Fluorene compound and producing method and use thereof

Abstract

To provide a novel fluorene compound having a 9,9-bisaryl fluorene skeleton, a producing method and use thereof.SOLUTION: A fluorene compound represented by the following formula (1) is prepared. In the formula, Z1a and Z1b independently represents an arene group, R2a and R2b independently represents a hydrocarbon group, and X1a and X1b independently represents a halogen atom.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Compounds having a 9,9-bisarylfluorene skeleton (cardo skeleton or 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 also 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 bisaniline, and in the examples, it is described that fluorenone and 2-fluoroaniline are reacted by a specified method to produce 9,9-bis(4-aminophenyl)fluorene.

[0004] In addition, JP 2011-84502 A (Patent Document 2) discloses a method for producing 9,9-bis(3-fluoro-4-aminophenyl)fluorene by reacting fluorenone with 2-fluoroaniline in a specific manner, and describes that the obtained diamine compound is effective as a resin raw material for polyamides and polyimides.

[0005] Furthermore, in FIG. 3 of Masatoshi Hasegawa, “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, China Patent Application Publication No. 103936686 (Patent Document 3) discloses a tetrafunctional benzoxazine compound having a fluorene skeleton. In the examples of this document, it is described that the benzoxazine compound (BF-ap) was synthesized via 2,7-diamino-9,9-bis(4-hydroxyphenyl)fluorene as an intermediate (M-1) based on the synthetic route shown in the following diagram (Figure 1 of Patent Document 3), and the obtained benzoxazine compound was thermally cured to prepare a polybenzoxazine resin.

[0008] [ka] [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 62-149650 [Patent Document 2] JP 2011-84502 A [Patent Document 3] China Patent Publication No. 103936686 [Non-patent literature]

[0010] [Non-Patent Document 1] Masatoshi Hasegawa, “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 Summary of the Invention [Problem to be solved by the invention]

[0011] However, the properties of these compounds with a 9,9-bisarylfluorene skeleton may not be sufficient depending on the application, etc. Therefore, new compounds are required to improve the properties and expand the applications.

[0012] Therefore, an object of the present disclosure is to provide a novel fluorene compound having a 9,9-bisarylfluorene skeleton, a production method thereof, and uses thereof. [Means for solving the problem]

[0013] As a result of intensive research to achieve the above object, the present inventors have found that a novel fluorene compound having a specific chemical structure can be easily or efficiently prepared, and have completed the present disclosure. That is, the present disclosure may include the following aspects.

[0014] Aspect [1]: A fluorene compound represented by the following formula (1).

[0015] [ka]

[0016] (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 are independently an arene ring (e.g., a C ring such as a benzene ring or a naphthalene ring). 6-14 arene ring, etc.) R 2a and R 2b each independently represents a hydrocarbon group; X 1a and X 1b each independently represents a halogen atom; n1a and n1b each independently represent an integer of 0 or more; R 3a and R 3b each independently represents a substituent, and m3a and m3b each independently represent an integer of 0 or more.

[0017] Aspect [2]: In the formula (1), R 1a and R 1b are independently a hydrocarbon group, m1a and m1b are independently an integer of 0 to 2, Z 1a and Z 1b is independently C 6-14 is an arene ring, R 2a and R 2b are independently an alkyl group; X 1a and X 1b is a fluorine atom, n1a and n1b are independently an integer of 0 to 4, R 3a and R 3b m3a and m3b are independently an integer of 0 to 2.

[0018] Aspect [3]: In the formula (1), R 1a and R 1b is independently an alkyl group; m1a and m1b are independently 0 or 1; Z 1a and Z 1b But independently, C 6-12 Arene rings (e.g., benzene rings, naphthalene rings, etc.) 6-10 arene rings, etc. R 2a and R 2b But independently, C 1-6 is an alkyl group, X 1a and X 1b is a fluorine atom, n1a and n1b are independently an integer of 0 to 2, R 3a and R 3b is independently an alkyl group; and m3a and m3b are independently 0 or 1.

[0019] Aspect [4]: ​​A method for producing a fluorene compound represented by formula (1) according to any one of aspects [1] to [3], comprising a hydrolysis step of hydrolyzing a fluorene compound represented by the following formula (2):

[0020] [ka]

[0021] (In the formula, Z 2a and Z 2b each independently represents a benzene ring or a naphthalene ring, R 4a and R 4b each independently represents a substituent; m4a and m4b 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 5a and R 5b m5a and m5b each independently represent an integer of 0 or more; R 1a and R 1b , m1a and m1b, Z 1a and Z 1b , R 2a and R 2b , X 1a and X 1b , n1a and n1b, R 3a and R 3b , m3a and m3b are the same as in formula (1).

[0022] Aspect [5]: A fluorene compound represented by the following formula (2).

[0023] [ka]

[0024] (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 are independently an arene ring (e.g., a C ring such as a benzene ring or a naphthalene ring). 6-14 arene ring, etc.) R 2a and R 2beach independently represents a hydrogen atom or a hydrocarbon group, X 1a and X 1b each independently represents a halogen atom; n1a and n1b each independently represent an integer of 0 or more; R 3a and R 3b each independently represents a substituent; m3a and m3b 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 4a and R 4b each independently represents a substituent; m4a and m4b 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 5a and R 5b each independently represents a substituent, and m5a and m5b each independently represent an integer of 0 or more.

[0025] Aspect [6]: A method for producing a fluorene compound represented by formula (2) according to aspect [5], 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.

[0026] [ka]

[0027] (In the formula, X 2a and X 2b each independently represents a halogen atom, R 1a and R 1b , m1a and m1b, Z 1a and Z 1b , R 2a and R 2b , X 1a and X 1b , n1a and n1b, R3a and R 3b m3a and m3b are the same as those in formula (2).

[0028] [ka]

[0029] (In the formula, Z 2a and Z 2b , R 4a and R 4b , m4a and m4b, Z 3a and Z 3b , R 5a and R 5b m5a and m5b are the same as those in formula (2).

[0030] Aspect [7]: A fluorene compound represented by the following formula (3).

[0031] [ka]

[0032] (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 are independently an arene ring (e.g., a C ring such as a benzene ring or a naphthalene ring). 6-14 arene ring, etc.) R 2a and R 2b each independently represents a hydrocarbon group; X 1a and X 1b each independently represents a halogen atom; n1a and n1b each independently represent an integer of 0 or more; R 3a and R 3b each independently represents a substituent; m3a and m3b each independently represent an integer of 0 or more; X 2a and X2b each independently represents a halogen atom.)

[0033] Aspect [8]: A method for producing a fluorene compound represented by formula (3) according to aspect [7], comprising a cardo skeleton forming step of reacting a fluorene compound represented by formula (5) below with an arene compound represented by formula (6a) below and an arene compound represented by formula (6b) below.

[0034] [ka]

[0035] (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; X 2a and X 2b each independently represents a halogen atom.)

[0036] [ka]

[0037] (In the formula, Z 1a and Z 1b are independently an arene ring (e.g., a C ring such as a benzene ring or a naphthalene ring). 6-14 arene ring, etc.) R 2a and R 2b each independently represents a hydrocarbon group; X 1a and X 1b each independently represents a halogen atom; n1a and n1b each independently represent an integer of 0 or more; R 3a and R 3b each independently represents a substituent, and m3a and m3b each independently represent an integer of 0 or more.

[0038] Aspect [9]: A resin comprising a fluorene compound represented by the following formula (1) as a polymerization component.

[0039] [ka]

[0040] (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 are independently an arene ring (e.g., a C ring such as a benzene ring or a naphthalene ring). 6-14 arene ring, etc.) R 2a and R 2b each independently represents a hydrogen atom or a hydrocarbon group, X 1a and X 1b each independently represents a halogen atom; n1a and n1b each independently represent an integer of 0 or more; R 3a and R 3b each independently represents a substituent, and m3a and m3b each independently represent an integer of 0 or more.

[0041] Aspect

[10] : The resin according to aspect [9], which is a polyimide-based resin.

[0042] Aspect

[11] : A molded article comprising the resin according to aspect [9] or

[10] .

[0043] Aspect

[12] : The molded article according to aspect

[11] , which is a circuit board.

[0044] In addition, the present disclosure may achieve the following secondary objectives (solve secondary problems).

[0045] That is, another object of the present disclosure is to provide a fluorene compound capable of forming a resin having a low relative dielectric constant (particularly, a relative dielectric constant at high frequencies), and a production method and use thereof.

[0046] Still another object of the present disclosure is to provide a fluorene compound capable of forming a resin having low thermal expansion, and a production method and uses thereof.

[0047] Another object of the present disclosure is to provide a fluorene compound capable of forming a resin having high transparency (or transmittance), and a production method and uses thereof.

[0048] Still another object of the present disclosure is to provide a fluorene compound capable of forming a resin having high heat resistance, and a production method and use thereof.

[0049] Still another object of the present disclosure is to provide a fluorene compound capable of forming a resin with low water absorption, a production method thereof, and uses thereof.

[0050] In this specification and claims, the number of carbon atoms of a substituent is represented as C1, C6, C 10 For example, an alkyl group with one 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 "aryl group" etc.

[0051] In the present specification and claims, "independently" means that two components are independent components, and the ring Z 1a and Z 1b In this case, the ring Z 1a and Ring Z 1b This means that the arene rings do not necessarily have to be the same as each other, but may be different arene rings.

[0052] In this specification and claims, a numerical range indicated as "X to Y" may include the numerical values ​​X and Y. Effect of the Invention

[0053] According to the present disclosure, a novel fluorene compound having a 9,9-bisarylfluorene skeleton can be provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0054] The fluorene compounds of the present disclosure may be capable of forming a resin having a low dielectric constant (particularly, a dielectric constant at high frequency). The fluorene compounds of the present disclosure may be capable of forming a resin having low thermal expansion. The fluorene compounds of the present disclosure may be capable of forming a resin having high transparency (or transmittance). The fluorene compounds of the present disclosure may be capable of forming a resin having high heat resistance. The fluorene compounds of the present disclosure may be capable of forming a resin having low water absorption.

[0055] [Fluorene compound represented by formula (1)] The present disclosure encompasses a fluorene compound represented by the following formula (1) (hereinafter also referred to as fluorene compound (1) or diamine compound (1)).

[0056] [ka]

[0057] (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 are independently an arene ring (e.g., a C ring such as a benzene ring or a naphthalene ring). 6-14 arene ring, etc.) R 2a and R 2b each independently represents a hydrogen atom or a hydrocarbon group, X 1a and X 1b each independently represents a halogen atom; n1a and n1b each independently represent an integer of 0 or more; R 3a and R 3b each independently represents a substituent, and m3a and m3b each independently represent an integer of 0 or more.

[0058] In the formula (1), the two amino groups [-NH2] may be substituted at any of the 1-4 positions or the 5-8 positions of the fluorene skeleton, but are preferably symmetrical on the paper surface, such as the 1,8 positions, the 2,7 positions, the 3,6 positions, or the 4,5 positions, and more preferably the 2,7 positions.

[0059] R 1a ,R 1b Examples of the substituent represented by the formula (non-reactive substituent or non-polymerizable substituent) 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 include linear or branched alkyl groups, for example, C 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 111, 122, 133, 144, 155, 165, 176, 187, 198, 1 1-6 Examples of the aryl group include C aryl 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 a hydrocarbon group such as an alkyl group, and more preferably a linear or branched C 1-4 It is an alkyl group.

[0060] The substitution numbers m1a and m1b may each be selected from an integer of about 0 to 2, for example, and are 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 or m1b is 2 or more, two or more groups R substituted on one of the benzene rings forming the fluorene ring are 1a or 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 as long as it is a position other than the substitution positions of the two amino groups [-NH2].

[0061] Z 1a and Z1b Examples of the arene ring (aromatic hydrocarbon ring) represented by the formula (1) include a monocyclic arene ring such as a benzene ring, a polycyclic arene ring, etc. Examples of the polycyclic arene ring include a condensed polycyclic arene ring (condensed polycyclic aromatic hydrocarbon ring), a ring-assembled arene ring (ring-assembled polycyclic aromatic hydrocarbon ring), etc.

[0062] 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 ring and indene ring. 10-16 Examples of the fused tricyclic arene ring include fused tricyclic C arene rings such as anthracene ring and phenanthrene ring. 14-20 A preferred fused polycyclic arene ring is a fused polycyclic C ring such as a naphthalene ring. 10-14 It is an arene ring.

[0063] Examples of the ring assembly arene ring include biarene rings such as biphenyl ring, phenylnaphthalene ring, and binaphthyl ring; and terarene rings such as terphenyl ring. Preferred ring assembly arene rings are C 12-18 This is a biarene ring.

[0064] In the present specification and claims, a "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, a phenylnaphthalene ring, a binaphthyl ring, and the like 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 a naphthalene ring (non-ring assembly arene ring).

[0065] 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. 6-12C such as an arene ring, more preferably a benzene ring or a naphthalene ring 6-10 Among them, arene rings, and in particular, benzene rings are preferred since they are capable of forming resins with low relative dielectric constants (or dielectric constants), and naphthalene rings are particularly preferred since they are capable of forming resins with low relative dielectric constants and linear expansion coefficients. 1a ,Z 1b When the ring Z is a polycyclic arene ring (preferably a condensed polycyclic arene ring such as a naphthalene ring), it appears that a resin exhibiting a lower dielectric constant is easily formed. 1a and Z 1b The types of may be different from each other, but are preferably the same.

[0066] 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 , Z 1b When is a benzene ring, it may be at any position, and Z 1a , 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; Z 1a , Z 1b When is a biphenyl ring, it is at the 2-, 3- or 4-position, preferably the 3-position.

[0067] Group [-OR 2a ],[-OR 2b ] in which the group R 2a ,R 2b may be either a hydrogen atom or a hydrocarbon group, and is preferably a hydrocarbon group since it is possible to form a resin with low water absorption. 2a ,R 2b Examples of the hydrocarbon group represented by the formula (I) include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

[0068] The alkyl group may be a linear or branched alkyl group, for example, a C alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a s-butyl group, or a t-butyl group. 1-10 Alkyl groups are preferred, and C1-6 Alkyl groups, more preferably C 1-4 It is an alkyl group.

[0069] Examples of the cycloalkyl group include C cyclopentyl and cyclohexyl groups. 5-10 Cycloalkyl groups are included.

[0070] 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 group (or tolyl group), dimethylphenyl group (or xylyl group), etc. 1-4 Examples include alkyl-phenyl groups.

[0071] Examples of the aralkyl group include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl-C 1-4 Examples of such groups include alkyl groups.

[0072] Preferred groups R 2a ,R 2b is a hydrocarbon group such as an alkyl group, and more preferably a linear or branched C 1-6 A linear or branched C alkyl group, more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, or the like. 1-4 Alkyl groups, especially linear or branched C 1-3 Alkyl groups are preferred, especially C 1-2 Alkyl groups are preferred, with methyl groups being most preferred.

[0073] Group [-OR 2a ],[-OR 2b Ring Z of 1a , Z 1b The substitution position for Z is not particularly limited. 1a , Z 1b The group [-OR 2a ],[-OR 2b Ring Z of 1a , Z 1bThe substitution position for Z 1a ,Z 1b When Z is a benzene ring, it is preferred that the substituent is at any one of the 2-, 3-, or 4-position, particularly the 3- or 4-position, and particularly the 4-position, of the phenyl group bonded to the 9-position of the fluorene ring. 1a ,Z 1b When Z is a naphthalene ring, it is often substituted at any one of the 5-8 positions of the naphthyl group bonded to the 9-position of the fluorene ring. For example, the 1- or 2-position of the naphthalene ring is substituted with respect to the 9-position of the fluorene ring (substitution in a 1-naphthyl or 2-naphthyl relationship), and it is preferred that Z is substituted with respect to this substitution position in a 1,5-position or 2,6-position relationship, particularly in a 2,6-position relationship. 1a ,Z 1b is a ring assembly arene ring, the group [-OR 2a ],[-OR 2b The substitution position of Z is not particularly limited, and may be, for example, substituted on the arene ring bonded to the 9-position of the fluorene or on the arene ring adjacent to this arene ring. 1a , Z 1b is a biphenyl ring (or Z 1a ,Z 1b is a benzene ring, m3a and m3b are 1, R 3a ,R 3b is a phenyl group), the 3- or 4-position of the biphenyl ring, preferably the 3-position, may be bonded to the 9-position of the fluorene. When the 3-position of the biphenyl ring is bonded to the 9-position of the fluorene, the group [-OR 2a ],[-OR 2b The substitution position of ] may be, for example, any of the 2-, 4-, 5-, 6-, 2'-, 3'-, or 4'-position of the biphenyl ring, preferably the 6- or 4'-position, and particularly preferably the 6-position.

[0074] X 1a ,X 1b Examples of halogen atoms represented by the formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A fluorine atom is preferred because it is easy to form a resin with low water absorption and low relative dielectric constant (or permittivity). When the number of substitutions n1a and n1b is 1 or more, the ring Z 1a ,Z 1b The group X to be substituted1a and X 1b The types of may be different from each other, but are preferably the same.

[0075] The substitution numbers n1a and n1b are the ring Z 1a ,Z 1b may be selected according to the type of, for example, an integer of about 0 to 8, preferably an integer of 0 to 6, an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, more preferably 0 or 1, particularly 1. Also, it is preferable that each of the substitution numbers n1a and n1b is 1 or more, for example, 1 to 3. When n1a and n1b are in a moderate range that is not too small, it may be easy to prepare a resin with low water absorption and relative dielectric constant, and when they are in a moderate range that is not too large, it may be easy to prepare a resin with high adhesiveness (adhesion) to other materials. The substitution numbers n1a and n1b may be different from each other, but are preferably the same. When the substitution number n1a or n1b is 2 or more, the ring Z 1a , Z 1b Two or more groups X to substitute 1a or X 1b The types may be the same or different from each other.

[0076] Group X 1a ,X 1b The substitution position of is the group [-OR 2a ],[-OR 2b The position is not particularly limited as long as it is other than the substitution position of the group [-OR 2a ],[-OR 2b The substitution position adjacent to the substitution position of the group [-OR 2a ],[-OR 2b ]) is preferably in the ortho position relative to the substitution position of

[0077] R 3a ,R 3b is the group [-OR 2a ],[-OR 2b ] and group X 1a ,X 1b Any substituent (non-reactive or non-polymerizable substituent) different from the group [-R h ]), the group [-SRh ](wherein, R h represents a hydrocarbon group), an acyl group, a cyano group, etc.

[0078] R h Examples of the hydrocarbon group represented by the formula (I) include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

[0079] The alkyl group may be a linear or branched alkyl group, for example, a C alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a s-butyl group, or a t-butyl group. 1-10 Alkyl groups are preferred, and C 1-6 Alkyl groups, more preferably C 1-4 It is an alkyl group.

[0080] Examples of the cycloalkyl group include C cyclopentyl and cyclohexyl groups. 5-10 Cycloalkyl groups are included.

[0081] 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 group (or tolyl group), dimethylphenyl group (or xylyl group), etc. 1-4 Examples include alkyl-phenyl groups.

[0082] Examples of the aralkyl group include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl-C 1-4 Examples of such groups include alkyl groups.

[0083] The group [-SR h Examples of the hydrocarbon group R hExamples of the alkylthio group include groups having a C group 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 thiophenoxy group. 6-10 Examples of the aralkylthio group include C arylthio groups such as benzylthio groups. 6-10 Aryl-C 1-4 Examples of such groups include alkylthio groups.

[0084] Acyl groups include C such as acetyl groups. 1-6 Examples include alkyl-carbonyl groups.

[0085] Among these groups, representative R 3a and R 3b Examples of the groups R include a hydrocarbon group, an acyl group, and a cyano group. When m3a or m3b is 1 or more, preferred groups R 3a or R 3b Examples of the alkyl group include a hydrocarbon group such as an alkyl group (straight-chain or branched-chain alkyl group), specifically, 1-6 Alkyl groups, particularly C methyl groups, 1-4 Alkyl groups are preferred.

[0086] When the number of substitutions m3a and m3b is 1 or more, the ring Z 1a ,Z 1b The group R to be substituted 3a and R 3b The types of may be different from each other, but are preferably the same.

[0087] The substitution numbers m3a and m3b are 1a , Z 1bmay be selected depending on the type of ring Z, and each may be, for example, an integer of about 0 to 8, preferably an integer of 0 to 6, an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0. The substitution numbers m3a and m3b may be different from each other, but are preferably the same. When the substitution number m3a or m3b is 2 or more, the ring Z 1a ,Z 1b Two or more groups R 3a or R 3b The types may be the same or different from each other.

[0088] base R 3a ,R 3b The substitution position of is the group [-OR 2a ],[-OR 2b ] and the substitution position of the group X 1a ,X 1b There is no particular limitation as long as it is a position other than the substitution position of

[0089] The lower limit of the sum of n1a and m3a (n1a+m3a) and the sum of n1b and m3b (n1b+m3b) may be 0 or more, and the upper limit may be within the range of the ring Z 1a ,Z 1b may be determined according to the type of ring Z 1a ,Z 1b When is a benzene ring, the upper limit may be, for example, 4, and the ring Z 1a ,Z 1b When is a naphthalene ring, the upper limit may be, for example, 6, and when ring Z 1a ,Z 1b When is a biphenyl ring, the upper limit may be, for example, 8.

[0090] Preferred fluorene compounds (1) include R 1a and R 1b are independently a hydrocarbon group, m1a and m1b are independently an integer of 0 to 2, Z 1a and Z 1b is independently C 6-14 is an arene ring, R 2a and R2b are independently a hydrogen atom or an alkyl group, in particular an alkyl group; X 1a and X 1b is a fluorine atom, n1a and n1b are independently an integer of 0 to 4, R 3a and R 3b are independently a hydrocarbon group, and m3a and m3b are independently an integer of 0 to 2;

[0091] More preferably, R 1a and R 1b is independently an alkyl group; m1a and m1b are independently 0 or 1; Z 1a and Z 1b However, independently, C rings such as benzene ring, naphthalene ring, and biphenyl ring 6-12 an arene ring (e.g., a benzene or naphthalene ring, in particular a benzene ring); R 2a and R 2b But independently, C 1-6 is an alkyl group, X 1a and X 1b is a fluorine atom, n1a and n1b are independently an integer of 0 to 4, particularly an integer of 0 to 2, R 3a and R 3b are independently an alkyl group or an aryl group, particularly an alkyl group; and m3a and m3b are independently 0 or 1;

[0092] More preferably, R 1a and R 1b But independently, C 1-6 an alkyl group, m1a and m1b are independently 0 or 1; Z 1a and Z 1b However, independently, C rings such as benzene ring, naphthalene ring, and biphenyl ring 6-12 Arene rings (e.g., benzene rings, naphthalene rings, etc.) 6-10arene rings, in particular benzene rings), R 2a and R 2b But independently, C 1-4 is an alkyl group, X 1a and X 1b is a fluorine atom, n1a and n1b are independently an integer of 0 to 3, particularly an integer of 1 to 3; R 3a and R 3b independently an alkyl group, particularly C 1-6 an alkyl group; and m3a and m3b are independently 0 or 1.

[0093] Representative examples of the fluorene compound (1) include 9,9-bis(hydroxyaryl)-diaminofluorenes, specifically 9,9-bis(hydroxyphenyl)-2,7-diaminofluorene, and other 9,9-bis(hydroxyphenyl)-diaminofluorenes. 6-10 aryl)-diaminofluorene; 9,9-bis(alkoxyaryl)-diaminofluorene, specifically 9,9-bis(C aryl)-diaminofluorene such as 9,9-bis(4-methoxyphenyl)-2,7-diaminofluorene and 9,9-bis(6-methoxy-2-naphthyl)-2,7-diaminofluorene; 1-6 Alkoxy C 6-10 aryl)-diaminofluorene; 9,9-bis(hydroxy-mono- to octafluoroaryl)-diaminofluorene, specifically 9,9-bis(hydroxy-mono- to tetrafluoro-C, such as 9,9-bis(4-hydroxy-3-fluorophenyl)-2,7-diaminofluorene; 6-10 aryl)-diaminofluorene; 9,9-bis(alkoxy-mono- or octafluoroaryl)-diaminofluorene, specifically 9,9-bis(C 1-6 Alkoxy-mono to tetrafluoro C 6-10 aryl)-diaminofluorene and the like.

[0094] The fluorene compound (1) may be crystalline or amorphous.

[0095] [Fluorene compound represented by formula (2)] The present disclosure encompasses a fluorene compound represented by the following formula (2) (hereinafter also referred to as fluorene compound (2) or diimine compound (2)). By hydrolyzing this diimine compound (2), the corresponding diamine compound (1) can be easily and efficiently produced.

[0096] [ka]

[0097] (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 are independently an arene ring (e.g., a C ring such as a benzene ring or a naphthalene ring). 6-14 arene ring, etc.) R 2a and R 2b each independently represents a hydrogen atom or a hydrocarbon group, X 1a and X 1b each independently represents a halogen atom; n1a and n1b each independently represent an integer of 0 or more; R 3a and R 3b each independently represents a substituent; m3a and m3b 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 4a and R 4b each independently represents a substituent; m4a and m4b each independently represent an integer of 0 or more; Z 3a and Z 3b each independently represents a benzene ring or a naphthalene ring, R5a and R 5b each independently represents a substituent, and m5a and m5b each independently represent an integer of 0 or more.

[0098] In the formula (2), R 1a and R 1b , m1a and m1b, Z 1a and Z 1b , R 2a and R 2b , X 1a and X 1b , n1a and n1b, R 3a and R 3b , m3a and m3b each correspond to the embodiments described in the above formula (1), and may be the same as those described in the above formula (1), including preferred embodiments such as the type of group or ring, the number of substitutions and the substitution positions.

[0099] Preferred Ring Z 2a ,Z 2b ,Z 3a ,Z 3b The ring may be either a benzene ring or a naphthalene ring, with a benzene ring being particularly preferred.

[0100] 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 of may be different from each other, but are preferably the same.

[0101] R 4a ,R 4b ,R 5a ,R 5b The substituent (non-reactive group) represented by the formula (1) is, for example, R 3a ,R 3b The hydrocarbon groups exemplified as h ](wherein, Rh represents a hydrocarbon group), and in addition to the same groups as the acyl group, the group [-OR h ](wherein, R h represents a hydrocarbon group).

[0102] Group [-OR h ] in which the hydrocarbon group R h is the R exemplified in the above formula (1). h The same examples are given below. h Examples of the hydrocarbon group R h Examples of the alkoxy group include linear or branched alkoxy groups, such as C alkoxy groups, including methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, and t-butoxy groups. 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 C aryloxy groups such as benzyloxy groups. 6-10 Aryl-C 1-4 An example of such a group is an alkyloxy group.

[0103] Among these groups, the representative group R 4a ,R 4b ,R 5a ,R 5b Examples of the groups R include a hydrocarbon group and an acyl group. When m4a, m4b, m5a, and m5b are each 1 or more, preferred groups R 4a ,R 4b ,R 5a ,R 5b Examples of the alkyl group include a hydrocarbon group such as an alkyl group, more preferably an alkyl group (straight-chain or branched-chain alkyl group), specifically, 1-6 Alkyl groups, particularly C methyl groups, 1-4 Alkyl groups are preferred.

[0104] The substitution numbers m4a, m4b, m5a, and m5b are 2a ,Z 2b ,Z 3a ,Z 3b may be selected depending on the type of the group, 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, more preferably 0 or 1, and particularly preferably 0. The numbers of substitutions m4a, m4b, m5a, and m5b may be the same or different from each other. When the number of substitutions m4a, m4b, m5a, and m5b is 2 or more, two or more groups R 4a ,R 4b ,R 5a ,R 5b The types of groups R may be the same or different. 4a ,R 4b ,R 5a ,R 5b The substitution position is not particularly limited.

[0105] Imino group-containing group [-N=C(Z 2a (R 4a ) m4a )(Z 3a (R 5a ) m5a )],[-N=C(Z 2b (R 4b ) m4b )(Z 3b (R 5b ) m5b 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.

[0106] Preferred fluorene compounds (2) include R 1a and R 1b , m1a and m1b, Z 1a and Z 1b , R 2a and R 2b , X 1a and X 1b , n1a and n1b, R 3a and R 3bm3a and m3b correspond to the preferred fluorene compound (1) described in the above section [Fluorene compound represented by formula (1)], Ring Z 2a ,Z 2b ,Z 3a ,Z 3b are independently a benzene ring or a naphthalene ring, preferably a benzene ring; base R 4a ,R 4b ,R 5a ,R 5b independently represents a hydrocarbon group such as an alkyl group, preferably a C 1-6 Alkyl groups, more preferably C 1-4 is an alkyl group, The numbers of substitutions m4a, m4b, m5a and m5b are each independently an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1, and examples of such fluorene compounds include those having the numbers of substitutions m4a, m4b, m5a and m5b which are each independently an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1.

[0107] As a representative fluorene compound (2), for example, a fluorene compound (2) corresponding to the representative fluorene compound (1) described in the above section [Fluorene compound represented by formula (1)] can be used in which two amino groups bonded to the fluorene ring are substituted with the imino group-containing group [-N=C(Z 2a (R 4a ) m4a )(Z 3a (R 5a ) m5a )],[-N=C(Z 2b (R 4b ) m4b )(Z 3b (R 5b ) m5b )], specifically, di-C such as the group [-N=C(CH)2] (diphenylmethylideneamine-N-yl group). 6-10 Diimine compounds substituted with aryl-methylideneamine-N-yl groups, for example, 9,9-bis(4-methoxy-3-fluorophenyl)-N,N'-bis(diphenylmethylidene)-2,7-fluorenediamine, and the like, are exemplified.

[0108] The fluorene compound (2) may be crystalline or amorphous.

[0109] [Fluorene compound represented by formula (3)] The present disclosure encompasses a fluorene compound represented by the following formula (3) (hereinafter also referred to as fluorene compound (3)). By subjecting this fluorene compound (3) to a coupling reaction with an imine compound represented by the formula (4a) or (4b) described below, the corresponding diimine compound (2) can be easily and efficiently produced.

[0110] [ka]

[0111] (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 are independently an arene ring (e.g., a C ring such as a benzene ring or a naphthalene ring). 6-14 arene ring, etc.) R 2a and R 2b each independently represents a hydrogen atom or a hydrocarbon group, X 1a and X 1b each independently represents a halogen atom; n1a and n1b each independently represent an integer of 0 or more; R 3a and R 3b each independently represents a substituent; m3a and m3b each independently represent an integer of 0 or more; X 2a and X 2b each independently represents a halogen atom.)

[0112] In addition, in the formula (3), R 1a and R 1b , m1a and m1b, Z 1a and Z 1b , R 2a and R 2b , X 1a and X 1b, n1a and n1b, R 3a and R 3b , m3a and m3b each correspond to the embodiments described in the above formula (1), and may be the same as those described in the above formula (1), including preferred embodiments such as the type of group or ring, the number of substitutions and the substitution positions.

[0113] X 2a ,X 2b Examples of the halogen atom represented by the formula (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. 2a and X 2b The types of X may be the same or different. 2a and X 2b The substitution positions of correspond to the substitution positions of the two amino groups [-NH2] in the above formula (1), and may be the same including preferred embodiments.

[0114] Preferred fluorene compounds (3) include R 1a and R 1b , m1a and m1b, Z 1a and Z 1b , R 2a and R 2b , X 1a and X 1b , n1a and n1b, R 3a and R 3b m3a and m3b correspond to the preferred fluorene compound (1) described in the above section [Fluorene compound represented by formula (1)], X 2a and X 2b are independently 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.

[0115] A representative fluorene compound (3) is, for example, a fluorene compound (1) corresponding to the representative fluorene compound (1) described in the above section [Fluorene compound represented by formula (1)], in which two amino groups bonded to the fluorene ring are substituted with the halogen atom X 2a and X 2b Specifically, fluorene compounds substituted with bromine atoms, for example, 9,9-bis(4-methoxy-3-fluorophenyl)-2,7-dibromofluorene, etc., can be mentioned.

[0116] The fluorene compound (3) may be crystalline or amorphous.

[0117] [Method for producing fluorene compound represented by formula (1), (2) or (3)] The method for producing each of the fluorene compounds (1), (2) and (3) is not particularly limited. However, in terms of ease and efficiency of producing each of the fluorene compounds, it is preferable to produce each of the fluorene compounds according to the following reaction formula.

[0118] [ka]

[0119] (In the formula, R 1a and R 1b , m1a and m1b, Z 1a and Z 1b , R 2a and R 2b , X 1a and X 1b , n1a and n1b, R 3a and R 3b , m3a and m3b, Z 2a and Z 2b , R 4a and R 4b , m4a and m4b, Z 3a and Z 3b , R 5a and R 5b , m5a and m5b, X 2a and X 2bcorrespond to the descriptions of the fluorene compounds (1), (2) and (3), respectively, and are the same including preferred embodiments.

[0120] (Method for producing fluorene compound (3)) The fluorene compound (3) can be easily and efficiently produced by a method including a cardo skeleton formation step of reacting (electrophilic substitution reaction) a fluorene compound represented by formula (5) (hereinafter also referred to as fluorene compound (5)) with an arene compound represented by formula (6a) or (6b) (hereinafter also referred to as arene compound (6a) or (6b)), respectively.

[0121] The fluorene compound (5) corresponds to the desired fluorene compound (3), and may be, for example, dihalo-9-fluorenone such as 2,7-dibromo-9-fluorenone. The fluorene compound (5) may be used alone or in combination of two or more kinds, but is preferably used alone. The preferred fluorene compound (5) is 2,7-dihalo-9-fluorenone such as 2,7-dibromo-9-fluorenone.

[0122] The arene compounds (6a) and (6b) correspond to the target fluorene compound (3), and include, for example, hydroxyarenes (phenols), specifically, hydroxyarenes such as phenol and naphthol (1-naphthol, 2-naphthol, etc.). 6-10 arenes, etc.; alkoxyarenes, specifically, C such as methoxyphenol and methoxynaphthol 1-6 Alkoxy C 6-10 arenes; hydroxy-mono- or polyfluoroarenes, specifically hydroxy-mono- or tetrafluoro-C such as 2-fluorophenol; 6-10 arenes; alkoxy-mono- or polyfluoroarenes, specifically C such as 2-fluoroanisole 1-6 Alkoxy-mono to tetrafluoro C 6-10arenes. The arene compounds (6a) and (6b) may be used alone or in combination of two or more kinds, but are preferably used alone. The arene compounds (6a) and (6b) are preferably the same compound. Among these arene compounds (6a) and (6b), hydroxyarenes, alkoxyarenes, and alkoxy-mono- or polyfluoroarenes are preferred; hydroxyC 6-10 Arene, C. 1-4 Alkoxy C 6-10 Arene, C. 1-4 Alkoxy-mono to tetrafluoro C 6-10 Arenes are more preferred.

[0123] The ratio of the fluorene compound (5) to the total amount of the arene compounds (6a) and (6b) may be, for example, the former / latter (molar ratio)=about 1 / 2 to 1 / 10, and is preferably 1 / 2.2 to 1 / 5, 1 / 2.5 to 1 / 4, and 1 / 2.7 to 1 / 3.3 in the following stepwise manner.

[0124] The reaction may be carried out in the presence of an acid catalyst. Examples of the acid catalyst include inorganic acids, organic acids, and solid acids. Examples of the inorganic acids 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 acids 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 acids include inorganic solid acids, specifically, metal compounds such as metal oxides, composite metal oxides, metal sulfides, metal sulfates, and polyacids (such as 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 the strong acid cation exchange resins include ion exchange resins having sulfonic acid groups, such as Nafion manufactured by DuPont. Examples of the weakly acidic cation exchange resin include ion exchange resins having a carboxylic acid group, such as (meth)acrylic acid-divinylbenzene copolymer.

[0125] These acid catalysts can be used alone or in combination of two or more. Among these acid catalysts, organic acids are preferred, and (halo)alkanesulfonic acids are more preferred, in that they can efficiently proceed with the reaction and effectively suppress the production of by-products. 1-4 Alkanesulfonic acids such as alkanesulfonic acid, especially methanesulfonic acid, are preferred.

[0126] The ratio of the acid catalyst can be selected from the range of about 0.1 to 10 moles relative to 1 mole of the fluorene compound (5), and is preferably 1 to 8 moles, 1.5 to 5 moles, 2 to 4 moles, and 2.5 to 3.5 moles in the following stepwise manner. When the ratio of the acid catalyst is in a moderate range that is not too small, the reaction tends to proceed efficiently.

[0127] The reaction may be carried out in the presence of a thiol, such as a mercaptocarboxylic acid, an aminoalkanethiol, a thiocarboxylic acid, an alkyl mercaptan, an aralkyl mercaptan, or a salt thereof.

[0128] Examples of mercaptocarboxylic acids include 3-mercaptoalkanoic acids such as 3-mercaptopropionic acid (or β-mercaptopropionic acid), 2-mercaptoalkanoic acids, mercaptosuccinic acid, mercaptobenzoic acid, etc. Examples of 2-mercaptoalkanoic acids include 2-mercaptoalkanoic acids such as thioglycolic acid (mercaptoacetic acid or mercaptoethanoic acid), thiolactic acid (or α-mercaptopropionic acid), 2-mercaptobutyric acid (or 2-mercapto-n-butanoic acid), and 2-mercaptoisobutyric acid (or 2-mercapto-isobutanoic acid). 2-6 Alkanoic acid and the like.

[0129] Examples of aminoalkanethiols include amino C such as 2-aminoethanethiol (or cysteamine), 2-aminopropanethiol, 3-aminopropanethiol, 2-aminobutanethiol, 3-aminobutanethiol, 4-aminobutanethiol, 6-aminohexanethiol, 8-aminooctanethiol, 11-aminoundecanethiol, and 16-aminohexadecanethiol. 2-20 Alkanethiols and the like.

[0130] Examples of thiocarboxylic acids include thioacetic acid and thiooxalic acid.

[0131] Examples of alkyl mercaptans include C mercaptans such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, and dodecyl mercaptan. 1-16 Alkyl mercaptans and the like.

[0132] An example of the aralkyl mercaptan is benzyl mercaptan.

[0133] Representative examples of these salts include inorganic acid salts such as hydrochloride and sulfate, organic acid salts such as acetate, alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt and magnesium salt, tetraalkylammonium salts such as ammonium salt and tetramethylammonium salt, and double salts thereof. Preferred are alkali metal salts such as sodium salt, and specific examples of the compounds include sodium methyl mercaptan and sodium ethyl mercaptan.

[0134] These thiols may be used alone or in combination of two or more kinds. Among these thiols, mercaptoalkanoic acids such as 3-mercaptopropionic acid, thioglycolic acid, and thiolactic acid, and aminoalkanethiols such as cysteamine are preferred.

[0135] The ratio of the thiols may be, for example, about 0.001 to 0.5 mol relative to 1 mol of the fluorene compound (5), and is preferably 0.005 to 0.1 mol, 0.01 to 0.08 mol, and 0.02 to 0.05 mol in the following stepwise manner. When the ratio of the thiols is within a suitable range that is not too small, the reaction tends to proceed efficiently, and when the ratio is within a suitable range that is not too large, the thiols tend not to remain as impurities such as sulfur components.

[0136] The reaction may be carried out in a solvent, if necessary. Examples of the solvent include ethers, specifically, chain ethers such as diethyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether, cyclic ethers such as tetrahydrofuran (THF) and 1,4-dioxane, ketones, specifically, chain ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and cyclic ketones such as cyclohexanone, esters, specifically, chain esters such as methyl acetate, ethyl acetate, and butyl acetate, γ-butyrolactone, γ-butyl ether, and butyl ether. Cyclic esters (lactones) such as γ-caprolactone, γ-caprolactone (or γ-hexanolactone); carbonates, specifically, linear carbonates such as dimethyl carbonate (or dimethyl carbonate), diethyl carbonate (or diethyl carbonate), cyclic carbonates such as ethylene carbonate (or ethylene carbonate), propylene carbonate (or propylene carbonate); amides, specifically, N,N-dimethylformamide (DMF), N,N-diethylformamide, N,N-dimethylacetone, chain amides such as N-methyl-2-pyrrolidone (DMAc), and cyclic amides such as N-methyl-2-pyrrolidone (NMP); ureas, specifically, chain ureas such as tetramethylurea, tetraethylurea, and cyclic ureas such as 1,3-dimethyl-2-imidazolidinone (DMI or N,N'-dimethylethyleneurea), N,N'-dimethyl-N,N'-trimethyleneurea (or N,N'-propyleneurea); nitriles, specifically, cyanide hydrocarbons such as acetonitrile, propiononitrile, and benzonitrile; nitromethanamides, specifically, nitromethanamides, nitrated hydrocarbons such as benzene, nitroethane, nitropropane, nitrobenzene, etc.; phosphoramides such as hexamethylphosphoramide; sulfones, specifically, chain sulfones such as ethylmethylsulfone, cyclic sulfones such as sulfolane, etc.; sulfoxides such as dimethylsulfoxide (DMSO); hydrocarbons, specifically, aliphatic hydrocarbons such as hexane, heptane, octane, decane, etc., alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, etc.;Halogenated hydrocarbons, specifically, haloalkanes such as methylene chloride, chloroform, carbon tetrachloride, and 1,2-dichloroethane, and halobenzenes such as chlorobenzene and dichlorobenzene;

[0137] These solvents can be used alone or in combination of two or more. Among these solvents, it is preferable to include at least one selected from ethers, sulfones and ureas, and particularly, it is preferable to include at least one selected from cyclic compounds having a cyclic structure in the molecule (non-protonic polar solvents having a cyclic structure), particularly cyclic ethers such as 1,4-dioxane, cyclic sulfones such as sulfolane, and cyclic ureas such as DMI.

[0138] The ratio of the solvent is, for example, about 100 to 10,000 parts by mass, preferably 300 to 2,000 parts by mass, 400 to 1,500 parts by mass, and 500 to 1,000 parts by mass in the following stepwise manner, relative to 100 parts by mass of the fluorene compound (5). When the ratio of the solvent is in a moderate range, not too high, the concentration of the raw material tends to be too low, which tends to easily suppress a decrease in reactivity, and when the ratio of the solvent is in a moderate range, not too low, the viscosity tends to be too high, which tends to easily suppress a decrease in reactivity.

[0139] In the production method of the present disclosure, in order to efficiently proceed with the reaction, it is preferable to carry out the reaction in a slurry state without using a solvent.

[0140] The reaction temperature is, for example, about 0 to 150° C., preferably stepwise from 50 to 120° C., 60 to 100° C., and 70 to 90° C. The reaction time is, for example, about 30 minutes to 48 hours, preferably stepwise from 1 to 24 hours, 3 to 12 hours, and 4 to 6 hours.

[0141] The reaction may be carried out with stirring in air (atmospheric atmosphere) or in an inert atmosphere such as nitrogen gas or a rare gas, preferably in air, and may be carried out under normal pressure or increased pressure.

[0142] 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, column chromatography, or a combination of these.

[0143] (Modification of fluorene compound (3) with a modifying agent such as an alkylating agent) In addition, R 2a and R 2b In the case of preparing the fluorene compound (3) in which R is a hydrocarbon group, it is advantageous in that it can be produced efficiently and with high purity in a short process. 2a and R 2b It is preferable to prepare the compound by using the arene compound (6a) or (6b) in which R is a hydrocarbon group. 2a and R 2b Using arene compounds (6a) and (6b) in which R is a hydrogen atom, 2a and R 2b After producing a fluorene compound (3) in which R is a hydrogen atom, the resulting fluorene compound (3) is reacted with a modifying agent such as an alkylating agent to form R 2a and R 2b It is also possible to prepare a fluorene compound (3) in which R is a hydrocarbon group such as an alkyl group.

[0144] In the above (ii), the modifying agent such as an alkylating agent is 2a and R 2b Corresponding to the type of (hydrocarbon group such as alkyl group), for example, halogenated hydrocarbons, specifically, alkyl halides such as methyl iodide (or iodomethane), ethyl iodide, methyl bromide, etc., are mentioned, and alkyl iodides such as methyl iodide are preferred.

[0145] The ratio of the modifier, such as the alkylating agent, is R 2a and R 2bRelative to 1 mole of the fluorene compound (3) in which is a hydrogen atom, the amount may be, for example, about 2 to 20 moles, preferably 3 to 10 moles, 3.5 to 7 moles, or 4 to 6 moles, more preferably 2 to 6 moles, or 2.5 to 5.5 moles, in the following stepwise manner.

[0146] The reaction with a modifying agent such as an alkylating agent may be carried out in the presence of a base, such as, for example, a metal carbonate or hydrogen carbonate, a metal hydroxide, or a metal alkoxide.

[0147] Examples of the metal carbonates or hydrogen carbonates include alkali metal carbonates or hydrogen carbonates such as sodium carbonate, potassium carbonate, cesium carbonate, and sodium hydrogen carbonate.

[0148] Examples of metal hydroxides include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and cesium hydroxide, and alkaline earth metal hydroxides such as barium hydroxide.

[0149] Examples of metal alkoxides include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide.

[0150] These bases may be used alone or in combination. Preferred bases are metal carbonates or hydrogen carbonates, and alkali metal carbonates such as potassium carbonate are preferred. The ratio of bases is R 2a and R 2b The amount is, for example, about 2 to 10 moles, preferably 2.2 to 5 moles, 2.4 to 4 moles, and 2.5 to 3.5 moles, stepwise, relative to 1 mole of the fluorene compound (3) in which is a hydrogen atom.

[0151] The reaction with a modifying agent such as an alkylating agent may be carried out in a solvent. Examples of the solvent include amides, and specific examples thereof are the same as those exemplified as the solvents that may be used in the reaction of the fluorene compound (5) with the arene compounds (6a) and (6b) in the above-mentioned method for producing the fluorene compound (3). These solvents may be used alone or in combination of two or more. Among these solvents, amides such as DMF are preferred. The ratio of the solvent is as follows: R 2a and R 2b For example, about 10 to 1000 parts by mass, preferably 30 to 200 parts by mass, 50 to 150 parts by mass, and 80 to 120 parts by mass, stepwise, relative to 100 parts by mass of the fluorene compound (3) in which is a hydrogen atom.

[0152] The reaction temperature is, for example, about 0 to 100° C., and preferably stepwise from 10 to 50° C. and 20 to 40° C. The reaction time is, for example, about 1 to 24 hours, and preferably 4 to 12 hours.

[0153] The reaction may be carried out with stirring in air (atmospheric atmosphere) or in an inert atmosphere such as nitrogen gas or a rare gas, preferably in air, and may be carried out under normal pressure or increased pressure.

[0154] 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.

[0155] (Method for producing fluorene compound (2)) The fluorene compound (2) can be easily and efficiently produced by a method including a coupling step of subjecting the fluorene compound (3) to a coupling reaction (cross-coupling reaction) with an imine compound represented by the formula (4a) or (4b) (hereinafter also referred to as imine compound (4a) or (4b), respectively).

[0156] 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.

[0157] The fluorene compound (3) corresponds to the target fluorene compound (2), and examples thereof include the representative fluorene compounds (3) described above.

[0158] The imine compounds (4a) and (4b) correspond to the desired fluorene compound (2), and include, for example, 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.

[0159] 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 is preferably 1 / 2.1 to 1 / 5, 1 / 2.2 to 1 / 3, and 1 / 2.3 to 1 / 2.5 in the following stepwise manner.

[0160] The coupling reaction may be carried out in the presence of a catalyst. The catalyst may be, for example, a metal catalyst such as a palladium catalyst. 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.

[0161] 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].

[0162] Examples of palladium catalyst precursors include palladium(II) compounds such as palladium(II) acetate, [1,2-bis(diphenylphosphino)ethane]palladium(II) dichloride [or PdCl2(dppe)], [1,3-bis(diphenylphosphino)propane]palladium(II) dichloride [or PdCl2(dppp)], [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride [or PdCl2(dppf)], bis(triphenylphosphine)palladium(II) dichloride [or PdCl2(PPh3)2], and bis(tri-o-tolylphosphine)palladium(II) dichloride [or PdCl2(P(o-tolyl)3)2], and tris(dibenzylideneacetone)dipalladium(0) chloroform complex [or Pd2(dba)3·CHCl3].

[0163] These catalysts can be used alone or in combination of two or more. Among these catalysts, palladium (0) catalysts such as [Pd(dba)2] are preferred. The ratio of the catalyst (catalyst precursor) may be, for example, about 0.0001 to 0.05 mol relative to 1 mol of the fluorene compound (3), preferably 0.001 to 0.015 mol, 0.003 to 0.012 mol, 0.005 to 0.01 mol in the following stepwise manner, and more preferably 0.003 to 0.007 mol, 0.0035 to 0.006 mol, 0.004 to 0.0055 mol in the following stepwise manner. When the ratio of the catalyst (catalyst precursor) is within a moderate range that is not too high, purification tends to be easier.

[0164] 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 may be used alone or in combination of two or more. Among these ligands, BINAP is preferred. The proportion of the ligand may be, for example, about 0.0001 to 0.1 mol relative to 1 mol of the fluorene compound (3), and is preferably 0.001 to 0.05 mol, 0.005 to 0.03 mol, and 0.01 to 0.02 mol in the following stepwise manner.

[0165] 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 of two or more. Among these bases, alkali metal alkoxides such as sodium t-butoxide are preferred. 1-6 The ratio of the base may be, for example, about 2 to 10 mol, and preferably 2.2 to 5 mol, 2.3 to 4 mol, and 2.5 to 3 mol, stepwise, relative to 1 mol of the fluorene compound (3).

[0166] The reaction may be carried out in a solvent. Examples of the solvent include ethers, amides, and hydrocarbons, and specific examples thereof include the same as those exemplified as the solvents that may be used in the reaction of the fluorene compound (5) with the arene compounds (6a) and (6b) in the above-mentioned method for producing the fluorene compound (3). These solvents may be used alone or in combination of two or more. Among these solvents, ethers such as dimethyl ether, THF, and dioxane, aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons such as hexane are preferred, and aromatic hydrocarbons such as toluene are more preferred. The ratio of the solvent is, for example, about 10 to 2000 parts by mass relative to 100 parts by mass of the fluorene compound (3), and preferably 50 to 1000 parts by mass, 100 to 500 parts by mass, and 200 to 300 parts by mass in the following stepwise manner.

[0167] The reaction temperature is, for example, about 0 to 150° C., preferably stepwise from 50 to 120° C., 60 to 100° C., and 70 to 90° C. The reaction time is, for example, about 10 minutes to 12 hours, preferably stepwise from 30 minutes to 6 hours, and 40 minutes to 2 hours.

[0168] The reaction may be carried out with stirring, in an inert atmosphere of nitrogen gas or a rare gas, or under normal pressure or increased pressure.

[0169] 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.

[0170] (Method for producing fluorene compound (1)) The fluorene compound (1) can be easily and efficiently produced by a method including a hydrolysis step of hydrolyzing the fluorene compound (2).

[0171] The hydrolysis reaction may be carried out by a conventional method, for example, in the presence of water and an acid, and preferably in the presence of water and an acid. Examples of the acid include the same as those exemplified as the acid catalysts that may be used in the reaction of the fluorene compound (5) with the arene compounds (6a) and (6b) in the above-mentioned method for producing the fluorene compound (3). 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.

[0172] The ratio of the acid is, for example, about 1 to 50% by mass, preferably 3 to 30% by mass, 5 to 20% by mass, 7 to 15% by mass, stepwise, relative to the total amount of water and acid. The ratio of the total amount of water and acid is, for example, 10 to 1000 parts by mass, preferably 20 to 800 parts by mass, 30 to 500 parts by mass, 50 to 100 parts by mass, stepwise, relative to 100 parts by mass of the fluorene compound (2). The ratio of the acid may be, for example, about 0.1 to 5 moles, preferably 0.3 to 1.5 moles, 0.5 to 1 mole, 0.6 to 0.9 moles, stepwise, relative to 1 mole of the fluorene compound (2).

[0173] The reaction may be carried out in a solvent. Examples of the solvent include ethers, and specific examples thereof include the same as those exemplified as the solvents that may be used in the reaction of the fluorene compound (5) with the arene compounds (6a) and (6b) in the above-mentioned method for producing the fluorene compound (3). These solvents may be used alone or in combination of two or more. Among these solvents, cyclic ethers such as THF are preferred. The ratio of the solvent is, for example, about 10 to 2000 parts by mass relative to 100 parts by mass of the fluorene compound (2), preferably 50 to 1000 parts by mass, 100 to 500 parts by mass, and 200 to 300 parts by mass in the following stepwise manner.

[0174] The reaction temperature is, for example, about 0 to 100° C., preferably 10 to 50° C., and 20 to 40° C. in a stepwise manner. The reaction time is, for example, about 1 to 72 hours, preferably 6 to 48 hours, and 12 to 36 hours in a stepwise manner.

[0175] The reaction may be carried out with stirring in air or in an inert atmosphere such as nitrogen gas or a rare gas, and may be carried out under normal pressure or increased pressure.

[0176] 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, column chromatography, or a combination of these.

[0177] [Uses of fluorene compounds] Each fluorene compound can be used as a reaction intermediate, a resin raw material (or a polymerization component) for forming a resin, a resin additive for modifying a resin, a light-emitting material such as a fluorescent material or a phosphorescent material, etc. Among these, a resin raw material is preferable, and among them, fluorene compound (1) and fluorene compound (3), particularly fluorene compound (1) [or diamine compound (1)], can be effectively used as a resin raw material. Therefore, the present disclosure includes a resin containing fluorene compound (1) as a polymerization component or raw material.

[0178] (resin) The resin is not particularly limited as long as it contains at least the fluorene compound (1) as 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, such as polyamide resins, polyimide resins (including polyamideimide resins), and polyurea resins.

[0179] The polyamide resin may contain, as polymerization components, a diamine component and a dicarboxylic acid component.

[0180] Examples of diamine components different from the fluorene compound (1) include aliphatic diamine components, specifically, diamino C such as 1,4-diaminobutane and 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 kinds.

[0181] 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.

[0182] 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.

[0183] Examples of the alicyclic dicarboxylic acid component include cycloalkane dicarboxylic acids, specifically, C 1,4-cyclohexane dicarboxylic acid. 5-10 Cycloalkane 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; bridged cyclic cycloalkene dicarboxylic acids, specifically, bi- or tricycloalkene dicarboxylic acids such as norbornene dicarboxylic acid; and the like.

[0184] 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 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, anthracene dicarboxylic acid, and phenanthrene dicarboxylic acid. 10-24 arene-dicarboxylic acids, etc.; biaryl dicarboxylic acids, specifically, 2,2'-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic 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.; diarylalkane dicarboxylic acids, specifically, di-C such as 4,4'-diphenylmethane dicarboxylic acid 6-10 Aryl C 1-6 Alkane-dicarboxylic acids, etc.; diaryl ketone dicarboxylic acids, specifically, di(C 6-10 aryl) ketone-dicarboxylic acids; diaryl ether dicarboxylic acids, specifically, di(C aryl ether dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid; 6-10 aryl) ether-dicarboxylic acids; diarylsulfone dicarboxylic acids, specifically, di(C aryl) ether-dicarboxylic acids such as 4,4'-diphenylsulfone dicarboxylic acid; 6-10 aryl)sulfone-dicarboxylic acids and the like.

[0185] 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.

[0186] Examples of the diamine component different from the fluorene compound (1) include the same diamine components as those exemplified for the polyamide resin. The diamine components may be used alone or in combination of two or more.

[0187] 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 kinds.

[0188] 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, etc. 2-20 Alkane diisocyanates, lysine diisocyanate, etc.; triisocyanates such as 1,3,6-hexamethylene triisocyanate, etc.

[0189] 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.

[0190] Examples of the aromatic polyisocyanate component 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.

[0191] Examples of the polyisocyanate component 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 compound 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 compound include the compounds exemplified as the diamine component.

[0192] Examples of the polyol component include the compounds exemplified above as the polyol compound.

[0193] These resins may be polymerized by a conventional method depending on the type of resin (or the type of polymerization component 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.

[0194] (Polyimide resin and its manufacturing method) The polyimide-based 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-based resin may be formed from a polymerization component 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).

[0195] The diamine component may contain a diamine component (second diamine component) different from the fluorene compound (1) [first diamine component]. 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.

[0196] Examples of the aliphatic diamine component include alkanediamines and aliphatic diamines having a heteroatom such as an oxygen atom or a sulfur atom.

[0197] Examples of alkanediamines include linear or branched C 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 Alkanediamines (preferably C 2-12 Alkanediamines).

[0198] Examples of the aliphatic diamine having a heteroatom include aliphatic (poly)ether-based diamines, aliphatic sulfide-based diamines, and N,N-bis(aminoalkyl)-alkylamines.

[0199] Examples of the 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.

[0200] Examples of the aliphatic sulfide diamines include bis(aminoalkyl)sulfides such as bis(2-aminoethyl)sulfide.

[0201] Examples of the N,N-bis(aminoalkyl)-alkylamine include N,N-bis(3-aminopropyl)methylamine.

[0202] Examples of the alicyclic diamine component include alicyclic diamines having a monocyclic skeleton, and alicyclic diamines having a bridged cyclic or spirocyclic skeleton.

[0203] Examples of alicyclic diamines having a monocyclic skeleton include diamines having a cycloalkane skeleton and diamines having a heterocyclic skeleton.

[0204] Examples of diamines having a cycloalkane skeleton include cycloalkane diamines such as cyclohexane diamine (1,2-cyclohexane diamine, 1,3-cyclohexane diamine, 1,4-cyclohexane diamine); bis(aminoalkyl)cycloalkanes such as 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane; 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, isophorone diamine, and menthene diamine.

[0205] Examples of diamines having a heterocyclic skeleton include piperazines such as piperazine, 2-methylpiperazine, 2-ethylpiperazine, 2,5-dimethylpiperazine, and N-(2-aminoethyl)piperazine.

[0206] Examples of alicyclic diamines having a bridged cyclic skeleton include bi- or tricycloalkane diamines 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 2,6 ]decane and other bis(aminoalkyl)bi- or tricycloalkanes.

[0207] Examples of alicyclic diamines having a spirocyclic skeleton include 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0208] Examples of the aromatic diamine component 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 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.

[0209] The diamine component may contain a fluorene compound (1) [first diamine component], and the ratio of the constituent units derived from the fluorene compound (1) [first diamine component] to the total constituent 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 in the following stepwise manner, and more preferably substantially 100 mol%. If the ratio of the constituent units derived from the fluorene compound (1) [first diamine component] is in a moderate range that is not too small, the relative dielectric constant, thermal expansion and / or water absorption rate tend to be easily reduced.

[0210] The proportion of the constitutional 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 constitutional units derived from the diamine component.

[0211] 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.

[0212] 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 a bis-half ester), or a derivative such as a tetracarboxylic acid dianhydride, and is preferably a tetracarboxylic acid dianhydride.

[0213] 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 kinds.

[0214] Examples of the aromatic tetracarboxylic acid component 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, etc. These may be used alone or in combination of two or more kinds.

[0215] 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.

[0216] 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.

[0217] 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 combined and linked. Examples of groups in which two or more are combined and linked 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-].

[0218] Examples of the optionally halogenated divalent hydrocarbon group include alkylene groups or alkylidene groups [C 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) 2-6 aliphatic hydrocarbon groups such as alkynylene groups; cycloalkanediyl 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 [e.g., diarylalkanediyl groups, specifically, di-C 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 such as alkane-diyl group, diphenylether-diyl group, specifically, diphenylether-4,4'-diyl group 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 such as aryl-ketone diyl group, diphenylsulfone diyl group, specifically, diphenylsulfone-4,4'-diyl group (bisphenol S residue) 6-10 arylsulfondiyl group, etc.], and halogenated (fluorinated, chlorinated, brominated, etc.) groups thereof. As the halogenation, fluorination is preferred.

[0219] 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, C groups which may be fluorinated 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.

[0220] 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-].

[0221] 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 in combination, and more preferably ether bonds [-O-].

[0222] Representative tetracarboxylic acids having two dicarboxyarene ring skeletons (or dicarboxyaryl groups) include, for example, biaryl tetracarboxylic acids, specifically, biphenyl tetracarboxylic acids such as 3,3',4,4'-biphenyl tetracarboxylic acid and 2,3,3',4'-biphenyl tetracarboxylic acid. 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 1-10Alkanes, 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, etc. 6-10 Aryloxy-C 6-10 Aryl)C 1-10 Alkanes and the like.

[0223] Examples of the alicyclic tetracarboxylic acid component include hydrogenated products of the aromatic tetracarboxylic acids.

[0224] The tetracarboxylic acid component, particularly aromatic tetracarboxylic acid components such as arene tetracarboxylic acid, tetracarboxylic acid having two dicarboxyarene ring skeletons (or dicarboxyaryl groups), and their imide-forming derivatives, may have a substituent. The substituent may be a non-reactive substituent that is inactive in the polymerization reaction. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an acyl group, a nitro group, a cyano group, and a disubstituted amino group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group (linear or branched alkyl group) include C groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. 1-10 Alkyl groups, preferably C 1-6 Alkyl groups, more preferably C 1-4Examples of the alkoxy group (linear or branched 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 alkoxy 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 and diacetylamino groups 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 preferable, and a halogen atom such as a fluorine atom is more preferable. The number of substitutions of the substituents is, for example, 0 to 6, preferably 0 to 4, 0 to 2 in the following stepwise manner, more preferably 0 or 1, particularly 0. When the number of substitutions is 2 or more, the types of the substituents may be the same or different.

[0225] 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 their imide-forming derivatives (dianhydrides, etc.); more preferred are tetracarboxylic acids in which two dicarboxyarene ring skeletons (or dicarboxyaryl groups) are bonded directly, via an optionally halogenated divalent hydrocarbon group, an ether bond [-O-], a ketone bond, or a carbonyl group [-C(=O)-], or a group in which two or more of these are combined and linked, and their imide-forming derivatives; particularly preferred are tetracarboxylic acids in which two dicarboxyarene ring skeletons (or dicarboxyaryl groups) are bonded via an ether bond [-O-], and their imide-forming derivatives. These may be used alone or in combination of two or more.

[0226] The proportion of constituent units derived from a preferred tetracarboxylic acid component such as an aromatic tetracarboxylic acid component [particularly, the proportion of constituent units derived from a tetracarboxylic acid having two dicarboxyarene ring skeletons (or two dicarboxyaryl groups) and their imide-forming derivatives] 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 is further preferably substantially 100 mol% based on the total constituent units derived from the tetracarboxylic acid component.

[0227] The bismaleimide component may have two maleimide skeletons, and examples of the bismaleimide component include aliphatic bismaleimide components and aromatic bismaleimide components. 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 bismaleimide which may have an alkyl group, specifically, C bismaleimide 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, which may have an alkyl group 6-10 Arylene-bismaleimide, etc.; bis(maleimidoaryl)alkanes which may have an alkyl group, specifically, C 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 6-10aryl) 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 kinds.

[0228] 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, components having a carboxyl group such as ethynylphthalic acid, methylethynylphthalic acid, phenylethynylphthalic acid, and their imide-forming derivatives), and the polyisocyanate component.

[0229] The polyimide resin is preferably formed from a polymerization component containing at least a diamine component and a tetracarboxylic acid component. In the polyimide resin, the total amount of the constitutional units derived from the diamine component and 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 more preferably substantially 100 mol%.

[0230] The polyimide resin can be produced by a conventional method depending on the type of polymerization component, 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 condensing the polyamic acid (or polyamic acid) obtained in the reaction step to form an imide ring skeleton.

[0231] In the reaction step, the ratio (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 is 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, and may be approximately equimolar.

[0232] 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 the solvent 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 such as dichloromethane and chloroform (particularly, chlorinated hydrocarbons); 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, and amides such as NMP are more preferred.

[0233] In the reaction step, the ratio 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 ratio of the total amount of the diamine component and the tetracarboxylic acid component is within an appropriate range that is not too small, it is easy to prevent a decrease in film formability when molding into a film, which makes it difficult to form the film itself or to make it thin, and it also tends to easily prevent foaming and cracking during the ring-closing step due to remaining solvent.

[0234] 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, ultraviolet absorbers, heat stabilizers, light resistance 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 (for example, 0.1 to 30 parts by mass) relative to 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.

[0235] In the reaction step, the reaction may be carried out in an atmosphere of an inert gas, for example, nitrogen gas; a rare gas such as helium or argon, and is preferably carried out under 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, and preferably, in the following stepwise manner, 5 to 50°C, 10 to 40°C, 15 to 35°C, 20 to 30°C, or room temperature. The reaction time may be, for example, about 1 to 100 hours, and preferably, in the following stepwise manner, 5 to 50 hours, 10 to 30 hours, and 15 to 25 hours.

[0236] After the reaction is completed, 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 it does not necessarily have to be purified. For example, 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 resin) as described below without purification.

[0237] In the reaction step, a polyamic acid (or polyamic acid) having a structural unit derived from or corresponding to the reacted diamine component and tetracarboxylic acid component is produced. The weight average molecular weight Mw of the polyamic acid may be, for example, about 10,000 or more, and preferably is 20,000 to 1,000,000, 30,000 to 500,000, 50,000 to 300,000, 60,000 to 200,000, and 70,000 to 150,000 in the following stepwise manner. If the weight average molecular weight of the polyamic acid is in a moderate range that is not too small, there is a tendency that the moldability is easily improved.

[0238] 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 in detail, can be measured by the method described in the examples below.

[0239] 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).

[0240] The mixed liquid containing the polyamic acid (or polyamic acid) obtained in the reaction step may be directly heated to effect ring closure, or the solvent may be removed and then heated to effect ring closure. However, when molding into a film or sheet, the mixed liquid (varnish or coating composition, liquid composition) may be coated onto a predetermined substrate, and the resulting polyamic acid film or sheet may be subjected to the ring closure step.

[0241] 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 it is, or by dissolving the polyamic acid in a solvent. The solvent is the same as the solvent exemplified in the reaction step, including preferred embodiments. The concentration of the polyamic acid in the varnish or coating composition may be appropriately adjusted in consideration of 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 preferably 20 to 30 mass%.

[0242] Additives may be added to the varnish or coating composition (liquid composition). Examples of additives contained in the liquid composition include crosslinking or curing agents, defoamers, coating improvers, thickeners, lubricants, stabilizers (antioxidants, ultraviolet 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 (for example, 0.1 to 30 parts by mass) relative to 100 parts by mass of polyamic acid, preferably 20 parts by mass or less, and more preferably 10 parts by mass or less.

[0243] The varnish or coating composition (liquid composition) may be degassed before coating, if necessary, to facilitate the formation of a film having excellent mechanical properties. Examples of the 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 performed by heating. The heating temperature is, for example, about 40 to 80°C, and preferably 50 to 70°C. The degassing treatment may be performed while increasing the temperature from room temperature to the heating temperature.

[0244] Examples of the coating method for 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.

[0245] The coating film obtained by coating the varnish or coating composition (liquid composition) may be dried. The drying method is not particularly limited and may be natural drying, but a method of drying by heating is preferable from the viewpoint of productivity and the like. In the method of drying by heating, the heating temperature may be, for example, about 150°C or less, and is preferably 40 to 120°C, 50 to 110°C, 60 to 100°C, and 70 to 90°C in the following stepwise manner. The drying time can be appropriately selected depending on the heating temperature and the like, and is, for example, about 1 to 180 minutes, and preferably 5 to 120 minutes, 10 to 60 minutes, and 20 to 40 minutes in the following stepwise manner. In this way, the coating film (polyamic acid film or sheet) of the varnish or coating composition may be subjected to a ring-closing process to form a polyimide-based resin.

[0246] In the ring-closing step, it is sufficient that the polyamic acid is ring-closed or condensed to form an imide ring. For example, the polyamic acid may be heat-treated to form an imide ring (ring-closing). The heating temperature in the ring-closing step may be, for example, about 150 to 450°C, and preferably 200 to 440°C, 300 to 430°C, 330 to 420°C, and 340 to 410°C in the following stepwise manner. The ring-closing step may be carried out under normal pressure, reduced pressure (or vacuum), or pressurized conditions, but reduced pressure (or vacuum) is preferred. The treatment time in 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.

[0247] (Resin characteristics) The resin (particularly, polyimide resin) of the present disclosure has excellent electrical properties and exhibits a low relative dielectric constant. The relative dielectric constant at a frequency of 1 GHz is, for example, about 10 or less, preferably in the following stepwise manner: 2 to 5, 2.5 to 4, 2.8 to 3.5, 3 to 3.3. The relative dielectric constant at a frequency of 10 GHz is, for example, about 10 or less, preferably in the following stepwise manner: 2 to 5, 2.5 to 4, 2.6 to 3.5, 2.7 to 3.3, 2.8 to 3.2, 2.9 to 3.1. If the relative dielectric constant is within a moderate range that is not too high, there is a tendency that the use is not easily restricted from the viewpoint of electrical properties.

[0248] In this specification and claims, the relative dielectric constant can be measured in accordance with ASTM D 2520 (cavity resonator perturbation method), and in detail, can be measured by the method described in the examples below.

[0249] The coefficient of linear thermal expansion (CTE) of the resin (particularly, polyimide-based resin) of the present disclosure may be, for example, less than about 65 ppm / K, and is preferably 40 to 60 ppm / K, 45 to 57 ppm / K, and 50 to 55 ppm / K in the following stepwise manner.

[0250] In this specification and claims, the coefficient of linear thermal expansion (CTE) can be measured by the method described in the examples below.

[0251] The resin of the present disclosure (particularly, polyimide-based resin) has excellent transparency, and the light transmittance at a wavelength of 360 nm may be, for example, 0% or more, preferably 0.1 to 10%, and more preferably 0.12 to 5%.

[0252] The light transmittance at a wavelength of 380 nm may be, for example, 0.1% or more, preferably 0.2 to 10%, more preferably 0.3 to 5%, and particularly preferably 0.4 to 1%.

[0253] The light transmittance at a wavelength of 400 nm may be, for example, 0.3% or more, and is preferably in the following stepwise manner: 0.4 to 15%, 1 to 10%, 3 to 8%, and 4 to 6%.

[0254] The light transmittance at a wavelength of 600 nm may be, for example, 40% or more, and is preferably in the following stepwise manner: 40 to 99.9%, 50 to 99%, 70 to 98%, 80 to 95%, and 85 to 90%.

[0255] The light transmittance at a wavelength of 800 nm may be, for example, 40% or more, and is preferably in the following stepwise manner: 40 to 99.9%, 50 to 99%, 70 to 98%, 80 to 95%, and 85 to 90%.

[0256] In this specification and claims, the light transmittance can be measured using an ultraviolet-visible spectrophotometer for a film having an average thickness of about 30 μm (e.g., 30 to 35 μm), and in detail, can be measured by the method described in the examples below.

[0257] (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. The resin composition or molded article may contain conventional additives, such as fillers or reinforcing agents, colorants such as dyes and pigments, conductive agents, flame retardants, plasticizers, lubricants, release agents, antistatic agents, dispersants, flow control agents, leveling agents, defoamers, surface modifiers, hydrolysis inhibitors, carbon materials, stabilizers, stress reducing agents, and the like. Examples of stabilizers include antioxidants, ultraviolet absorbers, and heat stabilizers. Examples of stress reducing agents include silicone oils, silicone rubbers, various plastic powders, and various engineering plastic powders. These additives may be used alone or in combination of two or more. The total proportion of these additives may be, for example, 50 parts by mass or less, preferably 30 parts by mass or less, 0 to 10 parts by mass, or about 0.1 to 5 parts by mass, stepwise, relative to 100 parts by mass of the resin.

[0258] 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.

[0259] The shape of the molded body is not particularly limited, and examples thereof include one-dimensional structures such as linear, fibrous, and thread-like structures, two-dimensional structures such as film-like, sheet-like, plate-like, and substrate-like structures, and three-dimensional structures such as lens-like structures such as concave or convex lenses, rod-like structures, and hollow (tubular) structures.

[0260] When the molded article has a two-dimensional structure such as a film, it can be produced by forming (molding) the film using a conventional film-forming method such as a casting method (solvent casting method), a melt extrusion method, or a calendar method.

[0261] 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, and preferably the following stepwise thicknesses: 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.

[0262] The film may be an unstretched or stretched film, and even if it is a stretched film, low birefringence can be maintained. Note that such a stretched film may be either a uniaxially stretched film or a biaxially stretched film.

[0263] 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, it may be equal stretching, for example, 1.5 to 5 times stretching in both the longitudinal and transverse directions, or uneven stretching, for example, 1.1 to 4 times stretching in the longitudinal direction and 2 to 6 times stretching in the transverse direction. In the case of uniaxial stretching, it may be longitudinal stretching, for example, 2.5 to 8 times stretching in the longitudinal direction, and transverse stretching, for example, 1.2 to 5 times stretching in the transverse direction.

[0264] 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.

[0265] Such a stretched film can be obtained by stretching the film (or 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 the stretched thickness, is preferred.

[0266] 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, the 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, 30 to 35 μm in the following stepwise manner. EXAMPLES

[0267] 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.

[0268] [Evaluation method] ( 1 H-NMR) The sample was dissolved in a heavy solvent (DMSO-d6) containing tetramethylsilane as an internal standard substance, and the NMR spectrum was measured using a nuclear magnetic resonance spectrometer (BRUKER's "AVANCE III HD"). 1 H-NMR spectrum was measured.

[0269] (HPLC) The HPLC (high performance or high performance liquid chromatograph) was performed using a Shimadzu Corporation "LC-20AD" and a Phenomenex Corporation "Kinetex XB-C18" column. The sample was dissolved in acetonitrile and measured, and the HPLC purity [area %] was calculated.

[0270] [Weight average molecular weight Mw] The weight average molecular weight of the resulting polyamic acid was measured using the following measuring instrument under the following measuring conditions.

[0271] (Measuring equipment and conditions) Chromatography system: GPC (Shodex "GPC-104") Pump: LC-10ADvp (Shimadzu Corporation) Detector: Shodex RI-71 (Showa Denko Co., Ltd.) Column: Shodex GPC KF-806L, KF-802 (Showa Denko Co., Ltd.) 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: The sample, adjusted to a concentration of 0.2 w / v%, is pretreated with a membrane filter.

[0272] Average Thickness The average thickness of the film was measured using a rackness gauge ("SMD-565J-L" manufactured by TECLOCK Corporation).

[0273] [Dielectric properties] Test pieces (L80 (mm) × W1.5 (mm) × t0.03 (mm)) were prepared using the obtained polyimide film, and the dielectric constants at 1 GHz and 10 GHz were measured in a test environment of 23℃±1℃ and 50% RH±5% RH in accordance with ASTM D2520 (cavity resonator perturbation method) using the following measuring equipment.

[0274] (Measuring equipment) PNA network analyzer N5222B (Keysight Technologies, Inc.) Cavity resonator for 1GHz: CP431 (manufactured by Kanto Electronics Application Development Co., Ltd.) Cavity resonator for 10GHz: CP431 (manufactured by Kanto Electronics Application Development Co., Ltd.)

[0275] [Coefficient of Linear Thermal Expansion (CTE)] The CTE of the obtained polyimide film was measured under the following measurement conditions using a thermomechanical analyzer ("TMA8311" manufactured by Rigaku Corporation).

[0276] Heating rate: 5℃ / min Measurement temperature range: Room temperature to 400℃ Measurement mode: Tensile (load 49mN) Atmosphere: Nitrogen flow (100mL / min) Number of measurements: n=1

[0277] [UV-vis transmittance (%T)] The transmittance of the obtained polyimide film was measured using an ultraviolet-visible spectrophotometer ("V-630" manufactured by JASCO Corporation).

[0278] [Example 1-1] Synthesis of 9,9-bis(4-methoxy-3-fluorophenyl)-2,7-dibromofluorene (also called DBrBFAniFL)

[0279] [ka]

[0280] In an air atmosphere, 2,7-dibromofluorenone (DBrFLN, 33.8 g, 0.10 mol), 2-fluoroanisole (37.8 g, 0.30 mol, 3.0 eq), and β-mercaptopropionic acid (0.3 g, 3.10 mmol, 0.03 eq) were added to a 300 mL four-necked eggplant flask and mixed at 50 ° C. Methanesulfonic acid (28.8 g, 0.3 mol, 3.0 eq) was slowly added dropwise to the obtained slurry and stirred at 50 ° C. for 0.5 hours. The temperature was raised to 80 ° C., and after 5 hours, 20 mL of distilled water and 170 mL of toluene were added and stirred at 70 ° C. After draining, 42.9 g of 10 mass % NaOH aqueous solution was added to the obtained organic layer. The organic layer was washed three times with 20 mL of distilled water (total of 60 mL), and the organic layer was cooled to room temperature to precipitate a solid, which was then filtered and dried to obtain the target product, 2,7-dibromobisfluoroanisolefluorene [DBrBFAniFL or 9,9-bis(4-methoxy-3-fluorophenyl)-2,7-dibromofluorene] (white solid, 41.2 g, yield 76%, HPLC purity 98%). 1The results of the H-NMR spectrum are shown below.

[0281] 1 H-NMR(DMSO-d6,300MHz):δ(ppm)3.8(s,6H),6.8-7.1(m,6H),7.6(m,4H),8.2(d,2H)

[0282] [Example 1-2] (Synthesis of 9,9-bis(4-hydroxy-3-fluorophenyl)-2,7-dibromofluorene (also known as DBrBFPFL))

[0283] [ka]

[0284] In an air atmosphere, 2,7-dibromofluorenone (DBrFLN, 152.1 g, 0.45 mol), 2-fluorophenol (201.8 g, 1.8 mol, 4 eq), and β-mercaptopropionic acid (1.5 g, 14.0 mmol, 0.03 eq) were added to a 1 L four-necked eggplant flask and stirred at 80 ° C. Methanesulfonic acid (64.9 g, 0.68 mol, 1.5 eq) was slowly added dropwise, and after the dropwise addition was completed, the mixture was stirred at 100 ° C for 1 hour. The temperature was lowered to 80 ° C, and 56 mL of methanol and 170 mL of toluene were added as an extraction solvent for the product. 100 g of 30 mass % NaOH aqueous solution was added and drained. Then, the obtained organic layer was washed with 100 mL of distilled water (water washing) three times (total 300 mL). The organic layer was concentrated to obtain crude 2,7-dibromobisfluorophenolfluorene [DBrBFPFL or 9,9-bis(4-hydroxy-3-fluorophenyl)-2,7-dibromofluorene] (white solid, yield 210 g, yield 86%, HPLC purity 95%). 1 The results of the H-NMR spectrum are shown below.

[0285] 1 H-NMR(DMSO-d6,300MHz):δ(ppm)6.7(m,2H),6.9(m,4H),7.6(m,4H),7.9(d,2H),9.9(s,2H)

[0286] (Synthesis of 9,9-bis(4-methoxy-3-fluorophenyl)-2,7-dibromofluorene)

[0287] [ka]

[0288] In an air atmosphere, 2,7-dibromobisfluorophenolfluorene [DBrBFPFL or 9,9-bis(4-hydroxy-3-fluorophenyl)-2,7-dibromofluorene] (13.6 g, 25 mmol), potassium carbonate (10.4 g, 75 mmol, 3 eq), and 14 mL of N,N-dimethylformamide (DMF) were added to a 1 L four-neck flask and stirred at room temperature (about 25 ° C). Further, iodomethane (17.7 g, 0.13 mol, 5 eq) was added. After 7 hours, 31 g of 10 mass % HCl aqueous solution was added. The reaction solution was concentrated, and 47 mL of isopropanol (IPA) was added to the concentrated solid, and the solid was dissolved by stirring at 80 ° C. The temperature was lowered to room temperature, and the precipitated solid was filtered and dried to obtain 2,7-dibromobisfluoroanisolefluorene [DBrBFAniFL or 9,9-bis(4-methoxy-3-fluorophenyl)-2,7-dibromofluorene] (light yellow solid, yield 8.0 g, yield 56%, HPLC purity 99%). 1 The results of the H-NMR spectrum are shown below.

[0289] 1 H-NMR(DMSO-d6,300MHz):δ(ppm)3.8(s,6H),6.8-7.1(m,6H),7.6(m,4H),8.2(d,2H)

[0290] [Example 1-3] Synthesis of 9,9-bis(4-methoxy-3-fluorophenyl)-2,7-dibromofluorene DBrBFAniFL was prepared in the same manner as in Example 1-1, except that 96% by mass sulfuric acid (19.6 g, 0.2 mol, 2 eq) was used instead of methanesulfonic acid. When the progress of the reaction was monitored by HPLC 5 hours after the start of the reaction, 78% of the raw material (DBrFLN) remained, 18% of the target product (DBrBFAniFL) was produced, and a total of 3% of by-products (compounds in which a fluorine atom or a methyl group in a methoxy group has been eliminated from DBrBFAniFL) were produced.

[0291] In Example 1-1, the progress of the reaction was monitored by HPLC 4.5 hours after the start of the reaction. It was found that the raw material (DBrFLN) had been completely consumed (0%), the target product (DBrBFAniFL) had been produced at 94%, and by-products (compounds in which a fluorine atom or a methyl group in a methoxy group has been eliminated from DBrBFAniFL) had been produced at a total of 3.5%.

[0292] [Example 1-4] Synthesis of 9,9-bis(4-hydroxy-3-fluorophenyl)-2,7-dibromofluorene DBrBFPFL was prepared in the same manner as in Example 1-2, except that tungstophosphoric acid 30-hydrate (22.0 g, 7.7 mmol, 0.017 eq) was used instead of methanesulfonic acid, and 1-dodecanethiol (1.5 g, 7.7 mmol, 0.017 eq) was used instead of β-mercaptopropionic acid. When the progress of the reaction was monitored by HPLC 5 hours after the start of the reaction, 49% of the raw material (DBrFLN) remained, and 42% of the target product (DBrBFPFL) was produced, but a total of 8% of by-products (compounds in which fluorine atoms have been removed from DBrBFPFL) were produced.

[0293] In Example 1-2, when the progress of the reaction was monitored by HPLC 2 hours after the start of the reaction, it was found that the raw material (DBrFLN) had been completely consumed (0%), 90% of the target product (DBrBFPFL) had been produced, and a total of 6% of by-products (compounds in which fluorine atoms have been removed from DBrBFPFL) had been produced.

[0294] [Example 1-5] Synthesis of 9,9-bis(4-methoxy-3-fluorophenyl)-2,7-dibromofluorene DBrBFAniFL was prepared in the same manner as in Example 1-1, except that the reaction temperature was changed from 80° C. to 116° C. The progress of the reaction was monitored by HPLC 6 hours after the start of the reaction, and it was found that 24% of the raw material (DBrFLN) remained, possibly due to the inactivation of methanesulfonic acid, and 59% of the target product (DBrBFAniFL) was produced. However, perhaps due to the high temperature, a total of 15% of by-products (compounds in which a fluorine atom or a methyl group in a methoxy group has been eliminated from DBrBFAniFL) were produced.

[0295] [Example 1-6] Synthesis of 9,9-bis(4-methoxy-3-fluorophenyl)-2,7-dibromofluorene DBrBFAniFL was prepared in the same manner as in Example 1-1, except that 140 mL of toluene was used as the reaction solvent. When the progress of the reaction was monitored by HPLC 2 hours after the start of the reaction, 40% of the raw material (DBrFLN) remained, 51% of the target product (DBrBFAniFL) was produced, and a total of 5% of by-products (compounds in which a fluorine atom or a methyl group in a methoxy group has been eliminated from DBrBFAniFL) were produced.

[0296] [Example 2] Synthesis of 9,9-bis(4-methoxy-3-fluorophenyl)-N,N'-bis(diphenylmethylidene)-2,7-fluorenediamine (also called DimineBFAniFL)

[0297] [ka]

[0298] 2,7-Dibromobisanisolefluorene [DBrBFAniFL or 9,9-bis(4-methoxy-3-fluorophenyl)-2,7-dibromofluorene] (34.3 g, 0.06 mol), benzophenone imine (26.1 g, 0.14 mol, 2.4 eq), sodium tert-butoxide (16.1 g, 0.17 mol, 2.8 eq), and 100 mL of toluene were added to a 300 mL four-necked eggplant flask, replaced with nitrogen, and stirred at 80°C to dissolve. 2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl (BINAP, 0.56g, 1.0mmol, 0.015eq) and bis(dibenzylideneacetone)palladium(0) [Pd(dba)2, 0.28g, 0.5mmol, 0.008eq] were added and stirred at 80°C for 1 hour. 222mL of tetrahydrofuran (THF) was added to dissolve the precipitate, and 9.8g of 10% by mass HCl aqueous solution was added and stirred. The operation of washing (water washing) with 60mL of distilled water was carried out three times (total 180mL), and after draining, the organic layer was concentrated to obtain 96g of crude material. 100mL of toluene was added to the obtained crude material, dissolved at 90°C, and the temperature was slowly lowered to room temperature to precipitate a solid. The precipitated solid was filtered and dried to obtain 2,7-diiminebisfluoroanisolefluorene [DimineBFAniFL or 9,9-bis(4-methoxy-3-fluorophenyl)-N,N'-bis(diphenylmethylidene)-2,7-fluorenediamine] (yellow solid, 39.1 g, yield 84.2%, HPLC purity 98%). 1 The results of the H-NMR spectrum are shown below.

[0299] 1 H-NMR(DMSO-d6,300MHz):δ(ppm)3.8(s,6H),6.4-6.6(m,6H),6.7-7.0(m,4H),7.0-7.3(m,10H),7.4-7.7(m,12H)

[0300] [Reference Example 1] Introduction of phthalimide To produce DABFAniFL according to the following reaction scheme, phthalimide was used as a protecting group instead of benzophenoneimine. DBrBFAniFL (2.23 g, 3.9 mmol), potassium phthalimide (1.44 g, 7.8 mmol, 2 eq), and 6.6 mL of dimethyl sulfoxide (DMSO) were added to a reaction vessel, and after replacing with nitrogen, copper iodide (0.15 g, 0.78 mmol, 0.2 eq) was added and reacted at 140°C for 5 hours, but the reaction did not proceed.

[0301] [ka]

[0302] [Example 3] Synthesis of 9,9-bis(4-methoxy-3-fluorophenyl)-2,7-diaminofluorene (also called DABFAniFL)

[0303] [ka]

[0304] 2,7-diiminebisfluoroanisolefluorene [DimineBFAniFL or 9,9-bis(4-methoxy-3-fluorophenyl)-N,N'-bis(diphenylmethylidene)-2,7-fluorenediamine] (30.1 g, 0.07 mol) and 89 mL of THF were added to a 300 mL four-necked eggplant flask, and after nitrogen replacement, the mixture was dissolved at room temperature. 18.9 mL of 10 mass% HCl aqueous solution was added and stirred at room temperature (about 25 ° C) for 24 hours. 80 mL of saturated NaHCO3 aqueous solution was added to the reaction solution and the liquids were separated. The obtained organic layer was concentrated to obtain a solution of 2,7-diaminobisfluoroanisolefluorene (brown oil, 33.0 g). Column purification was performed with toluene / ethyl acetate to obtain 2,7-diaminobisfluoroanisolefluorene [DABFAniFL or 9,9-bis(4-methoxy-3-fluorophenyl)-2,7-diaminofluorene] (white solid, 13.8 g, yield 46%, HPLC purity 84%). 1 The results of the H-NMR spectrum are shown below.

[0305] 1 H-NMR(DMSO-d6,300MHz):δ(ppm)3.8(s,6H),5.0(s,4H),6.5(m,4H),6.7-6.9(m,4H),7.0-7.1(t,2H),7.2-7.4(d,2H)

[0306] [Example 4] Synthesis of 9,9-bis(6-methoxy-2-naphthyl)-2,7-dibromofluorene (also called DBrBMNFL)

[0307] [ka]

[0308] In an air atmosphere, 2,7-dibromo-9,9-bisnaphtholfluorene [DBrBNF or 9,9-bis(6-hydroxy-2-naphthyl)-2,7-dibromofluorene] (60.8 g, 0.1 mol) prepared according to Synthesis Example 1 described in JP 2022-042002 A, potassium carbonate (41.5 g, 0.3 mol, 3 eq), and N,N-dimethylformamide (DMF) were added to a 300 mL four-neck flask, and stirred at room temperature (about 25 ° C). Further, iodomethane (42.6 g, 0.3 mol, 3 eq) was added. After 5 hours, 45 g of methanol was added and stirred at 5 to 10 ° C for 1 hour. The precipitated solid was filtered, the obtained solid was placed in a 300 mL recovery flask, 250 mL of water was added, and the mixture was stirred at room temperature (approximately 25°C) for 30 minutes. The solid was filtered and then dried to obtain DBrBMNFL (light yellow solid, yield 47 g, yield 74%, HPLC purity 99%). 1 The results of the H-NMR spectrum are shown below.

[0309] 1 H-NMR(DMSO-d6,300MHz):δ(ppm)3.9(s,6H),7.1(m,2H),7.2-7.4(m,4H),7.6-7.8(m,10H)8.0(d,2H)

[0310] [Example 5] Synthesis of 9,9-bis(6-methoxy-2-naphthyl)-N,N'-bis(diphenylmethylidene)-2,7-fluorenediamine (also called DimineBMNFL)

[0311] [ka]

[0312] In a 300 mL four-necked eggplant flask, DBrBMNFL (381.8 g, 0.6 mol), benzophenone imine (261.0 g, 1.4 mol, 2.4 eq), sodium tert-butoxide (161.4 g, 1.68 mol, 2.8 eq), and 1015 mL of toluene were added, substituted with nitrogen, and stirred at 60 ° C to dissolve. 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP, 5.6 g, 9.0 mmol, 0.015 eq), and bis(dibenzylideneacetone)palladium(0) [Pd(dba)2, 1.7 g, 3.0 mmol, 0.005 eq] were added, and the mixture was stirred at 80 ° C for 3 hours. 140 g of toluene and 200 mL of distilled water were added, and the organic layer was washed once, and then 100 mL of 10% by mass hydrochloric acid was added to the obtained organic layer to wash it. The organic layer was washed twice with 200 mL of distilled water, and then filtered through Celite to remove palladium. 8.5 L of methanol was added dropwise to 1790 g of the resulting toluene solution to precipitate a solid, which was then filtered and dried. 2.8 L of methanol, a poor solvent, was added to 377 g of the resulting solid, which was stirred for 1 hour (repulp washing), filtered, and dried to obtain DimineBMNFL (yellow solid, 350.7 g, yield 70%, HPLC purity 83%). 1 The results of the H-NMR spectrum are shown below.

[0313] 1 H-NMR(DMSO-d6,300MHz):δ(ppm)3.8(s,6H),6.7-6.8(m,4H),6.8-7.0(m,2H),7.0-7.2(m,12H),7.3-7.7(m,20H)

[0314] [Example 6] Synthesis of 9,9-bis(6-methoxy-2-naphthyl)-2,7-diaminofluorene (also called DABMNFL)

[0315] [ka]

[0316] DimineBMNFL (230g, 0.28mol) and 625mL of THF were added to a 2L four-necked flask, and after argon (Ar) replacement, they were dissolved at room temperature. 57mL of 10% by mass HCl aqueous solution was added and stirred at room temperature (about 25°C) for 29 hours. 230mL of 0.72M NaHCO3 aqueous solution was added to the reaction solution and stirred at room temperature. The reaction solution was concentrated, and 1L of ethyl acetate and 1L of distilled water were added. After separation, the organic layer was collected and washed with 0.5L of saline. The organic layer was collected, concentrated, and dried to obtain a solid of DABMNFL (250g). The solid was purified by column purification with a mixed solvent of toluene / ethyl acetate (volume ratio) = 95 / 5 to 90 / 10 to obtain DABMNFL (white solid, 42.1g, yield 30.1%, HPLC purity 97%). 1 The results of the H-NMR spectrum are shown below.

[0317] 1 H-NMR(DMSO-d6,300MHz):δ(ppm)3.8(s,6H),5.0(s,4H),6.5(m,2H),6.6(s,2H),7.1(m,2H),7.2-7.4(m,6H),7.5(s,2H),7.6(d,2H),7.8(d,2H)

[0318] [Example 7] Synthesis of polyimide resin using DABFAniFL The reactor was dried under reduced pressure and replaced with argon, and DABFAniFL (9.0709 g, 0.02 mol) and 44.9 g of NMP [1-methyl-2-pyrrolidone, CAS.872-50-4, Fujifilm Wako Pure Chemical Industries, Ltd.] were added so that the concentration of the resulting polyamic acid was 25% by mass, and the mixture was stirred. ODPA [4,4'-oxydiphthalic anhydride, CAS.1823-59-2, Tokyo Chemical Industry Co., Ltd. (TCI)] (6.3312 g, 0.02 mol) was added at 0 to 15 ° C., and the mixture was reacted at 25 ° C. for 20 hours to obtain a mixture containing polyamic acid A (DABFAniFL / ODPA, weight average molecular weight 110,000).

[0319] A polyethylene terephthalate (PET) film was attached onto a heat-resistant glass plate, and the mixture containing the obtained polyamic acid A was applied onto the PET film using an applicator ("SA-201" manufactured by Tester Sangyo Co., Ltd.) so that the coating thickness was 200 μm (the applicator was set to 203.2 μm). After drying at 80°C and 1 atm for 30 minutes, the mixture was peeled off from the PET film to prepare a cast film of polyamic acid A. A Kapton film was placed on a heat-resistant glass plate, the obtained cast film was placed on the Kapton film, and the outer periphery of the cast film was attached with polyimide tape to fix it to the Kapton film, and the polyimide film A (average thickness 34 μm) was obtained by heating at 350°C under vacuum for 1 hour. The obtained polyimide film A could be obtained as an independent single film even when peeled off from the Kapton film.

[0320] [Example 8] Synthesis of polyimide resin using DABMNFL A mixed solution containing polyamic acid B (DABMNFL / ODPA, weight average molecular weight 72,000) was obtained in the same manner as in Example 7, except that DABMNFL (10.5961 g, 0.02 mol) was used instead of DABFAniFL.

[0321] A cast film of polyamic acid B was prepared using a mixed solution containing the obtained polyamic acid B instead of the mixed solution containing polyamic acid A, and the heating conditions of the cast film of polyamic acid B were changed to heating at 350° C. under vacuum for 1 hour, and then heating at 400° C. under vacuum for 1 hour. Except for this, a polyimide film B (average thickness 33 μm) was obtained in the same manner as in Example 7. The obtained polyimide film B could be obtained as an independent single film even when peeled off from the Kapton film.

[0322] [Reference Example 2] Synthesis of polyimide resin using 9,9-bis(4-amino-3-fluorophenyl)fluorene (also called BOFAF) A polyimide resin was prepared using BOFAF (CAS. 127926-65-2, manufactured by Osaka Gas Chemicals Co., Ltd.) represented by the following formula.

[0323] [ka]

[0324] That is, a reactor that was dried under reduced pressure was replaced with argon, and BOFAF (7.7123 g, 0.02 mol) and 29 g of NMP were added so that the concentration of the resulting polyamic acid was 33 mass% and stirred. ODPA (6.3312 g, 0.02 mol) was added at 0 to 15°C, and the mixture was reacted at 25°C for 20 hours to obtain a mixed solution containing polyamic acid C (BOFAF / ODPA, weight average molecular weight 210,000).

[0325] The obtained mixture containing polyamic acid C was degassed under vacuum (reduced pressure), and NMP was added so that the polyamic acid concentration became 20% by mass. The obtained mixture was applied to a heat-resistant glass plate using an applicator so that the coating thickness was 200 μm, and then dried at 80° C. and 1 atm for 30 minutes, and heated at 350° C. under vacuum for 1 hour to obtain polyimide film C (average thickness 30 μm). The obtained polyimide film C could be obtained as an independent single film even when peeled off from the heat-resistant glass plate.

[0326] [Reference Example 3] Synthesis of polyimide resin using 9,9-bis(4-aminophenyl)fluorene (also called BAF) A polyimide resin was prepared using BAF (CAS.15499-84-0, manufactured by Osaka Gas Chemicals Co., Ltd.) represented by the following formula.

[0327] [ka]

[0328] The reactor was dried under reduced pressure and replaced with argon, and BAF (6.9794 g, 0.02 mol) and 53 g of NMP were added so that the concentration of the resulting polyamic acid was 20% by mass, followed by stirring. ODPA (6.3312 g, 0.02 mol) was added at 0 to 15°C, and the mixture was reacted at 25°C for 20 hours to obtain a mixture containing polyamic acid D (BAF / ODPA, weight average molecular weight 110,000).

[0329] The obtained mixed solution containing polyamic acid D was applied to a heat-resistant glass plate using an applicator to a coating thickness of 200 μm, and then dried at 80° C. and 1 atm for 30 minutes, followed by heating at 350° C. under vacuum for 1 hour to obtain polyimide film D (average thickness 33 μm). The obtained polyimide film D could be obtained as an independent film even when peeled off from the heat-resistant glass plate.

[0330] The evaluation results of each of the obtained polyimide films are shown below.

[0331] [Evaluation of relative dielectric constant]

[0332] [Table 1]

[0333] In applications such as circuit boards, the lower the dielectric constant (particularly the dielectric constant at high frequencies), the more preferable, and the polyimide resins obtained in the examples showed low dielectric constants. In addition, in Reference Examples 2 and 3, which used diamine components having a 9,9-bisarylfluorene skeleton (cardo skeleton), Reference Example 2, which contained fluorine atoms, had a higher dielectric constant than Reference Example 3, whereas Example 7 had a low dielectric constant even though it contained fluorine atoms.

[0334] [Evaluation of CTE]

[0335] [Table 2]

[0336] The results of measuring the CTE from room temperature (about 25° C.) to 250° C. are shown in Table 2. When a cardo skeleton is present, the CTE tends to be high, but as is clear from the results in Table 2, even though the cardo skeleton is present, the Examples showed lower CTEs than the Reference Examples.

[0337] [Transmittance evaluation]

[0338] [Table 3]

[0339] As is clear from the results in Table 3, the Examples were slightly inferior to the Reference Examples in terms of transparency at low wavelengths, but were relatively excellent. Comparing Examples 7 and 8, Example 7, which contains fluorine atoms, was more excellent in transparency. [Industrial Applicability]

[0340] Any of the fluorene compounds disclosed herein can be effectively used as a resin raw material (or polymerization component) for forming a resin; a resin additive for modifying a resin, such as a refractive index enhancer; or a light-emitting material such as a fluorescent material or a phosphorescent material.

[0341] Furthermore, resins using the fluorene compound of the present disclosure as a resin raw material (polymerization component) can be used in various applications, such as 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 parts (electric and electronic devices), specifically, antistatic agents, carrier transport agents, light emitting bodies, organic photoconductors, 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.

[0342] The resin can also be used as an optical member. Representative optical members include optical films (optical sheets) such as films for liquid crystal displays and films for organic EL displays, optical lenses such as lenses for glasses and lenses for cameras, prisms, holograms, optical fibers, etc.

[0343] Examples of optical films include polarizing films, polarizing elements and polarizing plate protective films that constitute polarizing films, phase difference films, alignment films (alignment films), viewing angle widening (compensation) films, diffusion 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 that can be used for these optical films 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.

[0344] Examples of optical lenses include glasses 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 devices or mobile devices with camera functions such as smartphones, mobile phones, and digital cameras; vehicle-mounted cameras such as drive recorders and backup cameras (rear cameras); and the like.

[0345] 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 laminates, insulating varnishes, insulating films (interlayer insulating films, anisotropic conductive films, etc.), circuit boards [printed boards or printed wiring boards such as flexible printed boards (FPCs)], materials for base station antennas, and other electrical and electronic materials or electrical and electronic components, 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 circuit boards such as materials for printed wiring boards for Wi-Fi communication, 5G or 6G communication.

Claims

1. The following formula (1) 【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 each independently represents a hydrocarbon group; X １ａ and X １ｂ each independently represents a halogen atom; n1a and n1b each independently represent an integer of 0 or more; R ３ａ and R ３ｂ each independently represents a substituent, and m3a and m3b each independently represent an integer of 0 or more. A fluorene compound represented by the formula:

2. In the formula (1), R １ａ and R １ｂ are independently a hydrocarbon group, m1a and m1b are independently an integer of 0 to 2, Z １ａ and Z １ｂ is independently C ６－１４ is an arene ring, R ２ａ and R ２ｂ are independently an alkyl group; X １ａ and X １ｂ is a fluorine atom, n1a and n1b are independently an integer of 0 to 4, R ３ａ and R ３ｂ The fluorene compound according to claim 1, wherein m3a and m3b are independently an integer of 0 to 2.

3. In the formula (1), R １ａ and R １ｂ is independently an alkyl group; m1a and m1b are independently 0 or 1; Z １ａ and Z １ｂ But independently, C ６－１２ is an arene ring, R ２ａ and R ２ｂ But independently, C １－６ is an alkyl group, X １ａ and X １ｂ is a fluorine atom, n1a and n1b are independently an integer of 0 to 2, R ３ａ and R ３ｂ The fluorene compound according to claim 1 or 2, wherein m3a and m3b are independently an alkyl group, and m3a and m3b are independently 0 or 1.

4. The following formula (2) 【Chemistry 2】 (In the formula, Z ２ａ and Z ２ｂ each independently represents a benzene ring or a naphthalene ring, R ４ａ and R ４ｂ m4a and m4b 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 ５ａ and R ５ｂ m5a and m5b each independently represent an integer of 0 or more; R １ａ and R １ｂ , m1a and m1b, Z １ａ and Z １ｂ , R ２ａ and R ２ｂ , X １ａ and X １ｂ , n1a and n1b, R ３ａ and R ３ｂ , m3a and m3b are the same as those in formula (1). A method for producing a fluorene compound represented by formula (1) according to claim 1 or 2, comprising a hydrolysis step of hydrolyzing a fluorene compound represented by formula (1).

5. The following formula (2) 【Chemistry 3】 (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 each independently represents a hydrogen atom or a hydrocarbon group, X １ａ and X １ｂ each independently represents a halogen atom; n1a and n1b each independently represent an integer of 0 or more; R ３ａ and R ３ｂ each independently represents a substituent; m3a and m3b 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 ４ａ and R ４ｂ m4a and m4b 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 ５ａ and R ５ｂ each independently represents a substituent, and m5a and m5b each independently represent an integer of 0 or more. A fluorene compound represented by the formula:

6. The following formula (3) 【Chemistry 4】 (In the formula, X ２ａ and X ２ｂ each independently represents a halogen atom, R １ａ and R １ｂ , m1a and m1b, Z １ａ and Z １ｂ , R ２ａ and R ２ｂ , X １ａ and X １ｂ , n1a and n1b, R ３ａ and R ３ｂ , and m3a and m3b are the same as those in formula (2). and an imine compound represented by the following formula (4a) and an imine compound represented by the following formula (4b): 【Chemistry 5】 (In the formula, Z ２ａ and Z ２ｂ , R ４ａ and R ４ｂ , m4a and m4b, Z ３ａ and Z ３ｂ , R ５ａ and R ５ｂ , and m5a and m5b are the same as those in formula (2). A method for producing a fluorene compound represented by formula (2) according to claim 5, comprising a coupling step of subjecting

7. The following formula (3) 【Chemistry 6】 (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 each independently represents a hydrocarbon group; X １ａ and X １ｂ each independently represents a halogen atom; n1a and n1b each independently represent an integer of 0 or more; R ３ａ and R ３ｂ each independently represents a substituent; m3a and m3b each independently represent an integer of 0 or more; X ２ａ and X ２ｂ each independently represents a halogen atom.) A fluorene compound represented by the formula:

8. The following formula (5) 【Chemistry 7】 (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; X ２ａ and X ２ｂ each independently represents a halogen atom.) and an arene compound represented by the following formula (6a) and an arene compound represented by the following formula (6b): 【Chemistry 8】 (In the formula, Z １ａ and Z １ｂ each independently represents an arene ring, R ２ａ and R ２ｂ each independently represents a hydrocarbon group; X １ａ and X １ｂ each independently represents a halogen atom; n1a and n1b each independently represent an integer of 0 or more; R ３ａ and R ３ｂ each independently represents a substituent, and m3a and m3b each independently represent an integer of 0 or more.

8. A method for producing a fluorene compound represented by formula (3) according to claim 7, comprising the step of forming a cardo skeleton by reacting

9. The following formula (1) 【Chemistry 9】 (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 each independently represents a hydrogen atom or a hydrocarbon group, X １ａ and X １ｂ each independently represents a halogen atom; n1a and n1b each independently represent an integer of 0 or more; R ３ａ and R ３ｂ each independently represents a substituent, and m3a and m3b each independently represent an integer of 0 or more. A resin comprising a fluorene compound represented by the formula (I) as a polymerization component.

10. The resin of claim 9 which is a polyimide resin.

11. A molded article comprising the resin according to claim 9 or 10.

12. The molded article according to claim 11, which is a circuit board.

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