electronics Packaging, vol. 16, No. 5 (2013), pp. 399-404 (Non-Patent Document 1), the following diamine compound having a cardo skeleton is exemplified as a raw material for low water absorption polyimide.

[0006] [ka]

[0007] In addition, in the specification of Chinese Patent Application Publication No. 114105815 (Patent Document 3), an organic compound having a symmetric structure used in organic EL (electroluminescence) is disclosed, and in Example 3 of this document, the following reaction formula is described.

[0008]

Chemical formula

Prior art documents

Patent documents

[0009]

Patent Document 1

Patent Document 2

Patent Document 3

Non-patent documents

[0010]

Non-patent Document 1

Summary of the invention

Problems to be solved by the invention

[0011] However, in the compounds having a 9,9-bisarylfluorene skeleton described in Patent Documents 1 to 2 and Non-patent Document 1, sufficient properties may not be obtained depending on the use and the like.

[0012] In addition, in Example 3 of Patent Document 3, it is described that a compound having an amino group at the 2,7-positions of a 9,9-bisphenylfluorene skeleton was used, but no specific description is given about its preparation method.

[0013] Therefore, an object of the present disclosure is to provide a method for easily or efficiently producing a fluorene compound (or a diamine compound or a salt thereof) having a 9,9-bisarylfluorene skeleton and two amino groups at the 1- to 8-positions of the fluorene skeleton (one amino group at the 1- to 4-positions and one amino group at the 5- to 8-positions), a novel fluorene compound (reaction intermediate or precursor) to be used in the method, and uses of the fluorene compound obtained by the method. [Means for solving the problem]

[0014] As a result of intensive research to achieve the above object, the present inventors have found that a specific fluorene compound (a diamine compound having a 9,9-bisarylfluorene skeleton) can be easily or efficiently prepared by hydrolyzing a fluorene compound having a specific chemical structure, and have completed the present disclosure. That is, the present disclosure may include the following aspects.

[0015] Aspect [1]: A method for producing a fluorene compound represented by the following formula (1) or a salt thereof, comprising a hydrolysis step of hydrolyzing a fluorene compound represented by the following formula (2).

[0016] [ka]

[0017] [In the formula, R 1a and R 1b each independently represents a substituent; m1a and m1b each independently represents an integer of 0 to 3; Z 1a and Z 1b each independently represents an arene ring, R 2a and R 2b are independently a hydrocarbon group, a halogen atom, a group [-SR h ](wherein, R h represents a hydrocarbon group; acyl group or cyano group; m2a and m2b each independently represent an integer of 0 or more; Z2a and Z 2b each independently represents a benzene ring or a naphthalene ring, R 3a and R 3b each independently represents a substituent; m3a and m3b each independently represent an integer of 0 or more; Z 3a and Z 3b each independently represents a benzene ring or a naphthalene ring, R 4a and R 4b each independently represents a substituent, and m4a and m4b each independently represent an integer of 0 or more.

[0018] [ka]

[0019] (In the formula, R 1a and R 1b , m1a and m1b, Z 1a and Z 1b , R 2a and R 2b , and m2a and m2b are the same as in formula (2).

[0020] Aspect [2]: In the formulas (1) and (2), R 1a and R 1b each independently represents a hydrocarbon group; m1a and m1b each independently represent an integer of 0 to 2; Z 1a and Z 1b independently C 6-14 represents an arene ring, R 2a and R 2b are independently a hydrocarbon group or a halogen atom, and m2a and m2b are independently an integer of 0 to 2.

[0021] Aspect [3]: In the formulas (1) and (2), R 1a and R 1beach independently represents an alkyl group; m1a and m1b each independently represent 0 or 1; Z 1a and Z 1b But independently C 6-12 represents an arene ring, R 2a and R 2b independently represent an alkyl group or a fluorine atom, and m2a and m2b independently represent 0 or 1.

[0022] Aspect [4]: ​​A fluorene compound represented by formula (2) according to any one of aspects [1] to [3].

[0023] Aspect [5]: A method for producing a fluorene compound represented by formula (2) according to any one of aspects [1] to [3], comprising a coupling step of coupling a fluorene compound represented by formula (3) below with an imine compound represented by formula (4a) below and an imine compound represented by formula (4b) below.

[0024] [ka]

[0025] (In the formula, X 1a and X 1b each independently represents a halogen atom, R 1a and R 1b , m1a and m1b, Z 1a and Z 1b , R 2a and R 2b , and m2a and m2b are the same as in formula (2).

[0026] [ka]

[0027] (In the formula, Z 2a and Z 2b , R 3a and R3b , m3a and m3b, Z 3a and Z 3b , R 4a and R 4b , and m4a and m4b are the same as in formula (2).

[0028] Aspect [6]: A resin containing the fluorene compound represented by formula (1) according to any one of aspects [1] to [3] or a salt thereof as a polymerization component.

[0029] Aspect [7]: The resin according to aspect [6], which is a polyimide-based resin.

[0030] Aspect [8]: A molded article comprising the resin according to aspect [6] or [7].

[0031] Aspect [9]: The molded article according to aspect [8], which is a circuit board.

[0032] In addition, the present disclosure may achieve the following secondary objectives (solve secondary problems).

[0033] That is, another object of the present disclosure is to provide a resin having excellent heat resistance, as well as a method for producing the same and uses thereof.

[0034] It is still another object of the present disclosure to provide a resin capable of forming a freestanding or self-supporting film, as well as a method for producing the same and uses thereof.

[0035] In this specification and claims, the number of carbon atoms in a substituent is represented by C1, C6, C 10 For example, an alkyl group with 1 carbon atom is represented as a "C1 alkyl group," and an aryl group with 6 to 10 carbon atoms is represented as a "C 6-10 It is sometimes referred to as an "aryl group".

[0036] In the present specification and claims, "independently" means that two components are independent components, and ring Z 1a and Z 1b In this case, the ring Z 1aand Ring Z 1b and do not necessarily have to be the same arene ring, but may be different arene rings.

[0037] In this specification and claims, a numerical range indicated as "X to Y" may include the numerical values ​​X and Y. [Effects of the Invention]

[0038] According to the present disclosure, it is possible to provide a method for easily or efficiently producing a fluorene compound (or a diamine compound) having a 9,9-bisarylfluorene skeleton and two amino groups at the 1- to 8-positions of the fluorene skeleton (one amino group at the 1- to 4-positions and one amino group at the 5- to 8-positions), a novel fluorene compound (reaction intermediate or precursor) to be used in the method, and uses of the fluorene compound obtained by the method. DETAILED DESCRIPTION OF THE INVENTION

[0039] The present disclosure encompasses a method for producing a fluorene compound represented by the following formula (1) [hereinafter also referred to as fluorene compound (1) or diamine compound (1)] or a salt thereof, which method includes a hydrolysis step of hydrolyzing a fluorene compound represented by the following formula (2) [hereinafter also referred to as fluorene compound (2) or diimine compound (2)], and also encompasses the fluorene compound (2), which is a novel compound.

[0040] [ka]

[0041] [In the formula, R 1a and R 1b each independently represents a substituent; m1a and m1b each independently represents an integer of 0 to 3; Z 1a and Z 1b each independently represents an arene ring, R 2a and R 2bare independently a hydrocarbon group, a halogen atom, a group [-SR h ](wherein, R h represents a hydrocarbon group; acyl group or cyano group; m2a and m2b each independently represent an integer of 0 or more; Z 2a and Z 2b each independently represents a benzene ring or a naphthalene ring, R 3a and R 3b each independently represents a substituent; m3a and m3b each independently represent an integer of 0 or more; Z 3a and Z 3b each independently represents a benzene ring or a naphthalene ring, R 4a and R 4b each independently represents a substituent, and m4a and m4b each independently represent an integer of 0 or more.

[0042] [ka]

[0043] [In the formula, R 1a and R 1b , m1a and m1b, Z 1a and Z 1b , R 2a and R 2b and m2a and m2b are the same as those in the formula (2) above, including preferred embodiments.]

[0044] [Fluorene compounds (1) and (2)] In the formula (1), the two amino groups [-NH2] may be substituted at any one of the 1- to 4-positions and any one of the 5- to 8-positions of the fluorene skeleton, respectively. For example, they may be substituted at positions symmetrical on the paper, such as the 1,8-positions, 2,7-positions, 3,6-positions, or 4,5-positions, and are preferably substituted at the 2,7-positions.

[0045] In the formula (2), the imino group-containing group [—N═C(Z 2a (R3a ) m3a )(Z 3a (R 4a ) m4a )] and [-N=C(Z 2b (R 3b ) m3b )(Z 3b (R 4b ) m4b The substitution positions of each of the amino groups [—NH2] in the formula (1) correspond to the substitution positions of the two amino groups [—NH2] in the formula (1), and may be the same, including preferred embodiments.

[0046] In the formulas (1) and (2), R 1a or R 1b The substituent represented by R may be a non-reactive group or a non-polymerizable group. 1a or R 1b Examples of the substituent represented by the formula (I) include hydrocarbon groups such as alkyl groups and aryl groups, halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms, and cyano groups. Examples of the alkyl groups (linear or branched alkyl groups) include C groups such as methyl groups, ethyl groups, and t-butyl groups. 1-6 Examples of aryl groups include C alkyl groups such as phenyl groups. 6-10 When the number of substitutions m1a or m1b is 1 or more, preferred R 1a or R 1b Examples of the alkyl group include hydrocarbon groups such as alkyl groups, and more preferably straight-chain or branched-chain C groups such as methyl groups. 1-4 It is an alkyl group.

[0047] The substitution numbers m1a and m1b are each an integer of 0 to 3, and may be selected from integers of, for example, about 0 to 2, preferably 0 or 1, and more preferably 0. The substitution numbers m1a and m1b may be different from each other, but are preferably the same. When the substitution number m1a is 2 or more, the number of two or more groups R substituted on one of the benzene rings forming the fluorene ring is 2 or more. 1a The types of m may be the same or different from each other, and when m is 2 or more, two or more groups R substituted on one of the benzene rings forming the fluorene ring 1bWhen the number of substitutions m1a and / or m1b is 2 or more, the number of groups R substituted on one of the benzene rings forming the fluorene ring may be the same or different. 1a and / or 2 or more R 1b The types of groups R substituted on both benzene rings forming the fluorene ring may be the same or different. 1a and R 1b The types of groups R may be different from each other, but are preferably the same. 1a and R 1b The substitution position of is not particularly limited, and in the formula (1), it may be a position other than the substitution positions of the two amino groups [-NH2], and in the formula (2), it may be a position other than the substitution positions of the two imino group-containing groups.

[0048] Z 1a or Z 1b Examples of the arene ring (aromatic hydrocarbon ring) represented by the formula (I) include a monocyclic arene ring such as a benzene ring, a polycyclic arene ring, etc. Examples of the polycyclic arene ring include a fused polycyclic arene ring (fused polycyclic aromatic hydrocarbon ring), a ring-assembled arene ring (ring-assembled polycyclic aromatic hydrocarbon ring), etc.

[0049] The fused polycyclic arene ring includes, for example, fused bicyclic arene rings, fused tricyclic arene rings, and other fused bicyclic to tetracyclic arene rings. The fused bicyclic arene ring includes, for example, fused bicyclic C rings such as naphthalene rings and indene rings. 10-16 Examples of the fused tricyclic arene ring include fused tricyclic C arene rings such as anthracene rings and phenanthrene rings. 14-20 Preferred fused polycyclic arene rings include fused polycyclic C arene rings such as naphthalene rings. 10-14 It is an arene ring.

[0050] Examples of the ring-assembled arene ring include biarene rings such as biphenyl ring, phenylnaphthalene ring, and binaphthyl ring; and terarene rings such as terphenyl ring. Preferred ring-assembled arene rings include C12-18 It is a biarene ring.

[0051] In this specification and claims, the term "ring assembly arene ring" refers to two or more ring systems (arene ring systems) directly linked by single bonds or double bonds, and the number of bonds directly linking the rings is one less than the number of ring systems. For example, as described above, phenylnaphthalene rings and binaphthyl rings are classified as ring assembly arene rings even though they have a fused polycyclic arene ring skeleton, and are clearly distinguished from "fused polycyclic arene rings" such as naphthalene rings (non-ring assembly arene rings).

[0052] Preferred Ring Z 1a and Z 1b As for C 6-14 arene rings, and more preferably C rings such as benzene rings, naphthalene rings, and biphenyl rings. 6-12 C rings such as arene rings, more preferably benzene rings and naphthalene rings 6-10 Ring Z is an arene ring, in particular a benzene ring. 1a and Z 1b The types may be different from each other, but are preferably the same.

[0053] In addition, Z bonded to the 9-position of the fluorene ring 1a and Z 1b The substitution position of is not particularly limited, and for example, Z 1a and / or Z 1b When Z is a benzene ring, it may be at any position. 1a and / or Z 1b When is a naphthalene ring, it is either the 1-position (1-naphthyl) or the 2-position (2-naphthyl), preferably the 2-position, and Z 1a and / or Z 1b When is a biphenyl ring, it is at the 2-position, 3-position or 4-position, preferably the 3-position.

[0054] R 2a or R 2b The substituent represented by R may be a non-reactive group or a non-polymerizable group. 2a or R2b Examples of the substituent represented by the formula (I) include hydrocarbon groups such as alkyl groups (linear or branched alkyl groups), cycloalkyl groups, aryl groups, and aralkyl groups; halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; and groups [-SR h ](wherein, R h represents a hydrocarbon group; an acyl group; a cyano group, etc.

[0055] Examples of the alkyl group (linear or branched alkyl group) include C alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl group. 1-10 alkyl group, and preferably C 1-6 alkyl group, more preferably C 1-4 It is an alkyl group.

[0056] Examples of the cycloalkyl group include C cyclopentyl and cyclohexyl groups. 5-10 Examples include a cycloalkyl group.

[0057] Examples of the aryl group include C phenyl, alkylphenyl, biphenylyl, and naphthyl groups. 6-12 Examples of the alkylphenyl group include mono- to tri-C alkylphenyl groups such as methylphenyl (or tolyl) and dimethylphenyl (or xylyl). 1-4 Examples include alkyl-phenyl groups.

[0058] Examples of the aralkyl group include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl-C 1-4 Examples include alkyl groups.

[0059] The group [—SR h ], R h Examples of the hydrocarbon group represented by the formula (I) include the same groups as the alkyl group (linear or branched alkyl group), cycloalkyl group, aryl group, and aralkyl group exemplified above as the hydrocarbon group.h Examples of the alkylthio group include an alkylthio group, a cycloalkylthio group, an arylthio group, and an aralkylthio group. Specific examples of the alkyl group include those corresponding to the specific examples of the alkyl group (straight-chain or branched-chain alkyl group), cycloalkyl group, aryl group, and aralkyl group exemplified above as the hydrocarbon group. That is, examples of the alkylthio group include C groups such as a methylthio group, an ethylthio group, a propylthio group, an n-butylthio group, and a t-butylthio group. 1-10 Examples of the cycloalkylthio group include a C alkylthio group such as a cyclohexylthio group. 5-10 Examples of the arylthio group include a C phenylthio group (thiophenoxy group) and the like. 6-10 Examples of the aralkylthio group include a C arylthio group such as a benzylthio group. 6-10 Aryl-C 1-4 Examples include an alkylthio group.

[0060] Acyl groups include C groups such as acetyl groups. 1-6 Examples include alkyl-carbonyl groups.

[0061] Among these groups, representative R 2a and R 2b Examples of the group R include a hydrocarbon group, a halogen atom, an acyl group, and a cyano group. When m2a or m2b is 1 or more, a preferred group R 2a or R 2b Examples of the alkyl group include hydrocarbon groups such as alkyl groups (linear or branched chain alkyl groups), specifically C 1-6 alkyl groups; halogen atoms such as fluorine atoms, and in particular alkyl groups, specifically C groups such as methyl groups. 1-4 Alkyl groups are preferred.

[0062] The substitution numbers m2a and m2b are 1a and Z 1bmay be selected depending on the type of ring Z, and are, for example, integers of about 0 to 9, preferably integers of 0 to 6, 0 to 4, 0 to 3, 0 to 2, more preferably 0 or 1, and particularly preferably 0. The substitution numbers m2a and m2b may be different from each other, but are preferably the same. When the substitution numbers m2a and m2b are 1 or more, the ring Z 1a and Z 1b The group R to be substituted 2a and R 2b The types of may be different from each other, but are preferably the same. 1a Two or more groups R 2a and / or ring Z 1b Replace with 2 or more R 2b The types of groups R may be the same or different. 2a and R 2b The substitution position of is not particularly limited.

[0063] In the formula (2), Z 2a ,Z 2b ,Z 3a or Z 3b may be either a benzene ring or a naphthalene ring, with a benzene ring being preferred.

[0064] Ring Z 2a and Z 2b The types of rings Z may be different from each other, but are preferably the same. 3a and Z 3b The types of rings Z may be different from each other, but are preferably the same. 2a and Z 3a The types of rings Z may be different from each other, but are preferably the same. 2b and Z 3b The types may be different from each other, but are preferably the same.

[0065] R 3a ,R 3b ,R 4a or R 4b The substituent represented by R may be a non-reactive group or a non-polymerizable group.3a ,R 3b ,R 4a or R 4b Examples of the substituent represented by R 2a and R 2b The hydrocarbon groups exemplified as h ](wherein, R h indicates a hydrocarbon group), and in addition to groups similar to acyl groups, the group [-OR h ](wherein, R h represents a hydrocarbon group).

[0066] Group [-OR h ] in which the hydrocarbon group R h is the group [—SR h ] R h Therefore, the group [-OR h ] includes, for example, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, etc., and specifically, the hydrocarbon group R h That is, examples of the alkoxy group include linear or branched alkoxy groups, for example, C alkoxy groups such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, and t-butoxy group. 1-10 Examples of the cycloalkyloxy group include a C alkoxy group such as a cyclohexyloxy group. 5-10 Examples of the aryloxy group include C aryloxy groups such as phenoxy groups. 6-10 Examples of the aralkyloxy group include a C aryloxy group such as a benzyloxy group. 6-10 Aryl-C 1-4 Examples thereof include an alkyloxy group.

[0067] Among these groups, the representative group R 3a ,R 3b ,R 4a and R 4b Examples of the groups R include hydrocarbon groups and acyl groups. When m3a, m3b, m4a, and m4b are 1 or more, preferred groups R 3a ,R3b ,R 4a ,R 4b Examples of the alkyl group include hydrocarbon groups such as alkyl groups, and more preferably alkyl groups (linear or branched alkyl groups), specifically, C 1-6 alkyl groups, particularly C 1-4 Alkyl groups are preferred.

[0068] The substitution numbers m3a, m3b, m4a and m4b are 2a ,Z 2b ,Z 3a and Z 3b may be selected depending on the type of m3a, m3b, m4a, and m4b, and each may be, for example, an integer of about 0 to 7, preferably an integer of 0 to 5, an integer of 0 to 3, an integer of 0 to 2, and more preferably 0 or 1, and particularly preferably 0. The numbers of substitutions m3a, m3b, m4a, and m4b may be the same or different from each other. When the number of substitutions m3a, m3b, m4a, and / or m4b is 2 or more, two or more groups R 3a ,R 3b ,R 4a and / or R 4b The types of groups R may be the same or different. 3a ,R 3b ,R 4a and R 4b The substitution position of is not particularly limited.

[0069] Preferred fluorene compounds (1) include those having R 1a and R 1b each independently represents a hydrocarbon group; m1a and m1b each independently represent an integer of 0 to 2; Z 1a and Z 1b independently C 6-14 represents an arene ring, R 2a and R 2b each independently represents a hydrocarbon group or a halogen atom, and m2a and m2b each independently represent an integer of 0 to 2;

[0070] More preferably, R 1a and R1b each independently represents an alkyl group; m1a and m1b each independently represent 0 or 1; Z 1a and Z 1b However, independently, C rings such as benzene ring, naphthalene ring, and biphenyl ring 6-12 represents an arene ring (e.g., a benzene ring or a naphthalene ring, particularly a benzene ring); R 2a and R 2b are independently an alkyl group or a fluorine atom (particularly, an alkyl group), and m2a and m2b are independently 0 or 1;

[0071] More preferably, R 1a and R 1b But independently C 1-6 an alkyl group, m1a and m1b independently represent 0 or 1; Z 1a and Z 1b However, independently, C such as benzene ring, naphthalene ring 6-10 represents an arene ring (particularly, a benzene ring), R 2a and R 2b But independently C 1-6 represents an alkyl group, and m2a and m2b independently represent 0 or 1.

[0072] In addition, preferred fluorene compounds (2) include those represented by the formula: R 1a and R 1b , m1a and m1b, Z 1a and Z 1b , R 2a and R 2b , m2a and m2b are the same as those corresponding to the above-mentioned preferred fluorene compound (1), Ring Z 2a ,Z 2b ,Z 3a and Z 3b each independently represents a benzene ring or a naphthalene ring, preferably a benzene ring; base R 3a ,R 3b ,R 4aand R 4b independently represents a hydrocarbon group such as an alkyl group, preferably a C 1-6 alkyl group, more preferably C 1-4 represents an alkyl group, Examples of the fluorene compounds include those in which the substitution numbers m3a, m3b, m4a, and m4b are independently an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1.

[0073] Representative fluorene compounds (1) include, for example, 9,9-diaryl-diaminofluorenes, specifically 9,9-diC such as 9,9-diphenyl-2,7-diaminofluorene. 6-10 Aryl-diaminofluorene and the like.

[0074] The fluorene compound (1) of the present disclosure may be in the form of a salt, such as an inorganic acid salt such as a hydrochloride or a sulfate, or an organic acid salt such as a carboxylate (e.g., an acetate) or a sulfonate (e.g., a paratoluenesulfonate).

[0075] A typical fluorene compound (2) is, for example, a compound corresponding to the typical fluorene compound (1) in which two amino groups bonded to the fluorene ring are substituted with the imino group-containing group [—N═C(Z 2a (R 3a ) m3a )(Z 3a (R 4a ) m4a )] and [-N=C(Z 2b (R 3b ) m3b )(Z 3b (R 4b ) m4b )], specifically, di-C groups such as the group [-N=C(C6H5)2] (diphenylmethylideneamine-N-yl group). 6-10 Examples of the diimine compounds include those substituted with aryl-methylideneamine-N-yl groups, such as 9,9-diphenyl-N,N'-bis(diphenylmethylidene)-2,7-fluorenediamine.

[0076] The fluorene compound (1) or a salt thereof may be crystalline or amorphous, and the fluorene compound (2) may be crystalline or amorphous.

[0077] [Method for producing fluorene compound (1) or a salt thereof] The fluorene compound (1) [diamine compound (1)] or a salt thereof can be easily and efficiently produced by a method including a hydrolysis step of hydrolyzing the fluorene compound (2).

[0078] In the hydrolysis step (hydrolysis reaction), the fluorene compound (2) may be reacted in the presence of water and an acid by a conventional method. Examples of the acid include inorganic acids, organic acids, and solid acids. Examples of the inorganic acid include sulfuric acid, hydrogen chloride, and phosphoric acid. The inorganic acid may be in the form of an aqueous solution, such as hydrochloric acid. Examples of the organic acid include sulfonic acids, specifically (halo)alkanesulfonic acids such as methanesulfonic acid and trifluoromethanesulfonic acid, and arenesulfonic acids such as p-toluenesulfonic acid. Examples of the solid acid include inorganic solid acids, specifically metal compounds such as metal oxides, composite metal oxides, metal sulfides, metal sulfates, and polyacids (e.g., tungstophosphoric acid), nonmetal sulfates, clay minerals, zeolites, and kaolin; and organic solid acids, specifically cation exchange resins such as strong acid cation exchange resins and weak acid cation exchange resins. Examples of strongly acidic cation exchange resins include ion exchange resins having sulfonic acid groups, such as Nafion manufactured by DuPont. Examples of weakly acidic cation exchange resins include ion exchange resins having carboxylic acid groups, such as (meth)acrylic acid-divinylbenzene copolymer.

[0079] These acids may be used alone or in combination of two or more. Among these acids, inorganic acids are preferred, and inorganic acids in the form of aqueous solutions such as hydrochloric acid are preferred.

[0080] The proportion of the acid may be, for example, about 1 to 50% by mass relative to the total amount of water and acid, and preferably, in the following stepwise manner, 3 to 30% by mass, 5 to 20% by mass, and 7 to 15% by mass. The proportion of the total amount of water and acid relative to 100 parts by mass of fluorene compound (2) may be, for example, 10 to 1000 parts by mass, and preferably, in the following stepwise manner, 30 to 500 parts by mass, 40 to 100 parts by mass, and 50 to 70 parts by mass. The proportion of the acid may be, for example, about 0.1 to 5 moles relative to 1 mole of fluorene compound (2), and preferably, in the following stepwise manner, 0.5 to 2 moles, 1 to 1.5 moles, and 1.1 to 1.2 moles. The proportion of water may be 2 moles or more relative to 1 mole of fluorene compound (2), and may be, for example, 2 to 10 moles, and preferably 2 to 2.5 moles.

[0081] The reaction may be carried out in a solvent. Examples of the solvent include ethers, specifically chain ethers such as diethyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and cyclic ethers such as tetrahydrofuran (THF) and 1,4-dioxane. These solvents can be used alone or in combination. Among these solvents, cyclic ethers such as THF are preferred. The proportion of the solvent is, for example, about 10 to 3,000 parts by mass, preferably 100 to 2,000 parts by mass, 500 to 1,500 parts by mass, and 1,000 to 1,200 parts by mass, relative to 100 parts by mass of the fluorene compound (2).

[0082] The reaction temperature is, for example, about 0 to 100° C., preferably 10 to 50° C., 15 to 40° C., and 20 to 30° C. in the following stepwise manner. The reaction time is, for example, about 0.1 to 72 hours, preferably 0.5 to 12 hours, and more preferably 1 to 3 hours.

[0083] The reaction may be carried out with stirring in air or in an inert atmosphere such as nitrogen gas or a rare gas, preferably in an inert atmosphere, and may be carried out under normal pressure or pressure.

[0084] After completion of the reaction, the reaction mixture (reaction solution or reaction mixture) may be separated (or purified) by a conventional method, such as filtration, concentration, extraction, neutralization, washing, drying, crystallization, reprecipitation, column chromatography, or a combination of these methods.

[0085] [Method for producing fluorene compound (2)] The method for producing fluorene compound (2) [diimine compound (2)] is not particularly limited. For example, fluorene compound (2) can be easily or efficiently produced by a method including a coupling step of coupling a fluorene compound represented by the following formula (3) [hereinafter also referred to as fluorene compound (3)] with an imine compound represented by the following formula (4a) or (4b) [hereinafter also referred to as imine compounds (4a) and (4b)] (cross-coupling reaction).

[0086] [ka]

[0087] (In the formula, X 1a and X 1b each independently represents a halogen atom, R 1a and R 1b , m1a and m1b, Z 1a and Z 1b , R 2a and R 2b and m2a and m2b are the same as those in the formula (2) above, including preferred embodiments.)

[0088] [ka]

[0089] (In the formula, Z 2a and Z 2b , R 3a and R 3b , m3a and m3b, Z 3a and Z 3b , R 4a and R 4band m4a and m4b are the same as those in the formula (2) above, including preferred embodiments.)

[0090] In the formula (3), X 1a or X 1b Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of ease of preparation of the diimine compound (2), a chlorine atom, a bromine atom, or an iodine atom is preferred, a bromine atom or an iodine atom is more preferred, and a bromine atom is particularly preferred. 1a and X 1b The types of X may be the same or different from each other. 1a and X 1b The substitution positions of the two imino group-containing groups in the formula (2) (or the two amino groups [—NH2] in the formula (1)) correspond to the substitution positions of the two imino group-containing groups in the formula (2) (or the two amino groups [—NH2] in the formula (1)), and may be similar, including preferred embodiments.

[0091] Preferred fluorene compounds (3) include R 1a and R 1b , m1a and m1b, Z 1a and Z 1b , R 2a and R 2b , m2a and m2b are the same as those corresponding to the preferred fluorene compound (1), X 1a and X 1b and independently represent a halogen atom, preferably a chlorine atom, a bromine atom, or an iodine atom, more preferably a bromine atom or an iodine atom, and particularly preferably a bromine atom.

[0092] A typical fluorene compound (3) is, for example, a compound in which two amino groups bonded to the fluorene ring are bonded to the halogen atoms X corresponding to the typical fluorene compound (1). 1a and X 1b Specifically, fluorene compounds in which fluorene atoms are substituted with bromine atoms, such as 9,9-diphenyl-2,7-dibromofluorene, can be mentioned.

[0093] The imine compounds (4a) and (4b) correspond to the target fluorene compound (2), and examples thereof include diaryl ketone imines such as benzophenone imine. The imine compounds (4a) and (4b) may be used alone or in combination of two or more, but are preferably used alone. It is preferable that the imine compounds (4a) and (4b) are the same compound.

[0094] The ratio of the fluorene compound (3) to the total amount of the imine compounds (4a) and (4b) may be, for example, the former / latter (molar ratio) = about 1 / 2 to 1 / 10, and preferably the following stepwise ratios: 1 / 2.1 to 1 / 5, 1 / 2.2 to 1 / 3, and 1 / 2.3 to 1 / 2.5.

[0095] The coupling reaction is not particularly limited as long as it can produce the fluorene compound (2), but the Hartwig-Buchwald cross-coupling reaction is preferred.

[0096] The coupling reaction may be carried out in the presence of a catalyst. Examples of the catalyst include metal catalysts such as palladium catalysts. The palladium catalyst may be, for example, a palladium(0) catalyst or a palladium catalyst precursor that can be reduced to a zero-valent palladium catalyst by a reducing compound such as a phosphine, an amine, or an organometallic reagent.

[0097] Examples of palladium(0) catalysts include palladium(0)-phosphine complexes such as tetrakis(triphenylphosphine)palladium(0) [or Pd(PPh3)4] and bis(tri-t-butylphosphine)palladium(0) [or Pd(P(t-Bu)3)2], bis(dibenzylideneacetone)palladium(0) [Pd(dba)2], and tris(dibenzylideneacetone)dipalladium(0) [Pd2(dba)3].

[0098] Examples of palladium catalyst precursors include palladium(II) compounds such as palladium(II) acetate, [1,2-bis(diphenylphosphino)ethane]palladium(II) dichloride [or PdCl(dppe)], [1,3-bis(diphenylphosphino)propane]palladium(II) dichloride [or PdCl(dppp)], [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride [or PdCl(dppf)], bis(triphenylphosphine)palladium(II) dichloride [or PdCl(PPh)], and bis(tri-o-tolylphosphine)palladium(II) dichloride [or PdCl(P(o-tolyl))]; and tris(dibenzylideneacetone)dipalladium(0) chloroform complex [or Pd(dba)·CHCl].

[0099] These catalysts can be used alone or in combination. Among these catalysts, palladium (0) catalysts such as Pd(dba)2 are preferred. The proportion of the catalyst (catalyst precursor) relative to 1 mole of the fluorene compound (3) may be, for example, about 0.0001 to 0.1 moles, preferably 0.001 to 0.05 moles, 0.002 to 0.02 moles, 0.003 to 0.01 moles, 0.0035 to 0.008 moles, and 0.004 to 0.006 moles in the following stepwise manner. When the proportion of the catalyst (catalyst precursor) is within a moderate range that is not too high, purification tends to be easier.

[0100] The coupling reaction may be carried out in the presence of a ligand. Examples of the ligand include bidentate ligands such as 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), and 1,1'-bis(diphenylphosphino)ferrocene (dppf). These ligands can be used alone or in combination. Among these ligands, BINAP is preferred. The proportion of the ligand relative to 1 mole of the fluorene compound (3) may be, for example, about 0.0001 to 0.1 moles, preferably 0.001 to 0.05 moles, 0.005 to 0.03 moles, and 0.01 to 0.02 moles in the following stepwise manner.

[0101] The coupling reaction may be carried out in the presence of a base. Examples of the base include metal alkoxides, specifically alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium t-butoxide, and potassium t-butoxide. These bases can be used alone or in combination. Among these bases, alkali metal alkoxides such as sodium t-butoxide are preferred. 1-6 The proportion of the base may be, for example, about 2 to 10 moles, preferably 2.2 to 5 moles, 2.3 to 4 moles, and 2.5 to 3 moles, stepwise, relative to 1 mole of the fluorene compound (3).

[0102] The reaction may be carried out in a solvent. Examples of solvents include ethers, specifically, chain ethers such as diethyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether, and cyclic ethers such as tetrahydrofuran (THF) and 1,4-dioxane; amides, specifically, chain amides such as N,N-dimethylformamide (DMF), N,N-diethylformamide, and N,N-dimethylacetamide (DMAc), and cyclic amides such as N-methyl-2-pyrrolidone (NMP); and hydrocarbons, specifically, aliphatic hydrocarbons such as hexane, heptane, octane, and decane; alicyclic hydrocarbons such as cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. These solvents can be used alone or in combination. Among these solvents, ethers such as dimethyl ether, THF, and dioxane, aliphatic hydrocarbons such as hexane, and aromatic hydrocarbons such as toluene and xylene are preferred, with aromatic hydrocarbons such as toluene being more preferred. The proportion of the solvent is, for example, about 10 to 2000 parts by mass, preferably 100 to 1000 parts by mass, and more preferably 300 to 700 parts by mass, relative to 100 parts by mass of the fluorene compound (3).

[0103] The reaction temperature is, for example, about 0 to 150° C., preferably 50 to 140° C., 80 to 130° C., and 100 to 120° C. in the following stepwise manner. The reaction time is, for example, about 10 minutes to 24 hours, preferably 1 to 12 hours, and more preferably 3 to 8 hours.

[0104] The reaction may be carried out with stirring, in an inert atmosphere such as nitrogen gas or a rare gas, or under atmospheric pressure or elevated pressure.

[0105] After completion of the reaction, the reaction mixture (reaction solution or reaction mixture) may be separated (or purified) by a conventional method, such as filtration, concentration, extraction, neutralization, washing, drying, crystallization, reprecipitation, column chromatography, or a combination of these methods.

[0106] [Uses of fluorene compounds] Fluorene compound (1) or its salt and fluorene compound (2) can be used as reaction intermediates, resin raw materials (or polymerization components) for forming resins, resin additives for modifying resins, and light-emitting materials such as fluorescent materials and phosphorescent materials. Among these, resin raw materials are preferred, and fluorene compound (1) [or diamine compound (1)] or its salt can be effectively used as a resin raw material. Therefore, the present disclosure encompasses resins containing fluorene compound (1) or its salt as a polymerization component or resin raw material.

[0107] (resin) The resin is not particularly limited as long as it contains fluorene compound (1) or its salt as at least a polymerization component or raw material, and may be a thermoplastic resin or a curable resin. Representative resins include resins containing a diamine component or a polyamine component as a polymerization component (e.g., polyamide-based resins, polyimide-based resins (including polyamideimide resins), polyurea-based resins, etc.); and bismaleimide-based resins (compounds in which the two amino groups of fluorene compound (1) are replaced with maleimide groups) obtained by ring-closing (condensation or dehydration) bismaleamic acid (bismaleamic acid) produced by reacting fluorene compound (1) or its salt with a maleic acid component (e.g., maleic anhydride). Preferred resins include polyamide-based resins, polyimide-based resins (including polyamideimide resins), and polyurea-based resins, which contain a diamine component containing fluorene compound (1) or its salt as a polymerization component.

[0108] The polyamide resin may contain, as polymerization components, a diamine component and a dicarboxylic acid component.

[0109] The polyamide resin contains at least the fluorene compound (1) or a salt thereof as a diamine component, and may or may not contain a diamine component different from the fluorene compound (1) as necessary. The diamine component different from the fluorene compound (1) may be a diamine component exemplified as the second diamine component in the section on polyimide resins described later, for example, an aliphatic diamine component, specifically, a diamino C such as 1,4-diaminobutane or hexamethylenediamine. 2-12 Alkanes, etc.; aromatic diamine components, specifically, diaminoarenes such as m-phenylenediamine and p-phenylenediamine, bis(aminoalkyl)arenes such as m-xylylenediamine, etc. The diamine components can be used alone or in combination of two or more.

[0110] Examples of the dicarboxylic acid component include an aliphatic dicarboxylic acid component, an alicyclic dicarboxylic acid component, and an aromatic dicarboxylic acid component. The dicarboxylic acid component can be used alone or in combination of two or more. The dicarboxylic acid component includes derivatives corresponding to the dicarboxylic acid, such as acid halides such as acid chlorides and acid bromides, and acid anhydrides.

[0111] Examples of the aliphatic dicarboxylic acid component include alkanedicarboxylic acids, specifically, C carboxylic acids such as succinic acid, adipic acid, sebacic acid, and decanedicarboxylic acid. 2-12 Alkane dicarboxylic acids, etc.; unsaturated aliphatic dicarboxylic acids, specifically C such as maleic acid, fumaric acid, and itaconic acid 2-10 Alkene-dicarboxylic acids and the like.

[0112] Examples of the alicyclic dicarboxylic acid component include cycloalkane dicarboxylic acids, specifically, C 1,4-cyclohexane dicarboxylic acids. 5-10Cycloalkane dicarboxylic acids, etc.; bridged cyclic cycloalkane dicarboxylic acids, specifically, bi- or tricycloalkane dicarboxylic acids such as decalin dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid, tricyclodecane dicarboxylic acid, etc.; cycloalkene dicarboxylic acids, specifically, C such as cyclohexene dicarboxylic acid, etc. 5-10 Cycloalkene-dicarboxylic acids and the like; bridged cyclic cycloalkene dicarboxylic acids, specifically, bi- or tricycloalkene dicarboxylic acids such as norbornene dicarboxylic acid and the like.

[0113] Examples of the aromatic dicarboxylic acid component include monocyclic aromatic dicarboxylic acids and polycyclic aromatic dicarboxylic acids. Examples of the monocyclic aromatic dicarboxylic acids include benzene dicarboxylic acids such as phthalic acid, terephthalic acid, and isophthalic acid; alkyl benzene dicarboxylic acids, specifically, C alkyl benzene dicarboxylic acids such as 4-methylisophthalic acid; 1-4 Examples of the polycyclic aromatic dicarboxylic acid include condensed polycyclic aromatic dicarboxylic acids, specifically polycyclic C dicarboxylic acids such as naphthalenedicarboxylic acids such as 2,3-naphthalenedicarboxylic acid, anthracenedicarboxylic acid, and phenanthrenedicarboxylic acid. 10-24 arene-dicarboxylic acids, etc.; biaryldicarboxylic acids, specifically, 2,2'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, etc.; bis[(carboxyalkoxy)-C 6-10 aryl]alkanes, specifically bis[(carboxy C 1-4 Alkoxy)-C 6-10 Aryl)C 1-6 Alkanes, etc.; diarylalkanedicarboxylic acids, specifically, di-C such as 4,4'-diphenylmethanedicarboxylic acid 6-10 Aryl C 1-6 Alkane-dicarboxylic acids, etc.; diaryl ketone dicarboxylic acids, specifically, di(C) such as 4,4'-diphenyl ketone dicarboxylic acid 6-10aryl) ketone-dicarboxylic acids; diaryl ether dicarboxylic acids, specifically, di(C) such as 4,4'-diphenyl ether dicarboxylic acid 6-10 aryl) ether-dicarboxylic acids; diarylsulfonedicarboxylic acids, specifically, di(C) such as 4,4'-diphenylsulfonedicarboxylic acid; 6-10 aryl) sulfone-dicarboxylic acids and the like.

[0114] The polyurea resin may contain, as polymerization components, a diamine component or a polyamine component and a polyisocyanate component, and may also contain a polyol component as necessary.

[0115] The polyurea resin contains at least a fluorene compound (1) as a diamine component, and may or may not contain a diamine component other than the fluorene compound (1) as necessary. Examples of the diamine component other than the fluorene compound (1) include the same diamine components as those exemplified as the second diamine component in the section on polyimide resins described below. The diamine components may be used alone or in combination of two or more.

[0116] Examples of the polyisocyanate component include an aliphatic polyisocyanate component, an alicyclic polyisocyanate component, an aromatic polyisocyanate component, and a polyisocyanate component having a polyol skeleton (a skeleton derived from a polyol compound (or a polyether skeleton)) or a polyamine skeleton (a skeleton derived from a polyamine compound). These polyisocyanate components can be used alone or in combination of two or more.

[0117] Examples of the aliphatic polyisocyanate component include aliphatic diisocyanate components, specifically alkane diisocyanates, such as hexamethylene diisocyanate (HDI or 1,6-hexane diisocyanate), 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, and the like. 2-20Examples include alkane diisocyanates, lysine diisocyanate, and the like; and triisocyanates such as 1,3,6-hexamethylene triisocyanate.

[0118] Examples of the alicyclic polyisocyanate component include alicyclic diisocyanate components, specifically cycloalkane diisocyanates such as methyl-2,4- or 2,6-cyclohexane diisocyanate, isocyanatoalkyl cycloalkane isocyanates such as isophorone diisocyanate (IPDI), bis(isocyanatoalkyl)cycloalkanes such as hydrogenated xylylene diisocyanate, bis(isocyanatocycloalkyl)alkanes such as hydrogenated diphenylmethane-4,4′-diisocyanate, polycycloalkane diisocyanates such as norbornane diisocyanate, and triisocyanates such as 1,3,5-triisocyanatocyclohexane.

[0119] Examples of aromatic polyisocyanate components include aromatic diisocyanate components, specifically, arene diisocyanates which may have a substituent such as o-, m-, or p-phenylene diisocyanate, chlorophenylene diisocyanate, tolylene diisocyanate (TDI), naphthalene diisocyanate (NDI), tolidine diisocyanate (TODI or 3,3'-dimethylbiphenyl-4,4'-diisocyanate), bis(isocyanatoaryl)alkanes such as diphenylmethane diisocyanate (MDI), aromatic aliphatic diisocyanates such as xylylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI), bis(isocyanatophenyl)ether, bis(isocyanatophenyl)sulfone, and the like; and tri- or tetraisocyanates such as 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate.

[0120] Examples of polyisocyanate components having a polyol skeleton or a polyamine skeleton include polyisocyanate compounds (adducts or prepolymers) obtained by reacting a polyol compound and / or a polyamine compound with a conventional polyisocyanate compound. Examples of the polyol compounds include low-molecular-weight polyols such as alkanediols, polyalkanediols, and trimethylolpropane; and high-molecular-weight polyols such as polyether polyols and polyester polyols. Examples of the polyamine compounds include the compounds exemplified above as diamine components.

[0121] Examples of the polyol component include the compounds exemplified above as the polyol compound.

[0122] These resins can be produced by polymerization using a conventional method depending on the type of resin (or the type of polymerization components to be reacted). Among these resins, polyimide resins are preferred because of their excellent properties such as low thermal expansion, heat resistance, low water absorption, and low dielectric constant.

[0123] (Polyimide resin and its manufacturing method) The polyimide resin is not particularly limited as long as it contains at least the fluorene compound (1) as a polymerization component or raw material [as long as it contains a structural unit derived from the fluorene compound (1)]. For example, the polyimide resin may be formed from polymerization components containing a diamine component and a tetracarboxylic acid component and / or a bismaleimide component, and the diamine component may contain at least the fluorene compound (1).

[0124] The diamine component must contain at least a fluorene compound (1) [first diamine component], and may or may not contain a diamine component (second diamine component) different from the fluorene compound (1) [first diamine component], as necessary. Examples of the second diamine component include an aliphatic diamine component, an alicyclic diamine component, and an aromatic diamine component. These second diamine components may be used alone or in combination of two or more.

[0125] Examples of the aliphatic diamine component include alkanediamines and aliphatic diamines having heteroatoms such as oxygen atoms and sulfur atoms.

[0126] Examples of alkanediamines include linear or branched C alkyl alkanediamines such as ethylenediamine, trimethylenediamine, propylenediamine, tetramethylenediamine, 2-methyl-1,2-propanediamine, 2-methyl-1,3-propanediamine, pentamethylenediamine, 1,3-pentanediamine, 2,2-dimethyl-1,3-propanediamine, hexamethylenediamine, 2-methylpentamethylenediamine, 2,3-dimethyl-2,3-butanediamine, heptamethylenediamine, octamethylenediamine, 2,5-dimethyl-2,5-hexanediamine, nonamethylenediamine, 2-methyloctamethylenediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, decamethylenediamine, undecamethylenediamine, and dodecamethylenediamine. 2-20 Alkanediamine (preferably C 2-12 Alkanediamines).

[0127] Examples of the aliphatic diamine having a hetero atom include aliphatic (poly)ether-based diamines, aliphatic sulfide-based diamines, and N,N-bis(aminoalkyl)-alkylamines.

[0128] Examples of aliphatic (poly)ether diamines include bis(aminoalkyl) ethers such as bis(2-aminoethyl) ether; (poly)alkylene glycol bis(aminoalkyl) ethers such as ethylene glycol bis(2-aminoethyl) ether, 1,4-butanediol bis(3-aminopropyl) ether, diethylene glycol bis(3-aminopropyl) ether, triethylene glycol bis(2-aminoethyl) ether, polyethylene glycol diamine, and polypropylene glycol diamine.

[0129] Examples of the aliphatic sulfide diamines include bis(aminoalkyl) sulfides such as bis(2-aminoethyl) sulfide.

[0130] Examples of N,N-bis(aminoalkyl)-alkylamines include N,N-bis(3-aminopropyl)methylamine.

[0131] Examples of the alicyclic diamine component include alicyclic diamines having a monocyclic skeleton and alicyclic diamines having a bridged cyclic or spirocyclic skeleton.

[0132] Examples of alicyclic diamines having a monocyclic skeleton include diamines having a cycloalkane skeleton and diamines having a heterocyclic skeleton.

[0133] Examples of diamines having a cycloalkane skeleton include cycloalkanediamines such as cyclohexanediamine (1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine); bis(aminoalkyl)cycloalkanes such as 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane; optionally halogenated (e.g., fluorinated) bis(aminocycloalkyl)alkanes such as bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, and 2,2-bis(4-aminocyclohexyl)hexafluoropropane; isophoronediamine, menthenediamine, and the like.

[0134] Examples of diamines having a heterocyclic skeleton include piperazines such as piperazine, 2-methylpiperazine, 2-ethylpiperazine, 2,5-dimethylpiperazine, and N-(2-aminoethyl)piperazine.

[0135] Examples of alicyclic diamines having a bridged cyclic skeleton include bi- or tricycloalkanediamines such as adamantane-1,3-diamine, 2,5- or 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane, bis(aminomethyl)tricyclo[5.2.1.0]heptane, and the like. 2,6 ]decane and other bis(aminoalkyl)bi- or tricycloalkanes.

[0136] Examples of alicyclic diamines having a spirocyclic skeleton include 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0137] Examples of aromatic diamine components include diaminoarenes such as phenylenediamine (m-phenylenediamine, p-phenylenediamine, etc.), toluenediamine, diaminoanisole, naphthalenediamine, benzidine, o-tolidine, dimethoxybenzidine, and 4,4'-diamino-p-terphenyl; aminoaralkylamines such as aminobenzylamine; bis(aminoalkyl)arenes such as xylylenediamine (m-xylylenediamine, etc.); bis(aminoaryl)alkanes such as bis(4-aminophenyl)methane, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3,5-dimethylphenyl)methane, 1,2-bis(4-aminophenyl)ethane, 2,2-bis(4-aminophenyl)propane, and 2,2-bis(4-aminophenyl)hexafluoropropane; bis(aminoaryl)ethers such as bis(4-aminophenyl)ether and 3,4'-diaminodiphenyl ether; and bis(4-aminophenyl)ketones. Bis(aminoaryl)ketones such as bis(4-aminophenyl)sulfide and bis(3-aminophenyl)sulfide; Bis(aminoaryl)sulfones such as bis(4-aminophenyl)sulfone and bis(3-aminophenyl)sulfone; Bis(aminoaryl)amides such as 4,4'-diaminobenzanilide; 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2 bis[(aminoaryloxy)aryl]alkanes such as 1,4-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane; bis(aminoaryloxy)arenes such as 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, and 4,4'-bis(4-aminophenoxy)biphenyl; and bis[(aminoaryloxy)aryl]sulfones such as bis[4-(4-aminophenoxy)phenyl]sulfone.

[0138] The diamine component may contain a fluorene compound (1) [first diamine component], and the proportion of the structural units derived from the fluorene compound (1) [first diamine component] relative to the total structural units derived from the diamine component is, for example, 10 to 100 mol%, preferably 30 mol% or more, 50 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, and more preferably substantially 100 mol%. When the proportion of the structural units derived from the fluorene compound (1) [first diamine component] is within a moderate range that is not too small, the dielectric constant, thermal expansion, and / or water absorption of the resin tend to be easily reduced.

[0139] The proportion of the structural units derived from the second diamine component is, for example, 0 to 50 mol%, preferably in the following stepwise manner: 30 mol% or less, 20 mol% or less, 10 mol% or less, 5 mol% or less, and 0 mol%, relative to all structural units derived from the diamine component.

[0140] The polyimide resin may be formed through a reaction (condensation reaction) between the diamine component and a tetracarboxylic acid component and / or a reaction (addition reaction) between the diamine component and a bismaleimide component.

[0141] The tetracarboxylic acid component may be any component capable of forming an imide ring skeleton together with the diamine component, and may be a tetracarboxylic acid or a derivative thereof (imide-forming derivative), for example, a tetracarboxylic acid ester (e.g., alkyl ester such as methyl ester or ethyl ester) such as a tetracarboxylic acid diester (or bis-half ester), or a derivative such as a tetracarboxylic acid dianhydride, with a tetracarboxylic acid dianhydride being preferred.

[0142] Examples of the tetracarboxylic acid component include aromatic tetracarboxylic acid components, alicyclic tetracarboxylic acid components, etc. These may be used alone or in combination of two or more.

[0143] Examples of aromatic tetracarboxylic acid components include arene tetracarboxylic acids, tetracarboxylic acids having two dicarboxyarene ring skeletons (or dicarboxyaryl groups) in which carboxyl groups are adjacent to each other (substituting adjacent carbon atoms), and imide-forming derivatives thereof, which may be used alone or in combination of two or more.

[0144] Examples of arene tetracarboxylic acids include C tetracarboxylic acids such as benzene tetracarboxylic acids (e.g., pyromellitic acid), naphthalene tetracarboxylic acids (e.g., 1,4,5,8-naphthalene tetracarboxylic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid), and perylene tetracarboxylic acids (e.g., 3,4,9,10-perylene tetracarboxylic acid). 6-20 arene-tetracarboxylic acids.

[0145] Examples of tetracarboxylic acids having two dicarboxyarene ring skeletons (or dicarboxyaryl groups) in which carboxyl groups are adjacent to each other (substituting adjacent carbon atoms) include tetracarboxylic acids in which the two dicarboxyarene ring skeletons (or dicarboxyaryl groups) are bonded via a direct bond or a linking group.

[0146] Examples of the linking group include divalent linking groups such as optionally halogenated (fluorinated, chlorinated, brominated, etc.) divalent hydrocarbon groups, ether bonds [-O-], ketone bonds or carbonyl groups [-C(=O)-], sulfone bonds or sulfonyl groups [-S(=O)2-], and groups in which two or more of these are linked together. Examples of groups in which two or more are linked together include groups in which ether bonds are linked to both sides of an optionally halogenated divalent hydrocarbon group, i.e., the group [-O-(optionally halogenated divalent hydrocarbon group)-O-].

[0147] Examples of the optionally halogenated divalent hydrocarbon group include alkylene groups or alkylidene groups [C groups such as methylene, ethylene, propylidene (2,2-propanediyl), propylene (1,2-propanediyl), trimethylene, 1,2-butanediyl, and tetramethylene groups]. 1-6 alkylene or alkylidene groups, etc.], alkynylene groups (C such as ethynylene groups, etc.) 2-6 aliphatic hydrocarbon groups such as alkynylene groups; cycloalkanediyl groups (C groups such as cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, and cyclododecanediyl groups); 3-12 alicyclic hydrocarbon groups such as cycloalkylene groups; arylene groups [e.g., alkylated phenylene groups, tolylene groups, xylylene groups, naphthylene groups, etc. (C 1-6 an arylene group (C 6-10 arylene groups, etc.], biaryl-diyl groups (e.g., biphenyl-4,4'-diyl group, biphenyl-3,3'-diyl group, etc.), 6-10 aryl-diyl group, etc.), bisphenol residues [for example, diarylalkanediyl groups, specifically, di-C groups such as diphenylpropane-4,4'-diyl group (bisphenol A residue) and diphenylmethane-4,4'-diyl group (bisphenol F residue)] 6-10 Aryl-C 1-6 Di-C groups such as alkane-diyl groups and diphenylether-diyl groups, specifically, diphenylether-4,4'-diyl groups 6-10 Di-C groups such as aryl ether diyl groups and diphenyl ketone diyl groups, specifically, diphenyl ketone-4,4'-diyl groups 6-10 Di-C groups such as aryl-ketonediyl groups and diphenylsulfonediyl groups, specifically, diphenylsulfone-4,4'-diyl groups (bisphenol S residues) 6-10 arylsulfondiyl group, etc.], and groups obtained by halogenating (fluorinated, chlorinated, brominated, etc.) these groups. As the halogenation, fluorination is preferred.

[0148] Preferred divalent hydrocarbon groups which may be halogenated are aliphatic hydrocarbon groups or aromatic hydrocarbon groups which may be halogenated, and more preferred are aliphatic hydrocarbon groups which may be fluorinated [alkylene groups or alkylidene groups, specifically, optionally fluorinated C groups such as methylene groups, propylidene groups (2,2-propanediyl groups), and hexafluoropropylidene groups (2,2-hexafluoropropanediyl groups)]. 1-6 alkylene or alkylidene group] or a bisphenol residue.

[0149] Examples of the group [-O-(optionally halogenated divalent hydrocarbon group)-O-] include a group in which ether bonds are linked to both sides of the bisphenol residue, i.e., a group [-O-(the bisphenol residue)-O-].

[0150] Preferred linking groups are optionally halogenated divalent hydrocarbon groups, ether bonds [—O—], ketone bonds or carbonyl groups [—C(═O)—], and groups formed by linking two or more of these, and more preferably ether bonds [—O—].

[0151] Representative tetracarboxylic acids having two dicarboxyarene ring skeletons (or dicarboxyaryl groups) include, for example, biaryltetracarboxylic acids, specifically, bi-C such as biphenyltetracarboxylic acids (3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, etc.). 6-10 aryl-tetracarboxylic acids, etc.; bis(dicarboxyaryl)alkanes, specifically, optionally fluorinated bis(dicarboxyaryl)alkanes such as 3,3',4,4'-tetracarboxydiphenylmethane, 2,2-bis(3,4-dicarboxyphenyl)propane, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane; 6-10 Aryl)C 1-10 Alkanes, etc.; bis(dicarboxyaryl) ethers, specifically, bis(dicarboxy C) such as 4,4'-oxydiphthalic acid and 3,4'-oxydiphthalic acid.6-10 aryl) ethers, etc.; bis(dicarboxyaryl) ketones, specifically, bis(dicarboxy C) such as 3,3',4,4'-benzophenonetetracarboxylic acid; 6-10 aryl) ketones, etc.; bis(dicarboxyaryl) sulfones, specifically, bis(dicarboxy C) such as 3,3',4,4'-diphenylsulfonetetracarboxylic acid; 6-10 aryl) sulfones, etc.; bis(dicarboxyaryloxyaryl)alkanes, specifically, bis(dicarboxy C) such as 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane; 6-10 Aryloxy-C 6-10 Aryl)C 1-10 Alkanes and the like.

[0152] Examples of the alicyclic tetracarboxylic acid component include hydrogenated products of the aromatic tetracarboxylic acids.

[0153] The tetracarboxylic acid component, particularly aromatic tetracarboxylic acid components such as arene tetracarboxylic acids, tetracarboxylic acids having two dicarboxyarene ring skeletons (or dicarboxyaryl groups), and imide-forming derivatives thereof, may have a substituent. The substituent may be a non-reactive substituent that is inactive in the polymerization reaction. Examples of the substituent include halogen atoms, alkyl groups, alkoxy groups, acyl groups, nitro groups, cyano groups, and disubstituted amino groups. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples of alkyl groups (linear or branched alkyl groups) include C groups such as methyl groups, ethyl groups, propyl groups, isopropyl groups, n-butyl groups, and t-butyl groups. 1-10 Alkyl groups, preferably C 1-6 alkyl group, more preferably C 1-4 Examples of the alkoxy group (linear or branched chain alkoxy group) include C alkoxy groups such as methoxy group, ethoxy group, propoxy group, n-butoxy group, and t-butoxy group. 1-10 Examples of acyl groups include C groups such as acetyl groups.1-6 Examples of disubstituted amino groups include di-C groups such as dimethylamino groups. 1-4 Bis(C) such as alkylamino group and diacetylamino group 1-4 These substituents may be used alone or in combination of two or more. Preferred substituents include halogen atoms such as fluorine atoms, C 1-4 Alkyl groups such as alkyl groups, C 1-4 An alkoxy group such as an alkoxy group is preferred, and a halogen atom such as a fluorine atom is more preferred. The number of substituents is, for example, 0 to 6, preferably 0 to 4, 0 to 2 in the following stepwise order, more preferably 0 or 1, particularly 0. When the number of substituents is 2 or more, the types of the substituents may be the same or different.

[0154] Preferred tetracarboxylic acid components are aromatic tetracarboxylic acid components such as arene tetracarboxylic acids, tetracarboxylic acids having two dicarboxyarene ring skeletons (or dicarboxyaryl groups), and imide-forming derivatives thereof (dianhydrides, etc.); more preferably, C 6-20 arene-tetracarboxylic acids, tetracarboxylic acids in which two dicarboxyarene ring skeletons (or dicarboxyaryl groups) are bonded via a direct bond, an optionally halogenated divalent hydrocarbon group, an ether bond [—O—], a ketone bond, or a carbonyl group [—C(═O)—], or a group linking two or more of these, and imide-forming derivatives thereof; more preferably, C 6-14 arene-tetracarboxylic acids, tetracarboxylic acids in which two dicarboxyarene ring skeletons (or dicarboxyaryl groups) are bonded by a direct bond or an ether bond [—O—], and imide-forming derivatives thereof; particularly preferred are C tetracarboxylic acids such as pyromellitic acid. 6-10arene-tetracarboxylic acids, tetracarboxylic acids in which two dicarboxyarene ring skeletons (or dicarboxyaryl groups) are bonded by a direct bond, and imide-forming derivatives thereof; and tetracarboxylic acids in which two dicarboxyarene ring skeletons (or dicarboxyaryl groups) are bonded by a direct bond, such as biphenyltetracarboxylic acid, and imide-forming derivatives thereof, which are excellent in heat resistance and can be easily formed into films (particularly, single or self-supporting films). These may be used alone or in combination.

[0155] The proportion of structural units derived from a preferred tetracarboxylic acid component such as an aromatic tetracarboxylic acid component [particularly the proportion of structural units derived from arenetetracarboxylic acid, tetracarboxylic acid having two dicarboxyarene ring skeletons (or dicarboxyaryl groups), and imide-forming derivatives thereof] relative to the total structural units derived from the tetracarboxylic acid component is, for example, 10 to 100 mol%, preferably 30 mol% or more, 50 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more in the following stepwise manner, and substantially 100 mol% is even more preferred.

[0156] The bismaleimide component may have two maleimide skeletons, and examples thereof include aliphatic bismaleimide components, aromatic bismaleimide components, etc. Examples of the aliphatic bismaleimide component include bismaleimide C such as bismaleimide alkanes, specifically 1,2-bismaleimide ethane, 1,4-bismaleimide butane, 1,6-bismaleimide hexane, and 1,6'-bismaleimide-(2,2,4-trimethyl)hexane. 2-12 Examples of the aromatic bismaleimide component include N,N'-arylene bismaleimides which may have an alkyl group, specifically C bismaleimides such as N,N'-1,4-phenylene bismaleimide, N,N'-1,3-phenylene bismaleimide, 4-methyl-N,N'-1,3-phenylene bismaleimide, and N,N'-1,2-phenylene bismaleimide. 1-6 N,N'-C optionally having an alkyl group 6-10Arylene-bismaleimide, etc.; bis(maleimidoaryl)alkanes which may have an alkyl group, specifically, C bismaleimide such as 4,4'-bismaleimidodiphenylmethane and 3,3'-dimethyl-5,5'-diethyl-4,4'-bismaleimidodiphenylmethane. 1-6 Bis(maleimide C) optionally having an alkyl group 6-10 Aryl)C 1-6 Alkanes, etc.; bis(maleimide aryl) ethers, specifically, bis(maleimide C) such as 4,4'-bismaleimide diphenyl ether 6-10 aryl) ethers, etc.; bis(maleimide aryl) sulfones, specifically, bis(maleimide C) such as 4,4'-bismaleimide diphenyl sulfone; 6-10 aryl) sulfones, etc.; bis(maleimidoaryloxy)arenes, specifically, bis(maleimido C) such as 1,3-bis(3-maleimidophenoxy)benzene and 1,3-bis(4-maleimidophenoxy)benzene; 6-10 Aryloxy)C 6-10 arenes, etc.; bis(maleimidoaryloxyaryl)alkanes, specifically, bis(maleimide C) such as 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane (or bisphenol A diphenyl ether bismaleimide); 6-10 Aryloxy C 6-10 Aryl)C 1-6 Alkanes, etc. These bismaleimide components may be used alone or in combination of two or more.

[0157] The polymerization components of the polyimide resin may or may not contain other polymerization components different from the diamine component, tetracarboxylic acid component, and bismaleimide component. Examples of the other polymerization components include the dicarboxylic acid component, tricarboxylic acid component (such as trimellitic acid or its imide-forming derivative), nadic acid skeleton-containing component (such as nadic acid, methylnadic acid, or their imide-forming derivatives), acetylene skeleton-containing component (such as components having an amino group, such as ethynylaniline, or components having a carboxyl group, such as ethynylphthalic acid, methylethynylphthalic acid, phenylethynylphthalic acid, or their imide-forming derivatives), and the polyisocyanate component.

[0158] The polyimide resin is preferably formed from polymerization components containing at least a diamine component and a tetracarboxylic acid component. In the polyimide resin, the total proportion of the structural units derived from the diamine component and the tetracarboxylic acid component relative to all structural units (structural units derived from monomer components) of the polyimide resin is, for example, 10 to 100 mol%, preferably 30 mol% or more, 50 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more in the following stepwise manner, and more preferably substantially 100 mol%.

[0159] Polyimide resins can be produced by conventional methods depending on the types of polymerization components, etc. For example, when producing a polyimide resin from a diamine component and a tetracarboxylic acid component (particularly, a dianhydride of a tetracarboxylic acid component), the polyimide resin can be produced by a method including a reaction step of reacting the diamine component with the tetracarboxylic acid component, and a ring-closing step of ring-closing (dehydrating or condensing) the polyamic acid (or polyamic acid) obtained in this reaction step to form an imide ring skeleton.

[0160] In the reaction step, the molar ratio of the diamine component to the tetracarboxylic acid component (particularly, the dianhydride of the tetracarboxylic acid component) can be selected, for example, from a range of about diamine component / tetracarboxylic acid component = 5 / 1 to 1 / 5, and preferably in the following stepwise manner: 3 / 1 to 1 / 3, 2 / 1 to 1 / 2, 1.5 / 1 to 1 / 1.5, 1.2 / 1 to 1 / 1.2, 1.1 / 1 to 1 / 1.1, or may be approximately equimolar.

[0161] In the reaction step, the reaction between the diamine component and the tetracarboxylic acid component (particularly, the dianhydride of the tetracarboxylic acid component) may be carried out in the presence or absence of a solvent. Examples of solvents include ethers, specifically, cyclic ethers such as tetrahydrofuran (THF) and 1,4-dioxane; esters such as ethyl acetate; ketones, specifically, chain ketones such as acetone and methyl ethyl ketone, and cyclic ketones such as cyclohexanone; halogenated hydrocarbons (particularly, chlorinated hydrocarbons) such as dichloromethane and chloroform; amides such as dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone (NMP); nitriles such as acetonitrile and propionitrile; and sulfoxides such as dimethyl sulfoxide. These solvents can be used alone or in combination. Among these, amides, halogenated hydrocarbons, and nitriles are preferred, with amides such as NMP being more preferred.

[0162] In the reaction step, the proportion of the solvent may be, for example, about 10 to 10,000 parts by mass relative to 100 parts by mass of the total amount of the diamine component and the tetracarboxylic acid component, and is preferably 50 to 1,000 parts by mass, 100 to 500 parts by mass, and 200 to 400 parts by mass in the following stepwise manner. When the proportion of the total amount of the diamine component and the tetracarboxylic acid component is within an appropriate range that is not too small, it tends to be easier to prevent difficulties in film formation and thinning when molding into a film, and also tends to be easier to prevent foaming and cracking due to residual solvent during the ring closure step.

[0163] In the reaction step, additives may be added in addition to the diamine component and the tetracarboxylic acid component. Examples of additives include conventional additives, such as reaction accelerators, reaction retarders, and stabilizers (antioxidants, UV absorbers, heat stabilizers, light stabilizers, etc.). These additives may be used alone or in combination of two or more. The total proportion of the additives may be, for example, 30 parts by mass or less (e.g., 0.1 to 30 parts by mass) per 100 parts by mass of the total amount of the diamine component and the tetracarboxylic acid component, preferably 20 parts by mass or less, and more preferably 10 parts by mass or less.

[0164] In the reaction step, the reaction may be carried out in an atmosphere of an inert gas, such as nitrogen gas or a rare gas such as helium or argon, preferably in an atmosphere of an inert gas such as argon gas. The reaction may be carried out either under normal pressure or under reduced pressure. The reaction temperature may be, for example, about 0 to 100°C, preferably 5 to 50°C, 10 to 40°C, 15 to 35°C, 20 to 30°C, or room temperature, in the following stepwise manner. The reaction time may be, for example, about 1 to 100 hours, preferably 5 to 50 hours, 10 to 30 hours, and 15 to 25 hours in the following stepwise manner.

[0165] After the reaction is complete, the reaction mixture (reaction liquid or reaction mixture) containing the polyamic acid (or polyamic acid) may be separated (or purified) by a conventional method, such as filtration, concentration, extraction, washing, drying, reprecipitation, column chromatography, or a combination of these, but does not necessarily have to be purified. For example, as described below, the mixture containing the polyamic acid (or polyamic acid) may be used as a varnish or coating composition (or a liquid composition for forming a polyimide-based resin) without purification.

[0166] In the reaction step, a polyamic acid (or polyamic acid) is produced, which has structural units derived from or corresponding to the diamine and tetracarboxylic acid components that are polymerization components. The weight-average molecular weight Mw of the polyamic acid may be, for example, about 10,000 or higher, preferably in the following stepwise order: 20,000 to 1,000,000, 30,000 to 500,000, 50,000 to 300,000, 60,000 to 200,000, 70,000 to 150,000, and more preferably in the following stepwise order: 10,000 to 100,000, 15,000 to 50,000, 20,000 to 35,000. When the weight-average molecular weight of the polyamic acid is within a moderate range that is not too small, moldability tends to be improved.

[0167] In this specification and claims, the weight average molecular weight of the polyamic acid can be measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, and specifically, can be measured by the method described in the examples.

[0168] The polyamic acid (or polyamic acid) obtained in the reaction step can be subjected to a ring-closing step to form a polyimide resin. In the ring-closing step, the polyamic acid may be heat-treated to form imide rings (close the ring).

[0169] The mixed solution containing the polyamic acid (or polyamic acid) obtained in the reaction step may be heated as is to effect ring closure, or the solvent may be removed and then heated to effect ring closure. When forming the mixed solution into a film or sheet, the mixed solution (varnish or coating composition, liquid composition) may be coated on a predetermined substrate, and the resulting polyamic acid film or sheet may be subjected to the ring closure step.

[0170] The varnish or coating composition (liquid composition) may be prepared by using the reaction mixture containing the polyamic acid (or polyamic acid) obtained in the reaction step as is, or by dissolving the separated and purified polyamic acid in a solvent. The solvent, including preferred embodiments, is the same as the solvent exemplified in the reaction step. The concentration of the polyamic acid in the varnish or coating composition may be appropriately adjusted taking into account the film thickness, coating properties, etc., and is, for example, about 5 to 50 mass %, preferably 10 to 40 mass %, more preferably 15 to 35 mass %, and particularly 20 to 30 mass %.

[0171] Additives may be added to the varnish or coating composition (liquid composition). Examples of additives include crosslinking or curing agents, antifoaming agents, coatability improvers, thickeners, lubricants, stabilizers (antioxidants, UV absorbers, heat stabilizers, light resistance stabilizers, etc.), dyes, pigments, antistatic agents, flame retardants, flame retardant assistants, antiblocking agents, fillers, gelling agents, etc. These additives may be used alone or in combination of two or more. The total proportion of these additives may be, for example, 30 parts by mass or less (e.g., 0.1 to 30 parts by mass) per 100 parts by mass of polyamic acid, preferably 20 parts by mass or less, and more preferably 10 parts by mass or less.

[0172] If necessary, the varnish or coating composition (liquid composition) may be degassed before coating to facilitate the formation of a film with excellent mechanical properties. Examples of degassing treatment include conventional degassing treatments, such as vacuum (reduced pressure) degassing, ultrasonic degassing, centrifugal degassing, stirring degassing, and static degassing. The degassing treatment may be carried out under heating. The heating temperature is, for example, about 40 to 80°C, preferably 50 to 70°C. The degassing treatment may be carried out while increasing the temperature from room temperature to the heating temperature.

[0173] Examples of methods for coating the varnish or coating composition (liquid composition) include conventional coating methods such as flow coating, spin coating, spray coating, screen printing, casting, bar coating, curtain coating, roll coating, gravure coating, dipping, and slitting.

[0174] The resulting coating film of the varnish or coating composition (liquid composition) may be dried. The drying method is not particularly limited and may be natural drying, but from the viewpoint of productivity, a method of drying by heating is preferred. In the method of drying by heating, the heating temperature may be, for example, about 150°C or less, preferably in the following stepwise manner: 40 to 120°C, 50 to 110°C, 60 to 100°C, and 70 to 90°C. The drying time can be appropriately selected depending on the heating temperature, but is, for example, about 1 to 180 minutes, preferably in the following stepwise manner: 5 to 120 minutes, 10 to 60 minutes, and 20 to 40 minutes. The coating film (polyamic acid film or sheet) of the varnish or coating composition prepared in this manner may be subjected to a ring-closing process to form a polyimide-based resin.

[0175] In the ring-closing step, for example, the polyamic acid may be heat-treated to close the ring (dehydrate or condense) and form an imide ring. The heating temperature in the ring-closing step may be, for example, about 150 to 450°C, preferably 200 to 440°C, 300 to 430°C, 330 to 420°C, or 340 to 410°C in the following stepwise manner, and more preferably 250 to 400°C, 280 to 390°C, 300 to 380°C, 320 to 370°C, or 340 to 360°C in the following stepwise manner. The ring-closing step may be performed under normal pressure, reduced pressure (or vacuum), or increased pressure, but is preferably performed under reduced pressure (or vacuum). The treatment time for the ring-closing step is, for example, about 10 minutes to 6 hours, preferably 30 minutes to 3 hours, and more preferably 1 to 2 hours.

[0176] The polyimide resin of the present disclosure may exhibit high heat resistance, with a survival rate at 600°C (600°C survival rate) of, for example, 50% or more (e.g., 60 to 100%), preferably 70% or more (e.g., 75 to 100%) and 80% or more (e.g., 80 to 90%) in stages thereafter.

[0177] In this specification and claims, the 600°C survival rate of polyamic acid can be measured by a thermogravimetric differential thermal analyzer (TG-DTA), specifically by the method described in the examples.

[0178] (Resin composition, molded body) The resin composition or molded article (molded article containing the resin composition) of the present disclosure may contain at least the resin described above. The resin composition or molded article may also contain conventional additives, such as fillers or reinforcing agents, colorants such as dyes and pigments, conductive agents, flame retardants, plasticizers, lubricants, mold release agents, antistatic agents, dispersants, flow control agents, leveling agents, antifoaming agents, surface modifiers, hydrolysis inhibitors, carbon materials, stabilizers, and stress-reducing agents. Examples of stabilizers include antioxidants, ultraviolet absorbers, and heat stabilizers. Examples of stress-reducing agents include silicone oil, silicone rubber, various plastic powders, and various engineering plastic powders. These additives may be used alone or in combination. The total proportion of these additives relative to 100 parts by mass of the resin may be, for example, 50 parts by mass or less, preferably 30 parts by mass or less, 0 to 10 parts by mass, or approximately 0.1 to 5 parts by mass, in increments of 100 parts by mass.

[0179] The molded article can be produced by, for example, injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, pressure molding, casting molding, or the like.

[0180] The shape of the molded body is not particularly limited, and examples thereof include one-dimensional structures such as linear, fibrous, thread-like, and rod-like structures, two-dimensional structures such as film-like, sheet-like, plate-like, and substrate-like structures, lens-like structures such as concave or convex lenses, and three-dimensional structures such as hollow (tubular) structures.

[0181] When the molded article has a two-dimensional structure such as a film, it may be formed into a film (or molded) using a conventional film-forming method, for example, a casting method (solvent casting method), a melt extrusion method, a calendar method, or the like. When a molded article containing a polyimide resin is molded into a film, it can be produced by subjecting a coating film (film or sheet) of a corresponding polyamic acid varnish or coating composition to a ring-closing step, as described above.

[0182] The average thickness of the film can be selected from the range of about 1 to 1000 μm depending on the application, for example, 1 to 200 μm, preferably 5 to 150 μm, 10 to 120 μm, 15 to 100 μm, 20 to 50 μm, 25 to 40 μm, and 30 to 35 μm in the following stepwise manner.

[0183] The film may be an unstretched or stretched film, and even a stretched film can maintain low birefringence. The stretched film may be either a uniaxially stretched film or a biaxially stretched film.

[0184] The stretching ratio in each direction in uniaxial or biaxial stretching is, for example, 1.1 to 10 times, preferably 1.2 to 8 times, and more preferably 1.5 to 6 times. In the case of biaxial stretching, equal stretching, for example, 1.5 to 5 times stretching in both the longitudinal and transverse directions, or unbalanced stretching, for example, 1.1 to 4 times stretching in the longitudinal direction and 2 to 6 times stretching in the transverse direction, may be used. In the case of uniaxial stretching, longitudinal stretching, for example, 2.5 to 8 times stretching in the longitudinal direction, or transverse stretching, for example, 1.2 to 5 times stretching in the transverse direction, may be used.

[0185] 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.

[0186] A stretched film can be obtained by stretching a film (or an unstretched film) after film formation. The stretching method is not particularly limited, and in the case of uniaxial stretching, either a wet stretching method or a dry stretching method may be used, and in the case of biaxial stretching, either a tenter method (flat method) or a tube method may be used, but the tenter method, which has excellent uniformity in stretched thickness, is preferred.

[0187] The molded article may be in the form of a plate such as a circuit board, etc. The average thickness of the molded article (particularly, a circuit board, etc.) may be appropriately selected depending on the application, etc., and may be, for example, about 10 to 120 μm, preferably 15 to 100 μm, 20 to 50 μm, 25 to 40 μm, or 30 to 35 μm in the following stepwise manner. [Example]

[0188] The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples. Details of evaluation items and raw materials are shown below.

[0189] [Evaluation method] ( 1 H-NMR) The sample was dissolved in a heavy solvent containing tetramethylsilane as an internal standard, and the NMR spectrum was measured using a nuclear magnetic resonance spectrometer (BRUKER "AVANCE III HD"). 1 H-NMR spectrum was measured.

[0190] (HPLC) The sample was dissolved in acetonitrile and measured using an HPLC (high performance or high performance liquid chromatograph) device "LC-20AD" manufactured by Shimadzu Corporation and a column "Kinetex XB-C18" manufactured by Phenomenex, and the HPLC purity [area %] was calculated.

[0191] (Weight average molecular weight Mw) The weight average molecular weight of the obtained polyamic acid was measured using the following measuring instrument under the following measuring conditions. Chromatography system: GPC (Shodex "GPC-104") Pump: LC-10ADvp (Shimadzu Corporation) Detector: Shodex RI-71 (Showa Denko K.K.) Column: Shodex GPC KF-806L, KF-802 (Showa Denko K.K.) Column temperature: 50℃ Eluent: N-methyl-2-pyrrolidone (NMP) [with lithium bromide and phosphoric acid (30 mmol / L each)] Standard material: polystyrene Flow rate: 0.8mL / min Pretreatment: Samples adjusted to a concentration of 0.2 w / v% are pretreated with a membrane filter

[0192] (600℃ residual rate) The resulting polyimide was measured for the survival rate of the sample at 600°C (600°C survival rate) using the following measuring instrument (TG-DTA) under the following measuring conditions. Measuring device: TG-DTA 8122 (Rigaku Corporation) Heating rate: 10℃ / min Measurement temperature: room temperature ~ 600℃ Atmosphere: Nitrogen flow (150 mL / min)

[0193] [Example 1] [Synthesis of 9,9-diphenyl-N,N'-bis(diphenylmethylidene)-2,7-fluorenediamine (DAmi-BPhF)]

[0194] [ka]

[0195] A 2 L four-necked flask was charged with 9,9-diphenyl-2,7-dibromofluorene (57.1 g, 0.12 mol), benzophenone imine (52.2 g, 0.29 mol, 2.4 eq), sodium tert-butoxide (32.3 g, 0.34 mol, 2.8 eq), and 330 mL of toluene. The mixture was purged with nitrogen and stirred at 80 °C. 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP, 1.1 g, 0.0018 mol, 0.015 eq) and Pd(dba) (0.345 g, 0.0006 mol, 0.005 eq) were then added and stirred at 110 °C for 6 hours. 1350 mL of tetrahydrofuran (THF) was added to dissolve the precipitate, and 39 g of 10% HCl aqueous solution and 100 g of distilled water were added and stirred. After separation and draining the aqueous layer, the resulting organic layer was filtered through Celite, and the filtrate was concentrated to yield 138 g of crude crystals. 1035 mL of toluene was added to the resulting crude crystals, which were dissolved at 95 °C and slowly cooled to room temperature (approximately 25 °C) to precipitate crystals. The precipitated crystals were filtered and dried to yield DAmi-BPhF (yellow solid, 68.6 g, yield 84.5%, HPLC purity 97.8%). 1 The results of H-NMR measurements are shown below.

[0196] 1 H-NMR(CDCl3,300MHz):δ(ppm)6.57(d,2H),6.79(dd,6H),7.03-7.24(m,16H),7.34-7.48(m,8H),7.68(dd,4H)

[0197] [Synthesis of 9,9-diphenyl-2,7-diaminofluorene (DA-BPhF)]

[0198] [ka]

[0199] In a 2L four-necked flask, add DAmi-BPhF (67.7g, 0.1mol) to THF. After purging with nitrogen, 837 mL of DA-BPhF was added and dissolved at room temperature (approximately 25°C). 40.5 mL of 10% by mass HCl aqueous solution was added and stirred at room temperature (approximately 25°C) for 2 hours. 100 g of water and 50 g of 10% by mass NaOH aqueous solution were added to the reaction solution, and the mixture was separated and the aqueous layer was drained. 1316 mL of n-heptane was added dropwise to the resulting organic layer at room temperature (approximately 25°C). After stirring at 10°C or below, the precipitate was filtered and dried to obtain DA-BPhF (pale yellow solid, 27.0 g, yield 77.5%, HPLC purity 83.7%).

[0200] [Reference example 1] As shown in the following formula, 9,9-diphenyl-2,7-bis(tert-butoxycarbonylamino)fluorene was synthesized, and a method for synthesizing 9,9-diphenyl-2,7-diaminofluorene was investigated by deprotecting the Boc group of the resulting compound.

[0201] [ka]

[0202] A 2L four-necked recovery flask was charged with 2,7-dibromobisphenylfluorene (0.95 g, 0.002 mol), tert-butyl carbamate (1.1 g, 0.01 mol, 4.8 eq), N,N'-dimethylethylenediamine (DMEDA, 0.71 g, 0.008 mol, 4.0 eq), potassium carbonate (1.1 g, 0.008 mol, 4.0 eq), CuI (1.5 g, 0.008 mol, 4.0 eq), and 4.4 mL of toluene. The mixture was purged with nitrogen and stirred at 110 °C for 20 hours. To the resulting reaction mixture, 7.6 g of toluene, 19.0 g of methyl isobutyl ketone (MIBK), and 10 g of water were added and stirred at 85 °C. The mixture was then separated, the aqueous layer was drained, and the organic layer was washed with water. The resulting organic layer was then washed with water three times. The resulting organic layer was filtered through Celite, and the filtrate was concentrated to obtain 1.0 g of crude crystals containing 9,9-diphenyl-2,7-bis(tert-butoxycarbonylamino)fluorene (weight including residual solvent due to undried state), but the yield and purity (HPLC purity 50.5%) were low. Since no residual solvent was detected by HPLC, the crude crystals also contained a large amount of impurities other than 9,9-diphenyl-2,7-bis(tert-butoxycarbonylamino)fluorene and residual solvent.

[0203] [Example 2] A vacuum-dried reactor was purged with argon, and DA-BPhF (5.4345 g, 0.015 mol) and NMP (1-methyl-2-pyrrolidone, CAS 872-50-4, Fujifilm Wako Pure Chemical Industries, Ltd.; 29.1 g) were added to the mixture to achieve a polyamic acid concentration of 25% by mass. BPDA (4,4'-biphthalic dianhydride, CAS 2420-87-3, Tokyo Chemical Industry Co., Ltd.; 4.5656 g, 0.015 mol) was added and reacted at 25°C for 20 hours to synthesize polyamic acid A (DA-BPhF / BPDA, weight-average molecular weight 28,000).

[0204] A polyethylene terephthalate (PET) film was attached to a heat-resistant glass plate, and the resulting mixture containing polyamic acid A was applied to the PET film using an applicator ("SA-201" manufactured by Tester Sangyo Co., Ltd.) to a film thickness of 200 μm. The mixture was dried at 80°C and 1 atmosphere for 30 minutes, and then peeled off from the PET film to prepare a cast film of polyamic acid A. A Kapton film was placed on the heat-resistant glass plate, and the resulting cast film was placed on the Kapton film. Polyimide tape was attached to the outer periphery of the cast film to secure it to the Kapton film. Polyimide film A was obtained by heating at 350°C under vacuum for 1 hour. The resulting polyimide film A remained as an independent film even after peeling from the Kapton film. The 600°C survival rate of the resulting polyimide film A was 84.8%.

[0205] [Example 3] A vacuum-dried reactor was purged with argon, and DA-BPhF (6.1932 g, 0.017 mol) and NMP (29.1 g) were added to the reactor to adjust the polyamic acid concentration to 25% by mass. PMDA (pyromellitic dianhydride, CAS 89-32-7, manufactured by Tokyo Chemical Industry Co., Ltd. (TCI); 3.8071 g, 0.017 mol) was added and reacted at 25°C for 20 hours to synthesize polyamic acid B (DA-BPhF / PMDA, weight-average molecular weight 21,000). This gave a mixture containing polyamic acid B.

[0206] Polyimide B was obtained in the same manner as in Example 2, except that the mixed solution containing polyamic acid B was used instead of the mixed solution containing polyamic acid A, and the cast film was heated at 300°C under vacuum for 1 hour. [Industrial Applicability]

[0207] The fluorene compounds or salts thereof of the present disclosure can be effectively used as resin raw materials (or polymerization components) for forming resins; resin additives for modifying resins, such as refractive index improvers, curing agents or curing accelerators for epoxy resins (or epoxy compounds), chain extenders or chain extenders for polyurethane-based resins, etc.; and light-emitting materials such as fluorescent materials and phosphorescent materials.

[0208] Furthermore, resins containing the fluorene compound or a salt thereof of the present disclosure as a resin raw material (polymerization component) can be used in a variety of applications, including coating agents or coating films, specifically, protective films for paints, inks, electronic devices, liquid crystal components, and the like; adhesives, pressure-sensitive adhesives; resin fillers; electric and electronic materials or electric and electronic components (electrical and electronic devices), specifically, antistatic agents, carrier transport agents, light-emitting bodies, organic photoreceptors, thermosensitive recording materials, photochromic materials, hologram recording materials, antistatic trays, conductive sheets, optical disks, inkjet printers, digital paper, color filters, organic EL elements, organic semiconductor lasers, dye-sensitized solar cells, sensors, EMI shielding films, and the like; and mechanical materials or mechanical parts (equipment), specifically, automotive materials or parts, aerospace-related materials or parts, sliding members, and the like.

[0209] The resin can also be used as an optical component, such as an optical film (optical sheet) for a liquid crystal display or an organic EL display; an optical lens for a spectacle or a camera; a prism, a hologram, or an optical fiber.

[0210] Examples of optical films include polarizing films, polarizing elements and polarizing plate protective films that constitute polarizing films, retardation films, alignment films (alignment films), viewing angle widening (compensation) films, diffuser plates (films), prism sheets, light guide plates, brightness enhancement films, near-infrared absorbing films, reflective films, anti-reflection (AR) films, reflection reducing (LR) films, anti-glare (AG) films, transparent conductive (ITO) films, anisotropic conductive films (ACF), electromagnetic shielding (EMI) films, films for electrode substrates, films for color filter substrates, barrier films, color filter layers, black matrix layers, and adhesive layers or release layers between optical films. These optical films can be effectively used as optical films for displays such as liquid crystal displays (LCDs), organic light-emitting diode displays (OLEDs), plasma displays (PDPs), field emission displays (FEDs), and electronic paper.Specific devices or apparatuses include televisions; personal computers (PCs) such as desktop PCs, notebook PCs, and tablet PCs; smartphones, mobile phones; car navigation systems; and devices or apparatuses equipped with flat panel displays (FPDs) such as touch panels.

[0211] Examples of optical lenses include eyeglass lenses, contact lenses, camera lenses, VTR zoom lenses, pickup lenses, Fresnel lenses, solar concentrating lenses, objective lenses, rod lens arrays, etc. Typical examples of devices or apparatuses equipped with such optical lenses include small or mobile devices with camera functions such as smartphones, mobile phones, and digital cameras; and in-vehicle cameras such as drive recorders and backup cameras (rear cameras).

[0212] In particular, the resins such as polyimide-based resins have excellent thermal properties (low thermal expansion), low water absorption, electrical properties (low dielectric constant), optical properties (transparency), and the like, and therefore can be used for electrical and electronic materials or electrical and electronic components such as electrical laminates, insulating varnishes, insulating films (interlayer insulating films, anisotropic conductive films, etc.), circuit boards [printed boards or printed wiring boards such as flexible printed circuit boards (FPCs)], materials for base station antennas, transparent plastic substrates, optical materials or optical members such as optical waveguides, resin modifiers, sealants, adhesives, and the like, and are particularly useful as electrical and electronic materials or electrical and electronic components, specifically as circuit boards such as materials for printed wiring boards for Wi-Fi communication, 5G, or 6G communication.

Claims

1. A method for producing a fluorene compound represented by the following formula (1) or a salt thereof, comprising a hydrolysis step of hydrolyzing a fluorene compound represented by the following formula (2): 【Chemistry 1】 [In the formula, R １ａ and R １ｂ each independently represents a substituent; m1a and m1b each independently represent an integer of 0 to 3; Z １ａ and Z １ｂ each independently represents an arene ring, R ２ａ and R ２ｂ are independently a hydrocarbon group, a halogen atom, a group [—SR ｈ ] (wherein, R ｈ represents a hydrocarbon group; ), an acyl group or a cyano group; m2a and m2b each independently represent an integer of 0 or more; Z ２ａ and Z ２ｂ each independently represents a benzene ring or a naphthalene ring, R ３ａ and R ３ｂ each independently represents a substituent; m3a and m3b each independently represent an integer of 0 or more; Z ３ａ and Z ３ｂ each independently represents a benzene ring or a naphthalene ring, R ４ａ and R ４ｂ each independently represents a substituent, and m4a and m4b each independently represent an integer of 0 or more. 【Chemistry 2】 (In the formula, R １ａ and R １ｂ , m1a and m1b, Z １ａ and Z １ｂ , R ２ａ and R ２ｂ , and m2a and m2b are the same as those in formula (2).

2. In the formulas (1) and (2), R １ａ and R １ｂ each independently represents a hydrocarbon group; m1a and m1b each independently represent an integer of 0 to 2; Z １ａ and Z １ｂ is independently C ６－１４ represents an arene ring, R ２ａ and R ２ｂ m2a and m2b each independently represent an integer of 0 to 2.

3. In the formulas (1) and (2), R １ａ and R １ｂ each independently represents an alkyl group; m1a and m1b each independently represent 0 or 1; Z １ａ and Z １ｂ However, independently C ６－１２ represents an arene ring, R ２ａ and R ２ｂ independently represent an alkyl group or a fluorine atom, and m2a and m2b independently represent 0 or 1. The method according to claim 1 .

4. A fluorene compound represented by formula (2) according to any one of claims 1 to 3.

5. A method for producing a fluorene compound represented by formula (2) according to any one of claims 1 to 3, comprising a coupling step of coupling a fluorene compound represented by formula (3) below with an imine compound represented by formula (4a) below and an imine compound represented by formula (4b) below. 【Transformation 3】 (In the formula, X １ａ and X １ｂ each independently represents a halogen atom, R １ａ and R １ｂ , m1a and m1b, Z １ａ and Z １ｂ , R ２ａ and R ２ｂ , and m2a and m2b are the same as those in formula (2). 【Chemistry 4】 (In the formula, Z ２ａ and Z ２ｂ , R ３ａ and R ３ｂ , m3a and m3b, Z ３ａ and Z ３ｂ , R ４ａ and R ４ｂ , and m4a and m4b are the same as those in formula (2).

6. A resin comprising the fluorene compound represented by formula (1) or a salt thereof according to any one of claims 1 to 3 as a polymerization component.

7. The resin of claim 6, which is a polyimide resin.

8. A molded article comprising the resin according to claim 6.

9. 9. The molded article according to claim 8, which is a circuit board.

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