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

Abstract

新規なフルオレン化合物(フルオレン系アミン化合物)、およびその前駆体(フルオレン系アジド化合物)、ならびにそれらの製造方法および用途を提供する。【解決手段】下記式(1)で表されるアミン化合物またはその塩を調製する。TIFF2026112440000029.tif49153(式中、R1は、置換基を示し、m1は、0~8の整数を示し、Z1aおよびZ1bは、独立してアレーン環を示し、A1aおよびA1bは、独立してアルキレン基を示し、n1aおよびn1bは、独立して1以上の整数を示し、R2aおよびR2bは、独立して置換基を示し、m2aおよびm2bは、独立して0以上の整数を示す。)

Description

[Technical Field]

[0001] This disclosure relates to fluorene compounds having a 9,9-bisarylfluorene skeleton and an amino group (fluorene-based amine compounds), fluorene compounds having a 9,9-bisarylfluorene skeleton and an azide group (fluorene-based azide compounds), as well as methods for producing these compounds and their applications (resins, resin compositions, molded articles, etc.). [Background technology]

[0002] Compounds containing a 9,9-bisarylfluorene skeleton are often used as resin raw materials or polymerization components (monomers) or resin additives due to their excellent optical properties and heat resistance.

[0003] Japanese Patent Publication No. 5-031341 (Patent Document 1) describes a method of forming a polyimide by reacting a diamine component containing a predetermined aromatic diamine having a 9,9-bis(4-aminophenyl)fluorene skeleton with a tetracarboxylic dianhydride.

[0004] Japanese Patent Publication No. 61-283617 (Patent Document 2) describes the use of a compound having a 9,9-bis(aminophenyl)fluorene skeleton as a curing agent for epoxy resins. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 5-031341 [Patent Document 2] Japanese Patent Application Publication No. 61-283617 [Overview of the project] [Problems that the invention aims to solve]

[0006] The examples in Patent Documents 1 and 2 specifically describe the use of 9,9-bis(4-aminophenyl)fluorene (hereinafter also referred to as BAF).

[0007] However, as will be described later in the Examples section, the inventors' investigations revealed that BAF has low solubility in organic compounds (such as organic solvents). Therefore, it is difficult to apply to applications where high solubility is required, and there has been a need for the development of new amine compounds having a 9,9-bisarylfluorene skeleton.

[0008] Therefore, the object of this disclosure is to provide novel fluorene compounds (fluorene-based amine compounds), their precursors (fluorene-based azide compounds), and methods for producing them and their uses. [Means for solving the problem]

[0009] As a result of diligent research to achieve the above objectives, the present inventors have discovered that a specific fluorene compound (fluorene-based amine compound) combining an alkylene oxy group between a 9,9-bisarylfluorene skeleton and an amino group can be produced by a specific method, is a novel amine compound, and exhibits surprisingly high solubility, thus completing the present invention (or this disclosure). That is, this disclosure may include the following embodiments, etc.

[0010] Appearance [1]: An amine compound represented by the following formula (1) or a salt thereof.

[0011] [ka]

[0012] (In the formula, R 1 represents a substituent, and m1 represents an integer from 0 to 8. Z 1a and Z 1b These independently exhibit an arene ring, A1a and A 1b each independently represents an alkylene group, n1a and n1b each independently represent an integer of 1 or more, R 2a and R 2b each independently represents a substituent, and m2a and m2b each independently represent an integer of 0 or more.)

[0013] Aspect [2]: In the above formula (1), R 1 represents a hydrocarbon group, m1 represents an integer of 0 to 4, Z 1a and Z 1b each independently represents a C 6-14 arene ring, A 1a and A 1b each independently represents a C 2-6 alkylene group, n1a and n1b each independently represent an integer of 1 to 10, R 2a and R 2b each independently represents a hydrocarbon group, and m2a and m2b each independently represent an integer of 0 to 4, the amine compound or a salt thereof according to Aspect [1].

[0014] Aspect [3]: In the above formula (1), R 1 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, m1 represents an integer of 0 to 2, Z 1a and Z 1b each independently represents a C 6-12 arene ring, A 1a and A 1b each independently represents a C 2-4 alkylene group, n1a and n1b each independently represent an integer of 1 to 6, R 2a and R 2bThe amine compound or salt thereof according to embodiment [1] or [2], wherein m2a and m2b independently represent an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and m2a and m2b independently represent an integer from 0 to 2.

[0015] Appearance [4]: An amine compound or salt thereof according to any one of embodiments [1] to [3], wherein the 5% weight loss temperature is 230 to 350°C.

[0016] Appearance [5]: An amine compound or salt thereof according to any one of embodiments [1] to [4], wherein the refractive index at a temperature of 25°C and a wavelength of 589 nm is 1.6 to 1.68.

[0017] Appearance [6]: An amine compound or salt thereof according to any one of embodiments [1] to [5], which is soluble in at least one solvent selected from aromatic hydrocarbons, alcohols, ethers, ketones, esters, ether esters, and amides at a temperature of 25°C and a concentration of 10% by mass or more.

[0018] Appearance [7]: A crystalline amine compound or salt thereof as described in any of embodiments [1] to [6].

[0019] Appearance [8]: An amine compound or salt thereof according to any one of embodiments [1] to [7], wherein the amount of residual solvent is 5% by mass or less.

[0020] Appearance [9]: A method for producing an amine compound or a salt thereof according to any one of embodiments [1] to [8], comprising a reduction step of reducing an azide compound represented by the following formula (2).

[0021] [ka]

[0022] (In the formula, R 1represents a substituent, and m1 represents an integer from 0 to 8. Z 1a and Z 1b These independently exhibit an arene ring, A 1a and A 1b n1a and n1b independently represent an alkylene group, and n1a and n1b independently represent integers greater than or equal to 1. R 2a and R 2b (where m2a and m2b independently represent substituents, and m2a and m2b independently represent non-negative integers.)

[0023] Appearance

[10] : The manufacturing method according to embodiment [9], further comprising a crystallization step of precipitating the amine compound or a salt thereof according to any of embodiments [1] to [8] obtained in the reduction step from a solvent containing at least esters.

[0024] Appearance

[11] : An azide compound represented by formula (2) as described in [9].

[0025] Appearance

[12] : A method for producing an azide compound according to embodiment

[11] , comprising an azidation step of reacting a compound represented by the following formula (3) with an azidating agent.

[0026] [ka]

[0027] (In the formula, R 1 represents a substituent, and m1 represents an integer from 0 to 8. Z 1a and Z 1b These independently exhibit an arene ring, A 1a and A 1b n1a and n1b independently represent an alkylene group, and n1a and n1b independently represent integers greater than or equal to 1. R 2a and R 2b m2a and m2b independently represent substituents, and m2a and m2b independently represent integers greater than or equal to 0. L 1a and L 1b (It independently exhibits a leaving group.)

[0028] Appearance

[13] : A liquid composition comprising an amine compound represented by formula (1) or a salt thereof, as described in any of embodiments [1] to [8], and a solvent.

[0029] Appearance

[14] : The liquid composition according to embodiment

[13] , wherein the solvent comprises at least one selected from aromatic hydrocarbons, alcohols, ethers, ketones, esters, ether esters, and amides.

[0030] Appearance

[15] : A resin comprising, as a resin raw material, an amine compound or a salt thereof as described in any of embodiments [1] to [8], and / or an azide compound as described in embodiment

[11] .

[0031] Appearance

[16] : The resin according to embodiment

[15] , which is a polyamic acid or polyimide resin and comprises, as polymerization components, a diamine component containing an amine compound or a salt thereof as described in any of embodiments [1] to [8] and a tetracarboxylic acid component.

[0032] Appearance

[17] : A resin composition comprising, as an additive, an amine compound or a salt thereof as described in any of embodiments [1] to [8], and / or an azide compound as described in embodiment

[11] .

[0033] Appearance

[18] : A molded article comprising the resin described in embodiment

[15] or

[16] , and / or the resin composition described in embodiment

[17] .

[0034] Appearance

[19] : A molded article according to embodiment

[18] , which is in the form of a film.

[0035] Furthermore, this disclosure may achieve the following secondary objectives (solve secondary problems).

[0036] In other words, another object of this disclosure is to provide fluorene compounds (fluorene-based amine compounds) exhibiting high solubility, their precursors (fluorene-based azide compounds), and methods for producing them and their uses.

[0037] Another object of this disclosure is to provide fluorene compounds (fluorene-based amine compounds) exhibiting high heat resistance (high 5% weight loss temperature), their precursors (fluorene-based azide compounds), and methods for producing them and their uses.

[0038] Another object of this disclosure is to provide fluorene compounds (fluorene-based amine compounds) that exhibit high heat resistance (high 5% weight loss temperature) and are meltable at relatively low temperatures (low melting point or glass transition temperature Tg), as well as their precursors (fluorene-based azide compounds), and methods for producing them and their uses.

[0039] Another object of this disclosure is to provide fluorene compounds (fluorene-based amine compounds) exhibiting a high refractive index, their precursors (fluorene-based azide compounds), and methods for producing them and their uses.

[0040] Another object of this disclosure is to provide fluorene compounds (fluorene-based amine compounds) that exhibit low solvent residue and high handling properties (high handling or low viscosity), their precursors (fluorene-based azide compounds), as well as methods for producing them and their uses.

[0041] Another object of this disclosure is to provide fluorene compounds (fluorene-based amine compounds) capable of forming resins exhibiting excellent moldability (particularly film moldability) and / or high colorless transparency, as well as their precursors (fluorene-based azide compounds), and methods for producing them and their uses.

[0042] In this specification and the claims, the number of carbon atoms in a substituent is defined as C1, C6, C 10 These are sometimes used to indicate this. For example, an alkyl group with 1 carbon atom is called a "C1 alkyl group," and an aryl group with 6 to 10 carbon atoms is called a "C1 alkyl group." 6-10 It is sometimes referred to as an "aryl group," etc.

[0043] Furthermore, in this specification and the claims, “independently” means that multiple components are independent components, for example, Z 1a and Z 1b In this case, it means that the arene rings may be the same as the other arene rings, or they may be different arene rings.

[0044] Furthermore, in this specification and the claims, the numerical range indicated by "X~Y" may include the numerical values ​​X and Y. [Effects of the Invention]

[0045] This disclosure provides novel fluorene compounds (fluorene-based amine compounds), their precursors (fluorene-based azide compounds), and methods for producing them and their uses. [Brief explanation of the drawing]

[0046] [Figure 1] Figure 1 shows the 1H-NMR spectrum of BPEF-NH2 obtained in Example 2. [Figure 2] Figure 2 is a chart showing the powder X-ray diffraction pattern of the BPEF-NH2 crystal obtained in Example 2. [Figure 3] Figure 3 is a chart showing the powder X-ray diffraction pattern of the BPEF-NH2 crystal obtained in Example 3(3-1). [Modes for carrying out the invention]

[0047] The fluorene compounds (fluorene-based amine compounds) of this disclosure may have high solubility. Therefore, they can be effectively applied to applications requiring high solubility. Furthermore, the fluorene compounds of this disclosure may also have high heat resistance and / or a high refractive index. In addition, the fluorene compounds of this disclosure exhibit high heat resistance (high 5% weight loss temperature) and are meltable at relatively low temperatures (low melting point or glass transition temperature Tg), making them easily melt-mixed with other components (e.g., epoxy resins) and readily or efficiently forming a homogeneous composition (such as a curable composition). The fluorene compounds of this disclosure may have low solvent residue and high handling properties (high handling or low viscosity). Moreover, the fluorene compounds of this disclosure may be capable of forming resins that exhibit excellent moldability (especially film moldability) and / or high colorless transparency.

[0048] [Fluorene-based amine compounds] The fluorene-based amine compound (1) of this disclosure [hereinafter also referred to as fluorene-based amine compound (1) or amine compound (1)] is represented by the following formula (1).

[0049] [ka]

[0050] (In the formula, R 1 represents a substituent, and m1 represents an integer from 0 to 8. Z 1a and Z 1b These independently exhibit an arene ring, A 1a and A 1b n1a and n1b independently represent an alkylene group, and n1a and n1b independently represent integers greater than or equal to 1. R 2a and R 2b (where m2a and m2b independently represent substituents, and m2a and m2b independently represent non-negative integers.)

[0051] In the above equation (1), R 1The substituent represented by may be an inactive (or nonpolymerizable) group that is inert to the reaction. 1 Examples of substituents represented by [-OR] include halogen atoms, hydrocarbon groups, and groups. h ](where R h (represents a hydrocarbon group), group [-SR h ](where R h Examples include hydrocarbon groups, acyl groups, nitro groups, cyano groups, and substituted amino groups (mono or disubstituted amino groups).

[0052] In this specification and in the claims, R h The hydrocarbon groups represented by each symbol represent independent hydrocarbon groups, which may be identical or different from one another.

[0053] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0054] Hydrocarbon group (or R h ) may be a saturated or unsaturated hydrocarbon group, an aliphatic (including alicyclic) or aromatic hydrocarbon group, and a hydrocarbon group with a linear (linear or branched) or cyclic structure, or a combination of linear and cyclic structures. Note that the hydrocarbon group (or R) h The number of carbon atoms in the compound is not particularly limited, but may be as low as 20, for example, and preferably in the following increments: 1-16, 1-12, 1-10, 1-8, and 1-6.

[0055] Typical hydrocarbon groups (or R h Examples of alkyl groups include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups.

[0056] Examples of alkyl groups (linear or branched alkyl groups) include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl groups. 1-10 Examples include alkyl groups, preferably C 1-6 Alkyl alkyl groups, more preferably C1-4 It is an alkyl group.

[0057] Examples of cycloalkyl groups include cyclopentyl groups, cyclohexyl groups, and other C groups. 5-10 Examples include cycloalkyl groups.

[0058] Examples of aryl groups include phenyl groups, alkylphenyl groups, biphenylyl groups, naphthyl groups, etc. 6-12 Examples include aryl groups. Alkylphenyl groups include mono- or tri-C groups such as methylphenyl (or tolyl) and dimethylphenyl (or xylyl) groups. 1-4 Alkylphenyl groups are one example.

[0059] Examples of aralkyl groups include benzyl groups, phenethyl groups, and other C groups. 6-10 Aryl-C 1-4 Alkyl groups are examples.

[0060] The group [-OR h ] and base [-SR h In ], R h As a hydrocarbon group represented by R 1 Examples of hydrocarbon groups include those similar to the hydrocarbon groups exemplified above, including preferred embodiments (e.g., alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, etc.). The group [-OR h ] and base [-SR h Examples of such groups include the groups corresponding to the examples of hydrocarbon groups mentioned above, and representative groups include [-OR h Examples include alkoxy groups, cycloalkyloxy groups, aryloxy groups, and aralkyloxy groups; representative groups [-SR] h Examples of these groups include alkylthio groups, cycloalkylthio groups, arylthio groups, and aralkylthio groups.

[0061] Examples of alkoxy groups (linear or branched alkoxy groups) include methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, and t-butoxy groups.1-10 An alkoxy group can be mentioned. Examples of the cycloalkyloxy group include a C 5-10 cycloalkyloxy group. Examples of the aryloxy group include a C 6-10 aryloxy group. Examples of the aralkyloxy group include a C 6-10 aryl-C 1-4 alkoxy group can be mentioned.

[0062] Examples of the alkylthio group include C such as methylthio group, ethylthio group, propylthio group, n-butylthio group, t-butylthio group, etc. 1-10 An alkylthio group can be mentioned. Examples of the cycloalkylthio group include a C 5-10 cycloalkylthio group. Examples of the arylthio group include a C 6-10 arylthio group. Examples of the aralkylthio group include a C 6-10 aryl-C 1-4 alkylthio group can be mentioned.

[0063] Examples of the acyl group include C 1-12 an acyl group etc., for example, C such as an acetyl group 1-6 an alkyl-carbonyl group etc. can be mentioned.

[0064] Examples of the mono- or di-substituted amino group include a mono- or dialkylamino group, a mono- or diacylamino group, etc. Examples of the mono- or dialkylamino group include a mono- or diC 1-4 alkylamino group. Examples of the mono- or diacylamino group include a mono- or diC 1-7 acylamino group [for example, a mono- or di(C 1-4 alkyl-carbonyl)amino group etc.] can be mentioned.

[0065] Typical R1 Examples include a halogen atom (such as a fluorine atom), a hydrocarbon group (for example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, etc.), a group [-OR h (such as an alkoxy group), an acyl group, etc., and preferably a hydrocarbon group such as an alkyl group or an aryl group. Examples of the alkyl group (linear or branched alkyl group) include C 1-6 alkyl groups such as a methyl group, an ethyl group, a t-butyl group, etc., and a C 1-4 alkyl group such as a methyl group is preferred. Examples of the aryl group include C 6-10 aryl groups such as a phenyl group, etc.

[0066] R 1 The substitution number m1 of represents an integer from 0 to 8, for example, an integer of about 0 to 6, preferably, in a stepwise manner, an integer of 0 to 4, an integer of 0 to 2, more preferably 0 or 1, or 0 or 2, and particularly preferably 0. When m1 is 2 or more, the types of two or more R 1 may be the same as or different from each other. Also, among the two benzene rings forming the fluorene skeleton, when R 1 is substituted on both benzene rings, the type of R 1 on one benzene ring and the type of R 1 on the other benzene ring may be the same as or different from each other; when two or more R 1 are substituted on one benzene ring, the types of two or more R 1 substituted on one benzene ring may be the same as or different from each other. Also, the substitution position of R 1 is not particularly limited, and may be, for example, the 2-position, the 3-position, the 2,7-position, etc.

[0067] Z 1a Or the arene ring (aromatic hydrocarbon ring) represented by Z 1b Examples include monocyclic arene rings such as benzene rings, polycyclic arene rings, etc. Examples of the polycyclic arene ring include condensed polycyclic arene rings (condensed polycyclic aromatic hydrocarbon rings), ring-assembled arene rings (ring-assembled aromatic hydrocarbon rings), etc.

[0068] Examples of fused polycyclic arene rings include fused bicyclic arene rings, fused tricyclic arene rings, and other fused dicyclic to tetracyclic arene rings. Examples of fused bicyclic arene rings include naphthalene rings and indene rings. 9-16 Examples include arene rings. Examples of fused tricyclic arene rings include anthracene rings and phenanthrene rings. 14-20 Examples include arene rings. Preferred fused polycyclic arene rings include naphthalene rings and other fused polycyclic C rings. 10-14 It is an arene ring, and more preferably a naphthalene ring.

[0069] Examples of ring-assembled arene rings include bialene rings such as biphenyl rings, phenylnaphthalene rings, and binaphthyl rings; and telarene rings such as terphenyl rings (m-terphenyl rings, etc.). Preferred ring-assembled arene rings are bi or telarene rings, and more preferably biphenyl rings, m-terphenyl rings, etc. 12-18 It is a bialene ring, and more specifically, a biphenyl ring.

[0070] In this specification and in the claims, "ring-assembled arene ring" means a ring in which two or more ring systems (arene ring systems) are directly connected by single or double bonds, and the number of bonds directly connecting the rings is one less than the number of ring systems. For example, as mentioned above, phenylnaphthalene rings and binaphthyl rings are classified as ring-assembled arene rings even though they have a fused polycyclic arene ring skeleton, and are clearly distinguished from "fused polycyclic arene rings" such as naphthalene rings (aring-assembled arene rings).

[0071] Z 1a ,Z 1b The arene ring represented by is preferably C 6-14 Examples include arene rings, and more preferably benzene rings, naphthalene rings, biphenyl rings, etc. 6-12 C such as an arene ring, more preferably a benzene ring, naphthalene ring, etc. 6-10It is an arene ring, and a benzene ring is particularly preferred from the viewpoint of having excellent heat resistance, refractive index, and solubility. Also, Z 1a and Z 1b The types may be the same or different from each other, but it is preferable that they be the same.

[0072] Note that Z is bonded at the 9-position of the fluorene ring. 1a and Z 1b The substitution position is not particularly limited; for example, Z 1a ,Z 1b If it is a benzene ring, it can be in any position, Z 1a ,Z 1b If it is a naphthalene ring, it is at either the 1-position (1-naphthyl) or the 2-position (2-naphthyl), preferably at the 2-position, Z 1a ,Z 1b If it is a biphenyl ring, it is at one of the 2-, 3-, or 4-positions, preferably at the 3-position.

[0073] A 1a Or A 1b Examples of alkylene groups (linear or branched alkylene groups) represented by this symbol include ethylene, propylene (1,2-propanediyl), trimethylene, 1,2-butanediyl, and tetramethylene groups. 2-6 Examples include alkylene groups, preferably C 2-4 C such as an alkylene group, more preferably an ethylene group, a propylene group, etc. 2-3 Alkylene groups, particularly ethylene groups, are preferred. Also, A 1a and A 1b The types may be the same or different from each other, but it is preferable that they be the same.

[0074] [-(A 1a -O)-] or [-(A 1bThe number of repeating alkylene oxy groups (number of added moles) n1a and n1b, represented by -O)-], should each be 1 or greater, and may be selected from integers of approximately 1 to 15, preferably in the following increments: integers from 1 to 10, integers from 1 to 8, integers from 1 to 6, integers from 1 to 4, integers from 1 to 3, integers from 1 to 2, and more preferably 1. In this specification and in the claims, the "number of repeating groups (number of added moles)" may be an average value (arithmetic mean) or average number of added moles. Therefore, n1a and n1b may each be selected from a range of approximately 1 to 15, and preferably in the following increments: 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, 1 to 2. When n1a and / or n1b are within a moderate range that is not too large, it tends to be easier to suppress the decrease in heat resistance and refractive index.

[0075] Furthermore, n1a and n1b may be the same or different from each other. If n1a is 2 or more, then 2 or more alkylene oxy groups [-(A 1a The types of -O)-] may be different from each other, but are preferably the same; if n1b is 2 or more, 2 or more alkylene oxy groups [-(A 1b The types of -O)-] may be different from each other, but it is preferable that they be the same.

[0076] The sum of n1a and n1b (total number of added moles), n1a+n1b, may be 2 or more, and may be selected from a range of approximately 2 to 30, preferably in the following increments: 2-20, 2-16, 2-12, 2-8, 2-6, 2-4, and 2-3. When n1a+n1b is within a moderate range that is not too large, it tends to suppress the decrease in heat resistance and refractive index. n1a+n1b may be an integer or an average value (arithmetic mean, arithmetic mean, or average number of added moles).

[0077] Base [-(OA 1a ) n1a -NH2],[-(OA 1b ) n1b -NH2] (hereinafter also referred to as the amino group-containing group) Z 1a ,Z 1bThe substitution position for Z is not particularly limited, 1a ,Z 1b The substitution should be made at the appropriate positions. 1a ,Z 1b The substitution position for Z is Z 1a ,Z 1b If is a benzene ring, the phenyl group bonded to the 9-position of the fluorene ring is preferably at the 2-, 3-, or 4-position, and most preferably at the 3- or 4-position, and especially at the 4-position. Also, Z 1a ,Z 1b When is a naphthalene ring, substitution often occurs at one of the 5-8 position 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 for the 9-position of the fluorene ring (substitution in the relationship of 1-naphthyl or 2-naphthyl), and it is preferable that this substitution occurs in the relationship of 1,5-position, 2,6-position, and especially the relationship of 2,6-position. Also, Z 1a ,Z 1b If is a ring-assembled arene ring, the substitution position of the amino group-containing group is not particularly limited, and may be substituted on the arene ring bonded to the 9-position of fluorene or on the arene ring adjacent to this arene ring. For example, Z 1a ,Z 1b is a biphenyl ring (or Z 1a ,Z 1b is a benzene ring, m2a and m2b are 1, R 2a ,R 2b In the case of a phenyl group, it is preferable that the 3-position of the biphenyl ring is bonded to the 9-position of fluorene, and the 6-position of the biphenyl ring is bonded to the amino group-containing group.

[0078] R 2a or R 2b The substituent represented by may be an inactive (or nonpolymerizable) group that is inert to the reaction. 2a or R 2b Examples of substituents represented by R 1 (or R h Examples include groups similar to the substituents listed as ). 2a or R 2bTypical substituents represented by are halogen atoms (such as fluorine atoms), hydrocarbon groups (e.g., alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, etc.), and groups [-OR] h Examples include C11 (alkoxy group, etc.) and acyl group, preferably hydrocarbon groups such as alkyl groups and aryl groups. Examples of alkyl groups (linear or branched alkyl groups) include C11, methyl group, ethyl group, t-butyl group, etc. 1-6 Examples include alkyl groups, such as methyl groups and C 1-4 Alkyl groups are preferred. Examples of aryl groups include C such as phenyl groups. 6-10 Examples include aryl groups. 2a and R 2b The types may be different from each other, but it is preferable that they be the same. Also, R 2a ,R 2b When R is an aryl group, 2a ,R 2b These are Z 1a ,Z 1b They may form a ring-assembled arene ring together.

[0079] R 2a or R 2b The number of substitutions m2a and m2b can each be non-negative integers, Z 1a ,Z 1b The type can be appropriately selected, for example, it may be an integer of about 0 to 6, preferably an integer of 0 to 4, more preferably an integer of 0 to 2, even more preferably 0 or 1, and especially 0. m2a and m2b may be different from each other, but it is preferable that they be the same. Also, if m2a is 2 or more, then 2 or more R 2a The types may be the same or different from each other; if m2b is 2 or more, then 2 or more R 2b The types may be the same as or different from each other.

[0080] R 2a ,R 2b The substitution position of Z is not particularly restricted, 1a ,Z 1bIn this case, any position other than the bond position with the 9-position of the fluorene ring and the bond position with the amino group-containing group is acceptable, for example, Z 1a ,Z 1b The amino group-containing group in the above-mentioned material may be substituted for or bonded to the ortho position (the carbon atom adjacent to the carbon atom to which the amino group-containing group is bonded).

[0081] A typical fluorene-based amine compound (1) is, for example, in formula (1) above, R 1 represents a hydrocarbon group (for example, a hydrocarbon group with 20 or fewer carbon atoms), and m1 represents an integer from 0 to 4. Z 1a and Z 1b C 6-14 Showing an arene ring, A 1a and A 1b C 2-6 It represents an alkylene group, and n1a and n1b independently represent integers from 1 to 10. R 2a and R 2b Examples include compounds where m2a and m2b independently represent a hydrocarbon group (for example, a hydrocarbon group with 20 or fewer carbon atoms), and m2a and m2b independently represent integers from 0 to 4;

[0082] Preferably, R 1 m1 represents an alkyl group, cycloalkyl group, aryl group, or aralkyl group, and m1 represents an integer from 0 to 2. Z 1a and Z 1b These are independently C2 rings such as benzene rings, naphthalene rings, and biphenyl rings. 6-12 Showing an arene ring, A 1a and A 1b C 2-4 It represents an alkylene group, and n1a and n1b independently represent integers from 1 to 6. R 2a and R 2bExamples of compounds where m2a and m2b independently represent an alkyl group, cycloalkyl group, aryl group, or aralkyl group;

[0083] More preferably, R 1 C 1-6 Alkyl or C 6-10 It indicates an aryl group, and m1 represents an integer from 0 to 2. Z 1a and Z 1b These are independently C2 rings such as benzene rings and naphthalene rings. 6-10 Showing an arene ring, A 1a and A 1b These are independently C groups such as ethylene and propylene. 2-3 It represents an alkylene group (preferably an ethylene group), and n1a and n1b independently represent integers from 1 to 3 (preferably 1 or 2). R 2a and R 2b C 1-6 Alkyl or C 6-10 Examples of compounds exhibiting an aryl group include those in which m2a and m2b independently represent integers from 0 to 2.

[0084] Specific examples of fluorene-based amine compounds (1) include, for example, 9,9-bis[4-(2-aminoethoxy)phenyl]fluorene, 9,9-bis[6-(2-aminoethoxy)-2-naphthyl]fluorene, 9,9-bis[5-(2-aminoethoxy)-1-naphthyl]fluorene, etc. 2-4 Alkoxy)C 6-12 Examples include fluorene and aryl fluorene.

[0085] The fluorene-based amine compound (1) of this disclosure may also be in the form of a salt. Examples of salts include inorganic salts such as hydrochloride salts and organic salts such as acetate salts.

[0086] (Properties and uses of fluorene-based amine compounds (1)) The fluorene-based amine compound (1) or its salt may be crystalline or amorphous, but it is preferable that it be crystalline, and particularly preferable that it be in powder form, due to its excellent handling properties.

[0087] When the fluorene-based amine compound (1) or its salt is crystalline, its melting point is, for example, 80 to 300°C (e.g., 90 to 250°C), preferably 100 to 200°C (e.g., 110 to 150°C), and more preferably 120 to 130°C. In particular, when the fluorene-based amine compound (1) is 9,9-bis[4-(2-aminoethoxy)phenyl]fluorene, its melting point is, for example, 123 to 129°C, preferably 124 to 128°C, and more preferably 125 to 127°C.

[0088] Furthermore, the glass transition temperature Tg of the fluorene-based amine compound (1) or its salt is, for example, 70 to 200°C (e.g., 80 to 180°C), preferably 90 to 150°C, and more preferably 100 to 120°C.

[0089] Fluorene-based amine compounds (1) or their salts have relatively low melting points or glass transition temperatures (Tg), making them meltable at low temperatures and readily mixable with other components (e.g., epoxy resins), thus facilitating the preparation of homogeneous compositions (e.g., curable compositions) easily or efficiently.

[0090] In this specification and in the claims, the melting point and glass transition temperature Tg can be measured by the methods described in the examples below.

[0091] The 5% weight loss temperature Td5 of the fluorene-based amine compound (1) or its salt may be, for example, around 150°C or higher (e.g., 180°C or higher), specifically 200°C or higher (e.g., around 230-350°C), preferably in stages as follows: 250-300°C, 260-295°C, 270-290°C, 275-285°C, and more preferably in stages as follows: 190°C or higher, 200°C or higher, 250-350°C, 280-345°C, 290-340°C, 300-335°C, 310-330°C. The fluorene-based amine compound (1) or its salt appears to easily maintain high heat resistance even with relatively low melting points and glass transition temperatures Tg.

[0092] In this specification and in the claims, the 5% weight loss temperature Td5 can be measured by the method described in the examples below.

[0093] The amount of solvent remaining in the fluorene-based amine compound (1) or its salt may be, for example, about 10% by mass or less, and is preferably in the following stages for excellent handling properties: 8% by mass or less, 6% by mass or less, 5% by mass or less, 4% by mass or less, and 3.5% by mass or less. When the amount of solvent remaining is within a moderate range that is not too much, it tends to improve handling properties (improve handling properties or reduce viscosity).

[0094] In this specification and in the claims, the amount of solvent remaining (100 - amount of solids [mass%]) can be measured based on the method described in the examples below.

[0095] The refractive index nD of the fluorene-based amine compound (1) or its salt may be selected from a range of approximately 1.6 or higher (e.g., approximately 1.6 to 1.68) at a temperature of 25°C and a wavelength of 589 nm, preferably 1.61 to 1.67, more preferably 1.62 to 1.66 (e.g., 1.625 to 1.655), and particularly 1.63 to 1.65 (e.g., 1.635 to 1.645).

[0096] In this specification and in the claims, the refractive index nD can be measured using a refractometer by the method described in the examples below.

[0097] Fluorene-based amine compounds (1) or their salts exhibit surprisingly high solubility (or compatibility) with organic compounds (such as organic solvents) compared to conventional amine compounds having a 9,9-bisarylfluorene skeleton, thus satisfying the requirements of high solubility, high heat resistance, and high refractive index. Fluorene-based amine compounds (1) or their salts may be soluble in at least one solvent selected from aromatic hydrocarbons, alcohols, ethers, ketones, esters, glycol ether acylates, and amides at a temperature of 50-60°C (preferably 25°C) at a concentration of 10% by mass or more (preferably 20% by mass or more) within 1 hour.

[0098] Aromatic hydrocarbons include, for example, benzene and alkylbenzenes (mono- or hexa-C, such as toluene and xylene). 1-6 Examples include alkylbenzenes, etc., and mono- or tri-C toluene. 1-4 Alkylbenzene is preferred.

[0099] Examples of alcohols include alkanols (e.g., methanol, ethanol, n-propanol, isopropanol, butanol, etc.) 1-6 Alkanols, etc., alkylene glycols (for example, ethylene glycol, etc.) 2-4 Examples include alkylene glycols, and methanol, among others. 1-4 Alkanol is preferred.

[0100] Examples of ethers include linear ethers, specifically dialkyl ethers (for example, diethyl ether, diisopropyl ether, etc.). 1-6(such as alkyl ethers), (mono or tetra)alkylene glycol dialkyl ethers [for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc. (mono or tetra) C 2-4 Alkylene glycol C 1-6 Examples include alkyl ethers, etc.; cyclic ethers such as tetrahydrofuran (THF) and 1,4-dioxane are examples, with cyclic ethers such as THF and 1,4-dioxane being preferred.

[0101] Examples of ketones include linear ketones [for example, dialkyl ketones, specifically acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), etc.]. 1-6 [Alkyl ketones, etc.], cyclic ketones (e.g., cycloalkanones, specifically cyclohexanone, etc.) 4-7 Examples include cycloalkanones, and C such as MEK and MIBK. 3-8 C such as dialkylketones and cyclohexanone 5-10 Cycloalkanones are preferred.

[0102] Examples of esters include chain esters [for example, alkanate esters (for example, acetate esters (methyl acetate, ethyl acetate, alkyl acetate such as butyl acetate, etc.) C] 1-4 Alkanic acid esters, etc., lactate esters (such as methyl lactate and other lactate C) 1-4 Examples include alkyl esters, etc.; cyclic esters (lactones) such as γ-butyrolactone, γ-valerolactone, γ-caprolactone (or γ-hexanolactone), and ε-caprolactone; and acetate esters (e.g., ethyl acetate). 1-4 Alkyl esters, etc., are preferred.

[0103] Examples of ether esters include alkylene glycol monoalkyl ether acylates such as methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate (PGMEA), and alkoxycarboxylic acid esters such as ethyl 3-ethoxypropionate. 2-4 Alkylene glycol mono C 1-4 Alkyl ether acetate is preferred.

[0104] Examples of amides include chain amides [for example, N,N-dialkyl(form or acyl)amides such as N,N-dimethylformamide (DMF), N,N-diethylformamide, and N,N-dimethylacetamide (DMAc)], and cyclic amides (lactams) [for example, N-methyl-2-pyrrolidone (NMP)], with cyclic amides (lactams) such as NMP being preferred.

[0105] This disclosure encompasses liquid compositions (or solutions) comprising a fluorene-based amine compound (1) or a salt thereof and a solvent. Examples of solvents in the liquid composition include the aromatic hydrocarbons, alcohols, ethers, ketones, esters, ether esters, amides, etc., which may be included alone or in combination of two or more.

[0106] Preferred solvents include alcohols (especially methanol and other C23 1-4 Alkanols), ethers (especially cyclic ethers such as THF and 1,4-dioxane), ketones (especially diC acetone, MEK, MIBK, etc.) 1-4 C such as alkyl ketones and cyclohexanone 5-7 These include cycloalkanones, amides (especially chain amides such as DMF, and cyclic amides (lactams) such as NMP).

[0107] In a liquid composition (or solution), the proportion of the fluorene-based amine compound (1) or its salt may be, for example, about 1 to 50% by mass relative to the total amount of the fluorene-based amine compound (1) or its salt and the solvent, and preferably in the following increments: 5 to 45% by mass, 10 to 40% by mass, 15 to 35% by mass, 20 to 30% by mass, and may be adjusted as appropriate depending on the application.

[0108] The liquid composition (or solution) may be a reaction solution containing a fluorene-based amine compound (1) or a salt thereof as a reactant.

[0109] Fluorene-based amine compounds (1) or their salts can also be used as resin raw materials or polymerization components (monomer components) for forming resins. Examples of resins include curable resins (thermally or photocurable resins) and thermoplastic resins, which will be described in detail later in the section on [Resins or resin compositions, and molded articles].

[0110] Fluorene-based amine compounds (1) or salts thereof can also be used as resin additives for modifying resins, such as refractive index improvers, curing agents or curing accelerators (e.g., curing agents for epoxy resins), crosslinking agents, chain extenders (or chain lengthening agents), and will be described in detail later in the section on [Resins or resin compositions, and molded articles].

[0111] [Fluorene-based azide compounds] This disclosure includes fluorene azide compounds represented by the following formula (2) [hereinafter also referred to as fluorene azide compound (2) or azide compound (2)] that can be used as precursors (or reaction intermediates) for producing fluorene amine compounds (1) or salts thereof.

[0112] [ka]

[0113] (In the formula, R 1 represents a substituent, and m1 represents an integer from 0 to 8. Z1a and Z 1b These independently exhibit an arene ring, A 1a and A 1b n1a and n1b independently represent an alkylene group, and n1a and n1b independently represent integers greater than or equal to 1. R 2a and R 2b (where m2a and m2b independently represent substituents, and m2a and m2b independently represent non-negative integers.)

[0114] The fluorene-based azide compound (2) corresponds to a compound obtained by replacing the two amino groups [-NH2] of the fluorene-based amine compound (1) with azide groups [-N3]. Therefore, in formula (2), R 1 , m1, Z 1a and Z 1b , A 1a and A 1b , n1a and n1b, R 2a and R 2b , m2a and m2b are the same as in formula (1), including preferred embodiments [preferred embodiments such as the type and number of rings and groups (number of substitutions and repeats), and substitution positions].

[0115] Examples of typical fluorene-based azide compounds (2) include compounds that correspond to the compounds described above as typical fluorene-based amine compounds (1), including preferred embodiments, and in which the two amino groups [-NH2] of amine compound (1) are replaced with azide groups [-N3].

[0116] Specific fluorene-based azide compounds (2) also correspond to the specific fluorene-based amine compounds (1) mentioned above, for example, 9,9-bis[4-(2-azidoethoxy)phenyl]fluorene, 9,9-bis[6-(2-azidoethoxy)-2-naphthyl]fluorene, 9,9-bis[5-(2-azidoethoxy)-1-naphthyl]fluorene, etc. 2-4 Alkoxy)C 6-12 Examples include fluorene and aryl fluorene.

[0117] Furthermore, the fluorene-based azide compound (2) can be used not only as a precursor (or reaction intermediate) for producing the fluorene-based amine compound (1) or its salt, but also as a resin raw material or polymerization component (monomer component) for forming resins [curable resins (thermoplastic or photocurable resins), thermoplastic resins, etc.] by utilizing the azide group [-N3]. For example, the azide group [-N3] of the fluorene-based azide compound (2) may be subjected to a cycloaddition reaction (or click reaction) with an alkyne compound having one or more C≡C triple bonds (e.g., polyyne compounds having two or more C≡C triple bonds such as diyne compounds, monoyne compounds having one C≡C triple bond and other polymerizable groups, etc.) to form a resin having a triazole ring skeleton (polytriazole resin, etc.). It can also be used as a resin additive for modifying resins [e.g., refractive index improvers, curing agents or curing accelerators, crosslinking agents, chain extenders (or chain lengthening agents), etc.]. The use of resin raw materials or resin additives will be discussed later in the section on [Resins or resin compositions, and molded articles].

[0118] [Method for producing fluorene-based amine compounds (1) and fluorene-based azide compounds (2)] The methods for producing the fluorene-based amine compound (1) or its salt, and the fluorene-based azide compound (2) are not particularly limited. For example, the method for producing the fluorene-based amine compound (1) or its salt may include a reduction step for reducing the fluorene-based azide compound (2); the method for producing the fluorene-based azide compound (2) may include an azidation step (or azation step) in which a fluorene compound represented by the following formula (3) [hereinafter also referred to as the fluorene compound (3) having a leaving group] is reacted with an azidating agent.

[0119] It is preferable to produce each fluorene compound according to the following reaction formula, as this allows for easy and efficient production.

[0120] [ka]

[0121] (wherein, L 1a and L 1b each independently represent a leaving group, R 1 , m1, Z 1a and Z 1b , A 1a and A 1b , n1a and n1b, R 2a and R 2b , m2a and m2b are the same as those in the above formula (1) including preferred embodiments.)

[0122] (Leaving group introduction step: Method for producing a fluorene compound (3) having a leaving group) The fluorene compound (3) having a leaving group may be produced by a method including a leaving group introduction step of introducing leaving groups L 1a , L 1b into the fluorene compound represented by the above formula (4) [hereinafter also referred to as fluorene-based diol compound (4)].

[0123] Examples of the fluorene-based diol compound (4) correspond to the fluorene-based amine compound (1) including preferred embodiments, and include compounds in which two amino groups [-NH2] of the amine compound (1) are each replaced with a hydroxyl group [-OH]. For example, 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorene, 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorene, etc., such as 9,9-bis[hydroxy(mono to deca)C 2-4 alkoxy-C 6-12 aryl]fluorene, particularly 9,9-bis[hydroxy(mono to deca)C 2-4Examples include alkoxy-phenyl]fluorene and the like.

[0124] The leaving group L in the above formula (3) 1a , L 1b Examples include a halogen atom (such as a fluorine atom, chlorine atom, bromine atom, iodine atom); a group [-O-SO2-R L (In the formula, R L represents a hydrocarbon group, a fluorinated hydrocarbon group, or a fluorine atom.) and other groups containing a sulfonyloxy group.

[0125] In the group [-O-SO2-R L , examples of the hydrocarbon group represented by R L include an alkyl group, a cycloalkyl group, an aryl group, and a group formed by combining two or more of these. Examples of the alkyl group include a C 1-6 alkyl group such as a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, etc. Examples of the cycloalkyl group include a C 5-10 cycloalkyl group such as a cyclopentyl group, cyclohexyl group, etc. Examples of the aryl group include a C 6-12 aryl group such as a phenyl group, naphthyl group, etc. Examples of the group formed by combining two or more of these include an alkylaryl group, an aralkyl group, etc. Examples of the alkylaryl group include a mono- to tri-C 1-6 alkyl C 6-10 aryl group such as a tolyl group, xylyl group, etc. Examples of the aralkyl group include a C 6-10 aryl C 1-6 alkyl group such as a benzyl group, phenethyl group, etc.

[0126] In the group [-O-SO2-R L , R LThe fluorinated hydrocarbon group represented by R can be any group in which at least one hydrogen atom in the hydrocarbon group is replaced with a fluorine atom, and a perfluoro hydrocarbon group in which all hydrogen atoms are replaced with fluorine atoms is particularly preferred. For example, the above R L Examples of hydrocarbon groups represented by the above include groups in which at least one hydrogen atom, preferably all hydrogen atoms, is replaced with fluorine atoms. Specific examples of fluorinated hydrocarbon groups include alkyl fluorides, specifically trifluoromethyl groups, nonafluorobutyl groups, etc. 1-6 Examples include perfluoroalkyl groups.

[0127] Preferred R L This refers to alkyl groups, specifically C such as methyl groups. 1-4 Alkyl groups; aryl groups, specifically phenyl groups, etc. 6-10 Aryl groups; alkylaryl groups, specifically mono or tri-C groups such as p-methylphenyl groups (p-tolyl groups). 1-4 Alkyl C 6-10 Aryl group; perfluoroalkyl group, specifically trifluoromethyl group, nonafluorobutyl group, etc. 1-6 Perfluoroalkyl group; a fluorine atom, and more preferably R L This is an alkyl group such as a methyl group.

[0128] L 1a and L 1b The types of leaving groups represented by may be different from each other, but it is preferable that they be the same. 1a ,L 1b Preferred leaving groups represented by are halogen atoms such as chlorine, bromine, and iodine atoms; and groups such as mesyloxy [-O-SO2-CH3], tosyloxy [-O-SO2-C6H4-CH3], fluorosulfonyloxy [-O-SO2-F], trifluoromethanesulfonyloxy [-O-SO2-CF3], and nonafluorobutanesulfonyloxy [-O-SO2-C4F9] [-O-SO2-R L ] and more preferably a group such as a mesyloxy group [-O-SO2-CH3] [-O-SO2-RL ]

[0129] In the leaving group introduction step, a fluorene-based diol compound (4) and L 1a ,L 1b A fluorene compound (3) having a leaving group can be prepared by reacting it with a leaving group introduction reagent, for example, by following the method described in Japanese Patent Application Publication No. 2021-134334.

[0130] Conventional reagents can be used as the leaving group introduction reagent, for example, L 1a ,L 1b If the atom is a halogen atom, examples include halogenating agents (such as tetrabromomethane); L 1a ,L 1b When the group is a sulfonyloxy group-containing group (such as a mesyloxy group or tosyloxy group), examples of sulfonylation agents include mesylation agents such as mesyl chloride and methanesulfonic anhydride, and tosylation agents such as tosyl chloride and p-toluenesulfonic anhydride.

[0131] The proportion of the leaving group introduction reagent (such as a mesylating agent) is, for example, 1 to 10 moles, preferably 1.1 to 3 moles, more preferably 1.15 to 2 moles, and particularly 1.2 to 1.5 moles, per mole of hydroxyl groups of the fluorene-based diol compound (4).

[0132] In the leaving group introduction step, from the viewpoint of efficient reaction, the leaving group introduction reagent (especially sulfonylated agents such as mesylating agents and tosylating agents) may be reacted in the presence of a base as needed. Bases can be broadly classified into inorganic bases and organic bases, for example. Bases may be used alone or in combination of two or more types.

[0133] Examples of inorganic bases include metal hydroxides, specifically alkali metal or alkaline earth metal hydroxides such as sodium hydroxide and calcium hydroxide; metal carbonates, specifically alkali metal or alkaline earth metal carbonates such as sodium carbonate and calcium carbonate; and metal bicarbonates, specifically alkali metal or alkaline earth metal bicarbonates such as sodium bicarbonate.

[0134] Examples of organic bases include amines, specifically trialkylamines such as triethylamine, aromatic tertiary amines such as benzyldimethylamine, and heterocyclic amines such as pyridine and N-methylmorpholine.

[0135] Among these bases, amines, such as trialkylamines including triethylamine, are commonly used. The amount of base used is not particularly limited, but is, for example, 1 to 2 moles, preferably 1.05 to 1.5 moles, and more preferably 1.1 to 1.3 moles, per mole of the leaving group introduction reagent (such as a mesylating agent).

[0136] The reaction may be carried out in the presence of a solvent. Examples of solvents include ethers, specifically dialkyl ethers such as diethyl ether, tetrahydrofuran (THF), and cyclic ethers such as 1,4-dioxane. The solvent may be used alone or in combination of two or more. A preferred solvent is cyclic ethers such as THF. The proportion of the solvent may be, for example, about 10 to 2000 parts by mass, preferably 100 to 1000 parts by mass, and more preferably 400 to 800 parts by mass, per 100 parts by mass of the total amount of the fluorene-based diol compound (4) and the leaving group introduction reagent (such as a mesyling agent).

[0137] The reaction temperature and reaction time can be appropriately selected depending on the type of raw materials used. The reaction temperature is, for example, -20°C to 50°C, preferably -10°C to 40°C, and more preferably 0 to 30°C. The reaction time is not particularly limited and may be, for example, 1 to 60 hours (e.g., 1 to 48 hours), preferably 1 to 24 hours (e.g., 1 to 12 hours), and more preferably 2 to 6 hours.

[0138] The reaction may be carried out in air or in an inert gas atmosphere such as nitrogen gas or a noble gas, under normal pressure, under pressurized pressure or reduced pressure, and while stirring is performed.

[0139] After the reaction is complete, the resulting fluorene compound (3) having a leaving group may be separated and purified by conventional methods, such as neutralization, washing, dehydration, filtration, adsorption, concentration, drying, extraction, crystallization, recrystallization, reprecipitation, centrifugation, column chromatography, or a combination thereof.

[0140] (Azidation process: Method for producing fluorene-based azide compound (2)) In the azidation step (or azide step), a fluorene compound (3) having a leaving group is reacted with an azidating agent (or azidating agent) to prepare a fluorene-based azide compound (2).

[0141] The fluorene compound (3) having a leaving group can correspond to, for example, a fluorene-based amine compound (1) and a preferred embodiment thereof, wherein the two amino groups [-NH2] of the amine compound (1) are each separated by a leaving group L 1a and L 1bExamples of compounds in which the leaving group L is replaced include 9,9-bis[4-(2-methyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-tosyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-bromoethoxy)phenyl]fluorene, 9,9-bis[4-(2-methyloxypropoxy)phenyl]fluorene, 9,9-bis[6-(2-methyloxyethoxy)-2-naphthyl]fluorene, and 9,9-bis[5-(2-methyloxyethoxy)-1-naphthyl]fluorene. 1a and L 1b 9,9-bis[hydroxy(mono or deca)C] is formed by introducing sulfonyl-containing groups (such as mesyl and tosyl groups, and halogen atoms such as bromine atoms). 2-4 Alkoxy-C 6-12 Aryl fluorene, in particular, 9,9-bis[hydroxy(mono or deca)C 2-4 Examples include alkoxyphenyl fluorene.

[0142] As an azidating agent (or azidating agent), the leaving group L of the fluorene compound (3) 1a ,L 1b The reagent is not particularly limited as long as it can remove the azide group and introduce the azide group [-N3], and may be a conventional azidating agent such as sodium azide, trimethylsilyl azide, diphenyl phosphate azide, or tetrabutylammonium azide, with sodium azide being preferred.

[0143] The proportion of the azidating agent is, for example, 1 to 10 moles, preferably 1.2 to 5 moles, more preferably 1.5 to 4 moles, and particularly 2 to 3 moles, per mole of leaving group of fluorene compound (3).

[0144] The reaction may be carried out in the presence of a solvent. Examples of the solvent include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), etc. The solvent may be used alone or in combination of two or more. The preferred solvent is DMF. The proportion of the solvent may be, for example, about 10 to 2000 parts by mass with respect to 100 parts by mass of the total amount of the fluorene compound (3) and the azidating agent, preferably 100 to 1500 parts by mass, more preferably 500 to 1000 parts by mass.

[0145] The reaction temperature and reaction time can be appropriately selected according to the types of raw materials used. The reaction temperature is, for example, 50 to 150 °C, preferably 60 to 100 °C, more preferably 70 to 90 °C. The reaction time is not particularly limited and may be, for example, 1 to 12 hours, preferably about 2 to 6 hours.

[0146] The reaction may be carried out in air or in an inert gas atmosphere such as nitrogen gas or noble gas, and may be carried out under normal pressure, increased pressure or reduced pressure, and may be carried out with stirring.

[0147] After the completion of the reaction, the produced fluorene-based azide compound (2) may be separated and purified by conventional methods, for example, separation and purification means such as washing, dehydration, filtration, adsorption, concentration, drying, extraction, crystallization, recrystallization, reprecipitation, centrifugation, column chromatography, etc., or means combining these.

[0148] (Reduction step: Method for producing fluorene-based amine compound (1)) Examples of the fluorene-based azide compound (2) include compounds corresponding to the fluorene-based amine compound (1) including preferred embodiments, and compounds described in the section of [fluorene-based azide compound], etc.

[0149] In the reduction step, the fluorene-based azide compound (2) is reduced to prepare the fluorene-based amine compound (1). The reduction method is not particularly limited as long as the azide group [-N3] of the fluorene-based azide compound (2) can be reduced to the amino group [-NH2]. For example, it may be a catalytic reduction method using a catalyst such as palladium carbon (such as a solid-supported catalyst); it may be a reduction method using a conventional reducing agent such as lithium aluminum hydride (LAH) (hydride reduction); or preferably a method of hydrolysis of an iminophosphorane (aza-phosphorylate) formed by reacting the azide group [-N3] with phosphines [a method utilizing the Staudinger reaction].

[0150] As for the phosphines, for example, trivalent phosphines are preferred, preferably triarylphosphines such as triphenylphosphine. The proportion of phosphines is, for example, 1 to 5 moles, preferably 1.05 to 2 moles, and more preferably 1.1 to 1.5 moles, per mole of the azide group [-N3] of the fluorene-based azide compound (2).

[0151] The reaction may be carried out in the presence of a solvent. Examples of solvents include ethers, specifically dialkyl ethers such as diethyl ether, tetrahydrofuran (THF), and cyclic ethers such as 1,4-dioxane. The solvent may be used alone or in combination of two or more. A preferred solvent is cyclic ethers such as THF. The proportion of the solvent may be, for example, about 10 to 2000 parts by mass, preferably 100 to 1000 parts by mass, and more preferably 400 to 800 parts by mass, per 100 parts by mass of the total amount of the fluorene-based azide compound (2) and phosphines.

[0152] The reaction temperature and reaction time can be appropriately selected depending on the type of raw materials used. The reaction temperature is, for example, 30 to 100°C, preferably 50 to 80°C, and more preferably 60 to 70°C, and may be carried out at reflux temperature. The reaction time is not particularly limited and may be, for example, 1 to 12 hours, preferably 2 to 6 hours.

[0153] The reaction may be carried out in air or in an inert gas atmosphere such as nitrogen gas or a noble gas, under normal pressure, under pressurized pressure or reduced pressure, and while stirring is performed.

[0154] The iminophosphoranes produced by the reaction of the azide group [-N3] of the fluorene-based azide compound (2) with phosphines may be produced by conventional separation and purification methods, or the reaction mixture may be subjected to hydrolysis directly.

[0155] Water may be added in the reduction step to hydrolyze the iminophosphorane and convert it to an amino group [-NH2]. The proportion of water is, for example, 1 to 10 moles, preferably 2 to 5 moles, and more preferably 2.5 to 3.5 moles, per mole of azide group [-N3] of the fluorene-based azide compound (2). Adding an excess amount of water relative to the fluorene-based azide compound (2) may allow the reaction (conversion of the starting material) to proceed completely. The water may be added all at once or in installments (for example, in two separate additions).

[0156] The reaction temperature and reaction time in the hydrolysis reaction can be appropriately selected depending on the type of raw material used. The reaction temperature is, for example, 30°C to 100°C, preferably 50°C to 80°C, and more preferably 60°C to 70°C, and may be carried out at reflux temperature. The reaction time is not particularly limited and may be, for example, 1 to 12 hours, preferably 2 to 6 hours.

[0157] The hydrolysis reaction may be carried out in air or in an inert gas atmosphere such as nitrogen gas or a noble gas, under normal pressure, under pressure or reduced pressure, and while stirring.

[0158] After the reaction is complete, the resulting fluorene-based amine compound (1) may be separated and purified by conventional methods, such as neutralization, washing, dehydration, filtration, adsorption, concentration, drying, extraction, crystallization, recrystallization, reprecipitation, centrifugation, column chromatography, or a combination thereof. For example, the resulting fluorene-based amine compound (1) may be washed with an organic solvent such as ethyl acetate in the form of a salt such as hydrochloride, crystallized in the form of a salt such as hydrochloride, and then the resulting salt crystals such as hydrochloride may be dissolved, neutralized, extracted, washed, and the extraction solvent removed to produce the compound. In this way, the fluorene-based amine compound (1) can be easily or efficiently separated from by-products such as triphenylphosphine oxide by passing through the form of an acid salt (such as hydrochloride).

[0159] (Crystalization process: Crystallization of fluorene-based amine compound (1)) From the viewpoint of improving handling ease, it is preferable to purify the fluorene-based amine compound (1) or its salt obtained in the reduction step by a crystallization step in which crystals are precipitated from a solvent (crystallization solvent) containing at least esters. The crystals obtained through the crystallization step appear to have a low amount of residual solvent and are easily obtained in powder form with excellent handling properties.

[0160] Examples of esters include acetate esters (methyl acetate, ethyl acetate, alkyl acetates such as butyl acetate, etc.), and ethyl acetate and other acetates. 1-4 Alkyl esters are preferred.

[0161] The crystallization solvent may further contain hydrocarbons. Examples of hydrocarbons include aliphatic hydrocarbons, specifically C such as n-hexane and n-heptane. 5-12 Examples include alkanes, and C such as n-heptane. 6-8 Alkanes are preferred.

[0162] The aforementioned esters (especially C acetate such as ethyl acetate) 1-4 Alkyl esters) and the aforementioned hydrocarbons (especially C such as n-heptane) 6-8The proportion of the total amount of alkanes is, for example, 50% by mass or more, preferably in stages, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, and may be substantially 100% by mass, relative to the total amount of crystallization solvent.

[0163] In the crystallization process, the temperature at which crystals are precipitated is, for example, 20°C or lower, preferably in stages, 15°C or lower, 10°C or lower (e.g., -10°C to 10°C), and 5°C or lower (e.g., -5°C to 5°C). The precipitated crystals may be separated from the crystallization solvent by conventional methods such as filtration, centrifugation, decantation, and drying.

[0164] [Resins or resin compositions, and molded articles] (resin) The resins of this disclosure may contain a fluorene-based amine compound (1) or a salt thereof, and / or a fluorene-based azide compound (2) as resin raw materials or polymerization components (monomer components), and it is preferable that they contain a fluorene-based amine compound (1) or a salt thereof.

[0165] The type of resin in this disclosure is not particularly limited and may be either a thermoplastic resin or a curable resin (thermo- or photocurable resin). Typical resins include those containing a fluorene-based amine compound (1) or a salt thereof as a resin raw material or polymerization component (monomer component), or resins using a diamine component or polyamine component as the polymerization component, such as polyamide resins [including polyamic acid (or polyamic acid) described later], polyimide resins (including polyamide-imide resins), and polyurea resins. Of these resins, polyimide resins are preferred from the viewpoint of heat resistance and other factors.

[0166] (Polyamide resin) Polyamide resins may contain a diamine component and a dicarboxylic acid component as polymerization components. Furthermore, if the polyamide resin is polyamic acid (or polyamic acid), it may contain a diamine component and a tetracarboxylic acid component (particularly tetracarboxylic dianhydride), as described later in the section on (polyimide resins).

[0167] The polyamide resin may contain only a fluorene-based amine compound (1) or a salt thereof [first diamine component] as the diamine component, and may or may not contain other diamine components different from the fluorene-based amine compound (1) (second diamine component) as needed. Examples of the second diamine component include those similar to the second diamine component exemplified in the (polyimide resin) section below. The first and second diamine components may each be used individually or in combination of two or more types.

[0168] Dicarboxylic acid components Examples of dicarboxylic acid components include aliphatic dicarboxylic acid components, alicyclic dicarboxylic acid components, and aromatic dicarboxylic acid components. Dicarboxylic acid components can be used individually or in combination of two or more. Dicarboxylic acid components also include derivatives corresponding to dicarboxylic acids, such as acid halides like acid chlorides and acid bromides, and amide-forming derivatives like acid anhydrides.

[0169] Examples of aliphatic dicarboxylic acid components include alkanedicarboxylic acids, specifically succinic acid, adipic acid, sebacic acid, decanedicarboxylic acid, etc. 2-12 Alkane-dicarboxylic acids, etc.; unsaturated aliphatic dicarboxylic acids, specifically maleic acid, fumaric acid, itaconic acid, etc. 2-10 Examples include alkene-dicarboxylic acids.

[0170] Examples of alicyclic dicarboxylic acid components include cycloalkanedicarboxylic acids, specifically 1,4-cyclohexanedicarboxylic acid and other C13 5-10 Cycloalkane-dicarboxylic acids, etc.; crosslinked cyclic cycloalkane-dicarboxylic acids, specifically decalin-dicarboxylic acid, norbornane-dicarboxylic acid, adamantane-dicarboxylic acid, tricyclodecane-dicarboxylic acid, etc. or tricycloalkane-dicarboxylic acids, etc.; cycloalkene-dicarboxylic acids, specifically cyclohexene-dicarboxylic acid, etc. 5-10Examples include cycloalkene-dicarboxylic acids; specifically, bi- or tricycloalkene dicarboxylic acids such as norbornene dicarboxylic acid.

[0171] Examples of aromatic dicarboxylic acid components include monocyclic aromatic dicarboxylic acids and polycyclic aromatic dicarboxylic acids. Examples of monocyclic aromatic dicarboxylic acids include benzene dicarboxylic acids such as phthalic acid, terephthalic acid, and isophthalic acid; alkylbenzene dicarboxylic acids, specifically C4-methylisophthalic acid. 1-4 Examples include alkylbenzene dicarboxylic acids. Polycyclic aromatic dicarboxylic acids include, for example, condensed polycyclic aromatic dicarboxylic acids, specifically naphthalenedicarboxylic acids such as 2,3-naphthalenedicarboxylic acid, anthracenedicarboxylic acid, and phenantradicarboxylic acid. 10-24 Allene-dicarboxylic acids, etc.; biaryldicarboxylic acids, specifically 2,2'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, etc.; bis[(carboxyalkoxy)-C 6-10 Aryl alkanes, specifically bis[(carboxymethyl)-1-naphthyl]methane and other bis[(carboxymethyl) 1-4 Alkoxy)-C 6-10 Ariel)C 1-6 Alkanes, etc.; diarylalkane dicarboxylic acids, specifically diC such as 4,4'-diphenylmethanedicarboxylic acid. 6-10 Aryl C 1-6 Alkane-dicarboxylic acids, etc.; diarylketone dicarboxylic acids, specifically, di(C) such as 4,4'-diphenylketone dicarboxylic acid. 6-10 Aryl)ketone-dicarboxylic acids, etc.; diaryl ether dicarboxylic acids, specifically, di(C)))))) 6-10 aryl) ether-dicarboxylic acids, etc.; diaryl sulfone dicarboxylic acids, specifically, di(C) ether-dicarboxylic acids such as 4,4'-diphenyl sulfone dicarboxylic acid. 6-10 Examples include aryl)sulfone-dicarboxylic acids.

[0172] Furthermore, polyamide resins may or may not contain other polymerization components (monomer components) different from the diamine and dicarboxylic acid components, as needed. Other polymerization components include, for example, aminocarboxylic acid components or lactam components [for example, aliphatic aminocarboxylic acid components (for example, aminoalkyl carboxylic acids, specifically aminoC6-aminohexanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc.]. 2-20 Alkyl carboxylic acids, etc.), alicyclic aminocarboxylic acid components (for example, aminocycloalkane carboxylic acid components, specifically aminoC such as aminocyclohexanecarboxylic acid) 5-10 Examples include cycloalkane-carboxylic acids, aromatic aminocarboxylic acid components (e.g., aminoarene carboxylic acids such as aminobenzoic acid), corresponding lactam components (e.g., lactams with 4 to 12 member rings such as ε-caprolactam and ω-laurolactam), polyfunctional polymerization components having three or more polymerizable groups (especially carboxyl groups and / or amino groups) [e.g., trivalent or higher polycarboxylic acids such as trimellitic acid and pyromellitic acid; polyalkylene polyamines such as diethylenetriamine, dipropylenetriamine, triethylenetetramine, and tetraethylenepentamine; trivalent or higher polyamines such as tri(aminopropyl)amine, triaminocyclohexane, triaminobenzene, tri(aminophenyl)methane, and tetraaminobiphenyl], diol components, hydroxycarboxylic acid components or lactone components, and diisocyanate components [polyisocyanate components exemplified in the (polyurea resins) section below].

[0173] Furthermore, components containing carboxyl groups, such as aminocarboxylic acid components, include not only the carboxylic acids exemplified above, but also corresponding amide-forming derivatives (such as aminocarboxylic acid halides like aminocarboxylic acid chlorides, and aminocarboxylic acid anhydrides).

[0174] Polyamide resins can be manufactured using conventional polymerization methods, depending on the type of polymerization component.

[0175] (Polyurea resin) Polyurea resins may contain polyamine components such as diamine components and polyisocyanate components as polymerization components, and may also contain polyol components as needed.

[0176] Polyurea resins may contain a diamine component or a polyamine component and a polyisocyanate component as polymerization components, and may also contain a polyol component as needed.

[0177] The polyurea resin may contain only a fluorene-based amine compound (1) [first diamine component] as the diamine component, or it may contain other diamine components (second diamine component) different from fluorene-based amine compound (1) as needed, or it may not contain any. Examples of the second diamine component include those similar to the second diamine component exemplified in the section on (polyimide resins) described later. The first and second diamine components may be used individually or in combination of two or more types.

[0178] Polyisocyanate components Examples of polyisocyanate components include aliphatic polyisocyanate components, alicyclic polyisocyanate components, aromatic polyisocyanate components, and polyisocyanate components having a polyol skeleton (a skeleton derived from a polyol compound (or polyether skeleton)) or a polyamine skeleton (a skeleton derived from a polyamine compound). These polyisocyanate components can be used individually or in combination of two or more.

[0179] In this specification and in the claims, the polyisocyanate component also includes modified (or derivative) forms of polyisocyanate compounds. Examples of modified (or derivative) forms of polyisocyanate compounds include dimers (uretdione), trimers (isocyanurate), carbodiimide, biuret, allohanate, and blocked isocyanate forms.

[0180] Examples of aliphatic polyisocyanate components include aliphatic diisocyanate components, specifically alkane diisocyanates, such as hexamethylene diisocyanate (HDI or 1,6-hexanediisocyanate), 2,2,4 or 2,4,4-trimethylhexamethylene diisocyanate, etc. 2-20 Examples include alkane diisocyanates, lysine diisocyanate, and triisocyanates such as 1,3,6-hexamethylene triisocyanate.

[0181] Examples of alicyclic polyisocyanate components include alicyclic diisocyanate components, specifically cycloalkane diisocyanates such as methyl-2,4- or 2,6-cyclohexane diisocyanate, isocyanatoalkylcycloalkane 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.

[0182] Examples of aromatic polyisocyanate components include aromatic diisocyanate components, specifically, o-,m- or p-phenylenediisocyanate, chlorophenylenediisocyanate, tolylenediisocyanate (TDI), naphthalenediisocyanate (NDI), allene diisocyanates which may have substituents such as tolidinediisocyanate (TODI or 3,3'-dimethylbiphenyl-4,4'-diisocyanate), bis(isocyanatoaryl)alkanes such as diphenylmethanediisocyanate (MDI), aromatic aliphatic diisocyanates such as xylylenediisocyanate (XDI) and tetramethylxylylenediisocyanate (TMXDI), bis(isocyanatophenyl) ethers, bis(isocyanatophenyl) sulfones, etc.; and tri or tetraisocyanates such as 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate.

[0183] Examples of polyisocyanate components having a polyol or polyamine skeleton include polyisocyanate compounds (adducts or prepolymers) obtained by reacting polyol compounds and / or polyamine compounds with conventional polyisocyanate compounds. Examples of the polyol compounds include low molecular weight polyols such as alkanediols, polyalkanediols, and trimethylolpropane; and high molecular weight polyols such as polyether polyols and polyester polyols. Examples of the polyamine compounds include the compounds exemplified as diamine components.

[0184] Examples of polyol components include the compounds exemplified above as polyol compounds.

[0185] Polyurea resins can be manufactured using conventional polymerization methods, depending on the type of polymerization component.

[0186] (Polyimide resin) Polyimide resins may contain a diamine component and a tetracarboxylic acid component and / or a bismaleimide component as polymerization components.

[0187] The polyimide resin may contain only a fluorene-based amine compound (1) [first diamine component] as the diamine component, or it may contain other diamine components (second diamine component) different from fluorene-based amine compound (1) as needed, or it may not contain any diamine components at all. The first diamine component and the second diamine component can each be used individually or in combination of two or more types.

[0188] Second diamine component Examples of the second diamine component include aliphatic diamine components, alicyclic diamine components, and aromatic diamine components.

[0189] Examples of aliphatic diamine components include alkanediamines and aliphatic diamines having heteroatoms such as oxygen atoms and sulfur atoms (for example, nitrogen atoms, oxygen atoms, sulfur atoms, etc.).

[0190] Examples of alkanediamines include linear or branched C25C2 such as ethylenediamine, trimethylenediamine, propylenediamine, tetramethylenediamine, 2-methyl-1,2-propanediamine, 2-methyl-1,3-propanediamine, pentamethylenediamine, 1,3-pentanediamine, 2,2-dimethyl-1,3-propanediamine, hexamethylenediamine, 2-methylpentamethylenediamine, 2,3-dimethyl-2,3-butanediamine, heptamethylenediamine, octamethylenediamine, 2,5-dimethyl-2,5-hexanediamine, nonamethylenediamine, 2-methyloctamethylenediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, decamethylenediamine, undecamethylenediamine, and dodecamethylenediamine. 2-20 Alkanediamine (preferably C 2-12 Examples include alkanediamines.

[0191] Examples of aliphatic diamines having heteroatoms (e.g., nitrogen, oxygen, sulfur atoms) include aliphatic (poly)ether diamines, aliphatic sulfide diamines, and N,N-bis(aminoalkyl)-alkylamines.

[0192] Examples of aliphatic (poly)ether diamines include bis(aminoalkyl) ethers such as bis(2-aminoethyl) ether; (poly)alkylene glycol bis(aminoalkyl) ethers such as ethylene glycol bis(2-aminoethyl) ether, 1,4-butanediol bis(3-aminopropyl) ether, diethylene glycol bis(3-aminopropyl) ether, triethylene glycol bis(2-aminoethyl) ether, polyethylene glycol diamine, and polypropylene glycol diamine.

[0193] Examples of aliphatic sulfide diamines include bis(aminoalkyl) sulfides such as bis(2-aminoethyl) sulfide.

[0194] Examples of N,N-bis(aminoalkyl)-alkylamines include N,N-bis(3-aminopropyl)methylamine.

[0195] Examples of alicyclic diamine components include alicyclic diamines having a monocyclic skeleton, and alicyclic diamines having a cross-linked cyclic or spirocyclic skeleton.

[0196] Examples of alicyclic diamines having a monocyclic skeleton include diamines having a cycloalkane skeleton and diamines having a heterocyclic skeleton.

[0197] Examples of diamines having a cycloalkane skeleton include cycloalkanediamines such as cyclohexanediamine (1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine); bis(aminoalkyl)cycloalkanes such as 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane; 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; isophoronediamines; and mensendiamines.

[0198] Examples of diamines having a heterocyclic skeleton include piperazines such as piperazine, 2-methylpiperazine, 2-ethylpiperazine, 2,5-dimethylpiperazine, and N-(2-aminoethyl)piperazine.

[0199] Examples of alicyclic diamines having a crosslinked cyclic skeleton include bi or tricycloalkanediamines such as adamantane-1,3-diamine, 2,5- or 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane, and bis(aminomethyl)tricyclo[5.2.1.0 2,6 Examples include bis(aminoalkyl)bi or tricycloalkanes such as decane. Examples of alicyclic diamines having a spirocyclic skeleton include 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0200] Aromatic diamine components include, for example, 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)keto Bis(aminoaryl) ketones such as bis(3-aminophenyl)ketone; bis(aminoaryl) sulfides 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 Examples include 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.

[0201] The diamine component only needs to contain at least a fluorene-based amine compound (1) or a salt thereof [the first diamine component], and the proportion of constituent units derived from the first diamine component is, for example, 10 to 100 mol%, preferably 30 mol% or more, 50 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, and substantially 100 mol% or more, relative to the total constituent units derived from the diamine component.

[0202] The proportion of constituent units derived from the second diamine component is, for example, 0 to 90 mol% (for example, 10 to 80 mol%) relative to the total constituent units derived from the diamine component, preferably in the following steps: 70 mol% or less, 50 mol% or less, 30 mol% or less, 20 mol% or less, 10 mol% or less, 5 mol% or less, and 0 mol%.

[0203] The polyimide resin may be formed by a reaction (condensation reaction) between the diamine component and the tetracarboxylic acid component and / or a reaction (addition reaction) with the bismaleimide component.

[0204] Tetracarboxylic acid components The tetracarboxylic acid component only needs to be able to form an imide ring skeleton together with the diamine component, and may be a tetracarboxylic acid or its derivatives (imide-forming derivatives), such as tetracarboxylic acid diesters (or bishalf esters) (alkyl esters such as methyl esters and ethyl esters), or derivatives of tetracarboxylic acid dianhydrides, with tetracarboxylic acid dianhydrides being preferred.

[0205] Examples of tetracarboxylic acid components include aromatic tetracarboxylic acid components and alicyclic tetracarboxylic acid components. These tetracarboxylic acid components can be used individually or in combination of two or more types.

[0206] Examples of aromatic tetracarboxylic acid components include arene tetracarboxylic acids, tetracarboxylic acids having two dicarboxyarene ring skeletons (or dicarboxyaryl groups) in which carboxyl groups are substituted on adjacent carbon atoms, and imide-forming derivatives thereof. Aromatic tetracarboxylic acid components may be used alone or in combination of two or more types.

[0207] Examples of arenetetracarboxylic acids include benzenetetracarboxylic acid (such as pyromellitic acid), naphthalenetetracarboxylic acid (such as 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, etc.), and perylenetetracarboxylic acid (such as 3,4,9,10-perylenetetracarboxylic acid), etc. 6-20 Examples include arene-tetracarboxylic acids, preferably C 6-14 C such as arene-tetracarboxylic acid, more preferably pyromellitic acid, naphthalenetetracarboxylic acid, etc. 6-10 It is an arene-tetracarboxylic acid.

[0208] Examples of tetracarboxylic acids having two dicarboxyarene ring skeletons (or dicarboxyaryl groups) in which carboxyl groups are substituted on adjacent carbon atoms include tetracarboxylic acids in which the two dicarboxyarene ring skeletons are directly bonded or linked by a linking group.

[0209] The aforementioned linking group may be, for example, a divalent hydrocarbon group (or R) which may be halogenated (fluorinated, chlorinated, brominated, etc.) hX Examples of divalent linking groups include ether bonds [-O-], ketone bonds or carbonyl groups [-C(=O)-], sulfone bonds or sulfonyl groups [-S(=O)2-], and groups formed by combining two or more of these. Examples of groups formed by combining two or more include groups in which ether bonds are linked on both sides of a divalent hydrocarbon group that may be halogenated, i.e., groups [-OR hX -O-](wherein, R hXThis indicates a divalent hydrocarbon group that may be halogenated. Examples include [examples of halogenated hydrocarbon groups].

[0210] The aforementioned R hX Examples of halogenated divalent hydrocarbon groups represented by include alkylene groups or alkylidene groups [methylene group, ethylene group, propylene group (2,2-propanediyl group), propylene group (1,2-propanediyl group), trimethylene group, 1,2-butanediyl group, tetramethylene group, etc.] 1-6 [such as alkylene groups or alkylidene groups], alkylylene groups (such as ethynylene groups, etc.) 2-6 Aliphatic hydrocarbon groups such as alkynylene groups; cycloalkanediyl groups (such as cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclododecane-diyl, etc.) 3-12 Alicyclic hydrocarbon groups such as cycloalkylene groups; arylene groups [for example, alkyl groups such as phenylene, torylene, xylylene, naphthylene, etc. (C 1-6 Arylene group (C) may be substituted with alkyl groups, etc. 6-10 [e.g., arylene group], biaryl-diyl group (e.g., biphenyl-4,4'-diyl group, biphenyl-3,3'-diyl group, etc.) 6-10 Diaryl-diyl groups, etc., bisphenol residues [for example, diarylalkanediyl groups, specifically 2,2-diphenylpropane-4,4'-diyl group (bisphenol A residue), diphenylmethane-4,4'-diyl group (bisphenol F residue), etc.] 6-10 Aryl-C 1-6 Alkane-diyl groups, diphenyl ether diyl groups, specifically diphenyl ether-4,4'-diyl groups and other diC groups. 6-10 DiC groups such as aryl ether diyl groups, diphenyl ketone diyl groups, specifically diphenyl ketone-4,4'-diyl groups. 6-10 Diphenylsulfondiyl groups, specifically diphenylsulfon-4,4'-diyl groups (bisphenol S residues), and other diC groups. 6-10Examples include aromatic hydrocarbon groups such as aryl sulfondiyl groups, and halogenated groups (fluorinated, chlorinated, brominated, etc.) derived from these groups. Fluorination is preferred as the halogenation method.

[0211] Preferred R hX (Divalent hydrocarbon group which may be halogenated) is a halogenated aliphatic or aromatic hydrocarbon group, more preferably a fluorinated aliphatic hydrocarbon group [alkylene group or alkylidene group, specifically a fluorinated C group such as methylene group, propyridene group (2,2-propanediyl group), hexafluoropropyridene group (2,2-hexafluoropropanediyl group)]. 1-6 [An alkylene group or alkylidene group] or a bisphenol residue.

[0212] The group [-OR hX Examples of the -O- group include a group in which ether bonds are linked to both sides of the bisphenol residue.

[0213] Preferred linking groups include directly bonded or halogenated divalent hydrocarbon groups [-R hX The group is a [-O-], ether bond [-O-], ketone bond or carbonyl group [-C(=O)-], or a group formed by linking two or more of these together, and more preferably a direct bond.

[0214] Typical tetracarboxylic acids having two dicarboxyarene ring skeletons (or dicarboxyaryl groups) include, for example, biaryltetracarboxylic acids [for example, biphenyltetracarboxylic acids (3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, etc.) and other bi-C 6-10[Aryl-tetracarboxylic acids, etc.]; Bis(dicarboxyaryl)alkanes [e.g., fluorinated bis(dicarboxyC)alkanes such as 3,3',4,4'-tetracarboxydiphenylmethane, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane]; 6-10 Ariel)C 1-10 Alkanes, etc.; Bis(dicarboxyaryl) ethers [e.g., bis(dicarboxyC) such as 4,4'-oxydiphthalic acid, 3,4'-oxydiphthalic acid, etc.] 6-10 [Aaryl ethers, etc.]; Bis(dicarboxyaryl) ketones [e.g., bis(dicarboxyC) such as 3,3',4,4'-benzophenonetetracarboxylic acid] 6-10 [Aaryl) ketones, etc.]; bis(dicarboxyaryl) sulfones [e.g., bis(dicarboxyC) such as 3,3',4,4'-diphenylsulfonetetracarboxylic acid] 6-10 [Aryl) sulfones, etc.]; bis(dicarboxyaryloxyaryl) alkanes [e.g., 2,2-bis[4-(3,4-dicarboxyphenyloxy)phenyl]propane, etc.] 6-10 Aryloxy-C 6-10 Ariel)C 1-10 Examples include alkanes, etc.

[0215] Examples of alicyclic tetracarboxylic acid components include hydrogenated aromatic tetracarboxylic acids, cycloalkanetetracarboxylic acids [for example, alkyl groups such as cyclobutanetetracarboxylic acid, tetramethylcyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, and cyclohexanetetracarboxylic acid (C 1-6 C may be substituted with alkyl groups, etc. 4-6 Examples include cycloalkanetetracarboxylic acids, crosslinked cyclic tetracarboxylic acids (such as bicyclooctanetetracarboxylic acid, bicyclooctenetetracarboxylic acid, tricyclododecanetetracarboxylic acid, and other bi or tricycloalkanetetracarboxylic acids), or imide-forming derivatives thereof.

[0216] Furthermore, the tetracarboxylic acid components, 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 substituents. The substituents may be non-reactive substituents that are inert to polymerization reactions. Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, acyl groups, nitro groups, cyano groups, and disubstituted amino groups. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples of alkyl groups (linear or branched alkyl groups) include methyl groups, ethyl groups, propyl groups, isopropyl groups, n-butyl groups, t-butyl groups, etc. 1-10 Alkyl alkyl group, preferably C 1-6 Alkyl alkyl groups, more preferably C 1-4 Alkyl groups are examples. Examples of alkoxy groups (linear or branched alkoxy groups) include methoxy, ethoxy, propoxy, n-butoxy, and t-butoxy groups. 1-10 Examples include alkoxy groups. Acyl groups include acetyl groups and other C groups. 1-6 Examples include alkyl-carbonyl groups. Examples of disubstituted amino groups include diC groups such as dimethylamino groups. 1-4 bis(C) groups such as alkylamino groups and diacetylamino groups 1-4 Examples include alkyl-carbonyl)amino groups. The substituents may be present individually or in combination of two or more. Preferred substituents include halogen atoms such as fluorine atoms, and C 1-4 Alkyl alkyl groups, C 1-4 The substituent is an alkoxy group such as an alkoxy group, and a halogen atom such as a fluorine atom is more preferred. The number of substituents is, for example, 0 to 6, preferably in stages from 0 to 4, 0 to 2, more preferably 0 or 1, and particularly preferably 0. When the number of substituents is 2 or more, the types of substituents may be the same or different from each other.

[0217] Preferred tetracarboxylic acid components are aromatic tetracarboxylic acid components such as arene tetracarboxylic acid, tetracarboxylic acid having two dicarboxyarene ring skeletons (or dicarboxyaryl groups), and their imide-forming derivatives (such as dianhydrides); more preferably C 6-14 Arene-tetracarboxylic acid, a divalent hydrocarbon group in which two dicarboxyarene ring skeletons (or dicarboxyaryl groups) are directly bonded, and which may be halogenated [-R hX These are tetracarboxylic acids linked by a [-O-], ether linkage [-O-], ketone linkage, or carbonyl group [-C(=O)-], or a group formed by linking two or more of these (especially by direct linkage), and imide-forming derivatives thereof. The tetracarboxylic acid component may be used alone or in combination of two or more.

[0218] The proportion of constituent units derived from aromatic tetracarboxylic acid components is, for example, 10 to 100 mol%, preferably in stages, 30 mol% or more, 50 mol% or more, 70 mol% or more, 80 mol% or more, and 90 mol% or more, with substantially 100 mol% being more preferable, relative to the total constituent units derived from tetracarboxylic acid components.

[0219] Bismaleimide component The bismaleimide component only needs to have two maleimide skeletons, and examples include aliphatic bismaleimide components and aromatic bismaleimide components.

[0220] Examples of aliphatic bismaleimide components include bismaleimide alkanes, specifically bismaleimide C such as 1,2-bismaleimideethane, 1,4-bismaleimidebutane, 1,6-bismaleimidehexane, and 1,6'-bismaleimide-(2,2,4-trimethyl)hexane. 2-12 Alkanes are one example.

[0221] Examples of aromatic bismaleimide components include N,N'-arylenebismaleimide which may have an alkyl group (e.g., N,N'-1,4-phenylenebismaleimide, N,N'-1,3-phenylenebismaleimide, 4-methyl-N,N'-1,3-phenylenebismaleimide, N,N'-1,2-phenylenebismaleimide, etc.). 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 [e.g., 4,4'-bismaleimidediphenylmethane, 3,3'-dimethyl-5,5'-diethyl-4,4'-bismaleimidediphenylmethane, etc.] 1-6 Bis(maleimide C) which may have an alkyl group 6-10 Ariel)C 1-6 Alkanes, etc.; Bis(maleimidoaryl) ethers [e.g., bis(maleimido C) ethers such as 4,4'-bismaleimidodiphenyl ether] 6-10 [Aaryl ethers, etc.]; Bis(maleimidoaryl) sulfones [e.g., bis(maleimido) C, such as 4,4'-bismaleimidodiphenylsulfone] 6-10 [Aryl) sulfones, etc.]; bis(maleimidoaryloxy)arenes [e.g., 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, etc., bis(maleimido C 6-10 Aryloxy)C 6-10 [Arenes, etc.]; Bis(maleimidearyloxyaryl)alkanes [e.g., 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane (or bisphenol A diphenyl ether bismaleimide) and other bis(maleimide C 6-10 Aryloxy C 6-10 Ariel)C 1-6 Examples include alkanes, etc.

[0222] The bismaleimide component may be used alone or in combination of two or more types.

[0223] Other polymer components 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, as needed. Examples of 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 like ethynylaniline, carboxyl group-containing components like ethynylphthalic acid, methylethynylphthalic acid, phenylethynylphthalic acid, and their imide-forming derivatives), and the polyisocyanate component.

[0224] 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 proportion of constituent 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, and substantially 100 mol% or more, relative to the total constituent units of the polyimide resin (constituent units derived from the monomer component).

[0225] (Method of manufacturing resin) The resins of this disclosure may be prepared or polymerized by conventional methods depending on their type (or the type of resin raw material or polymerization component to be reacted). A typical manufacturing method may include a polymerization step in which a polymerization component (monomer component) containing a diamine component is polymerized (subjected to a polymerization reaction).

[0226] The polymerization method in the polymerization process for preparing polyimide resins can be carried out by subjecting them to conventional reactions depending on the type of polymerization component. For example, if the polymerization component includes a bismaleimide component in addition to a diamine component, it may be produced by an addition reaction (polyaddition) between the amino group of the diamine component and the maleimide group of the bismaleimide component by heat treatment or the like. Alternatively, if the polymerization component includes a tetracarboxylic acid component (especially tetracarboxylic dianhydride) in addition to a diamine component, it can be produced by a method including a polymerization step [polyamic acid (or polyamic acid) formation step] in which the diamine component and the tetracarboxylic acid component are reacted, and a ring-closing step (imide ring formation step) in which the polyamic acid (or polyamic acid) obtained in this polymerization step is subjected to a condensation or dehydration reaction to form an imide ring skeleton.

[0227] Polymerization process [Polyamic acid (or polyamic acid) formation process] In the polymerization step [polyamic acid (or polyamic acid) formation step], the ratio (molar ratio) of the diamine component to the tetracarboxylic acid component (especially the tetracarboxylic acid component dianhydride) can be selected from a range of approximately 5 / 1 to 1 / 5, for example, diamine component / tetracarboxylic acid component = 3 / 1 to 1 / 3, preferably in stages as follows: 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 more preferably approximately equimolar (1 / 1).

[0228] In the polymerization step (polyamic acid formation step), the reaction between the diamine component and the tetracarboxylic acid component (especially tetracarboxylic dianhydride) may be carried out in or without a solvent. Examples of solvents include ethers [e.g., tetrahydrofuran (THF), cyclic ethers such as 1,4-dioxane, etc.]; esters (e.g., acetate esters such as ethyl acetate, etc.); ketones [e.g., chain ketones such as acetone, methyl ethyl ketone, etc., cyclic ketones such as cyclohexanone, etc.]; halogenated hydrocarbons (e.g., dichloromethane, chlorinated hydrocarbons such as chloroform, etc.); amides [e.g., chain amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), cyclic amides such as N-methyl-2-pyrrolidone (NMP), etc.]; nitriles (e.g., acetonitrile, propionitrile, etc.); and sulfoxides (dimethyl sulfoxide, etc.). Solvents can be used alone or in combination of two or more. Preferred solvents include amides, halogenated hydrocarbons, and nitriles, with amides such as NMP being even more preferred.

[0229] In the polymerization step (polyamic acid formation step), the proportion of solvent may be, for example, about 10 to 10,000 parts by mass (e.g., 100 to 1,000 parts by mass) per 100 parts by mass of the total amount of diamine and tetracarboxylic acid components, and preferably 200 to 600 parts by mass. If the proportion of solvent is within a moderate range that is not too low, it is easier to suppress a decrease in moldability (film formation ability or productivity) [for example, precipitation of polymerization components or reactants such as polyamic acid or its salts and / or increased viscosity of the reaction mixture, making film formation (or film formation) itself difficult or making thin films difficult]. If the proportion of solvent is within a moderate range that is not too high, foaming and cracking tend to occur less in the ring-closing step (imide ring formation step) due to residual solvent.

[0230] In the polymerization step (polyamic acid formation step), additives may be added in addition to the diamine component and the tetracarboxylic acid component. Examples of additives include conventional additives such as reaction accelerators, reaction retarders, and stabilizers (antioxidants, UV absorbers, heat stabilizers, light-resistant stabilizers, etc.). Additives can be used alone or in combination of two or more. The total proportion of additives may be, for example, 30 parts by mass or less (for example, 0.1 to 30 parts by mass) per 100 parts by mass of the total amount of the diamine component and the tetracarboxylic acid component, preferably 20 parts by mass or less, and more preferably 10 parts by mass or less.

[0231] In the polymerization process (polyamic acid formation process), the polymerization reaction is preferably carried out in an inert gas atmosphere (e.g., nitrogen gas; noble gases such as helium or argon). The reaction may also be carried out under normal pressure or reduced pressure.

[0232] In the polymerization process (polyamic acid formation process), the reaction temperature (polymerization temperature) may be, for example, 0°C or higher (e.g., about 20 to 120°C), preferably 25°C or higher (e.g., about 30 to 100°C), more preferably 40°C or higher (e.g., about 45 to 80°C), and particularly preferably 50 to 70°C (e.g., about 55 to 65°C). When the reaction temperature (polymerization temperature) is within a moderate range that is not too low, it tends to suppress a decrease in moldability (film formation ability or productivity) [for example, difficulty in film formation (or film formation itself) due to precipitation of polymerization components or reactants such as polyamic acid or its salts].

[0233] The reaction time can be appropriately selected depending on the reaction conditions, and may be, for example, 1 to 100 hours (e.g., 6 to 48 hours), but preferably 12 to 36 hours (e.g., 18 to 30 hours).

[0234] The reaction mixture (or polyamic acid composition) containing the polyamic acid (or polyamic acid) obtained by the reaction may be separated (or purified) by conventional methods, such as filtration, concentration, extraction, washing, drying, reprecipitation, column chromatography, or a combination thereof, and purification is not necessarily required. For example, the reaction mixture (polyamic acid composition) containing the polyamic acid (or polyamic acid) may be used as a varnish or coating composition (or liquid composition for forming a polyimide resin) containing a solvent without purification, as described later.

[0235] This disclosure also includes polyamic acids, i.e., polyamic acids obtained by polymerization (polymerization step or polyamic acid formation step) of a polymerization component containing a diamine component including a fluorene-based amine compound (1) and a tetracarboxylic acid component, and polyamic acid compositions (resin compositions) containing this polyamic acid.

[0236] The resulting polyamic acid (or polyamic acid) has constituent units derived from or corresponding to the reacted polymerization components (diamine component and tetracarboxylic acid component). The weight-average molecular weight Mw of the polyamic acid may be, for example, 10,000 or more (e.g., 30,000 to 1,000,000), preferably 35,000 to 100,000 (e.g., 40,000 to 50,000), and more preferably 42,000 to 48,000 (e.g., 44,000 to 46,000). When the weight-average molecular weight Mw of the polyamic acid is within a moderate range that is not too small, it tends to improve moldability. When the weight-average molecular weight of the polyamic acid is within a moderate range that is not too low, it tends to suppress the decrease in moldability (film formation or productivity).

[0237] In this specification and in the claims, the weight-average molecular weight of polyamic acid can be measured by gel permeation chromatography (GPC) using the method described in the examples below, by converting the standard substance to polystyrene.

[0238] Ring closure process (imide ring formation process) Polyimide resins can be produced by subjecting the polyamic acid (or polyamic acid) obtained in the polymerization step (polyamic acid formation step) to a condensation or dehydration reaction to form an imide ring skeleton in a ring-closing step (imide ring formation step). In the ring-closing step, the method of condensation or dehydration reaction is sufficient to form an imide ring skeleton. For example, as described later, the polyamic acid may be condensed or dehydrated by heat treatment to form an imide ring (ring closure).

[0239] Furthermore, the reaction mixture (polyamic acid composition) containing polyamic acid (or polyamic acid) obtained in the polymerization step (polyamic acid formation step) may be heated as is to close the ring, or the solvent may be removed before heating to close the ring. However, when forming into a film or sheet, the reaction mixture (polyamic acid composition which is a varnish, coating composition, or liquid composition) may be coated onto a predetermined substrate, and the resulting coated film (film or sheet) of the polyamic acid composition may be subjected to the ring-closing step.

[0240] The varnish or coating composition (liquid composition) may be prepared by using the reaction mixture containing polyamic acid (or polyamic acid) obtained in the polymerization step (polyamic acid formation step) as is, or by dissolving the polyamic acid in a solvent. The solvent can be the same as the solvent exemplified in the polymerization step (polyamic acid formation step), including preferred embodiments. The concentration of polyamic acid in the varnish or coating composition may be adjusted as appropriate considering the film thickness and coating properties, for example, to about 5 to 80% by mass (e.g., 8 to 50% by mass), preferably 10 to 40% by mass (e.g., 12 to 30% by mass), and more preferably 15 to 25% by mass. When the proportion of solvent is within a moderate range, not too low, it is easier to suppress a decrease in moldability (film formation ability or productivity) [for example, the precipitation of polymerization components or reactants such as polyamic acid or its salts, and / or the increased viscosity of the reaction mixture, which can make film formation (or film formation) itself difficult or make it difficult to form thin films]. Also, when the proportion is within a moderate range, not too high, foaming and cracking tend to occur less likely in the ring-closing process (imide ring formation process) due to residual solvent.

[0241] Furthermore, the viscosity of the varnish or coating composition may be adjusted as appropriate to suit the moldability (or coating properties), and may be, for example, around 100 to 20,000 mPa·s (e.g., 300 to 10,000 mPa·s), preferably 500 to 5,000 mPa·s (e.g., 800 to 3,000 mPa·s), and more preferably 1,000 to 2,000 mPa·s.

[0242] The varnish or coating composition (liquid polyamic acid composition) may contain additives. Examples of additives included in the liquid composition include crosslinking or curing agents, defoaming agents, coatability improvers, thickeners, lubricants, stabilizers (antioxidants, UV absorbers, heat stabilizers, light-resistant stabilizers, etc.), dyes, pigments, antistatic agents, flame retardants, flame retardant aids, antiblocking agents, fillers, and gelling agents. Additives may be used individually or in combination of two or more. The total proportion of additives may be, for example, 30 parts by mass or less (e.g., 0.1 to 30 parts by mass) per 100 parts by mass of polyamic acid, preferably 20 parts by mass or less, and more preferably 10 parts by mass or less.

[0243] The varnish or coating composition (liquid polyamic acid composition) may be degassed before coating, if necessary, to facilitate the formation of a film with excellent mechanical properties. Conventional degassing methods include vacuum (reduced pressure) degassing, ultrasonic degassing, centrifugal degassing, agitation degassing, and static degassing. Degassing may also be performed by heating. The heating temperature is, for example, around 40-80°C, preferably 50-70°C. Degassing may also be performed by gradually increasing the temperature from room temperature to the aforementioned heating temperature.

[0244] Conventional coating methods for varnish or coating compositions (liquid polyamic acid compositions) include 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 with varnish or a coating composition (liquid polyamic acid composition) may be dried. The drying method is not particularly limited and may be air-dried, but from the viewpoint of productivity, heat drying is preferred. In heat drying, the heating temperature may be, for example, 150°C or less, preferably 40 to 120°C (e.g., 60 to 100°C), and more preferably 70 to 90°C. The drying time can be appropriately selected according to the heating temperature, etc., for example 1 to 180 minutes, preferably 5 to 120 minutes (e.g., 10 to 60 minutes). In this way, the coating film of varnish or a coating composition (film-like or sheet-like polyamic acid composition) may be subjected to a ring-closing step (imide ring formation step) to undergo a condensation or dehydration reaction to form a polyimide resin.

[0246] In the ring-closing step (imide ring formation step), the polyamic acid may be dehydrated or condensed (i.e., ring-closed) by heat treatment to form an imide ring. The heating temperature in the ring-closing step (reaction temperature of the condensation or dehydration reaction) may be, for example, around 150 to 400°C (e.g., 180 to 350°C). From the standpoint of easier manufacturing with higher moldability (film-forming ability or productivity), it is preferably around 300°C or less, more preferably 290°C or less (e.g., 200 to 285°C), even more preferably 280°C or less (e.g., 210 to 275°C), most preferably 220 to 270°C (e.g., 230 to 265°C), and particularly preferably 240 to 260°C (e.g., 245 to 255°C). When the reaction temperature is within a moderate range and not too high, it is easier to suppress the decrease in moldability (film formation ability or productivity), especially the decrease in moldability or dimensional stability due to shrinkage. When the reaction temperature is within a moderate range and not too low, the reaction can proceed efficiently, and polyimide resins tend to be produced with high productivity.

[0247] The ring-closing process may be carried out under atmospheric pressure, reduced pressure (or vacuum), or pressurized pressure, with reduced pressure (or vacuum) being preferred. The processing time for the ring-closing process can be appropriately selected depending on the reaction conditions, for example, 10 minutes to 6 hours, preferably 30 minutes to 3 hours, and more preferably 1 to 2 hours.

[0248] (Properties of polyimide resins) The resins disclosed herein (polyamide resins, polyurea resins, polyimide resins, and especially polyamic acid and / or polyimide resins) appear to be colorless, highly transparent, and possess excellent moldability (particularly film moldability).

[0249] (Resin composition) The resin compositions of this disclosure may contain at least one selected from fluorene-based amine compounds (1) and fluorene-based azide compounds (2) as a resin raw material and / or resin additive. That is, the resin compositions of this disclosure may be resin compositions containing the resin of this disclosure [a resin using fluorene-based amine compound (1) and / or fluorene-based azide compound (2) as a resin raw material]; or they may be resin compositions containing fluorene-based amine compound (1) and / or fluorene-based azide compound (2) as resin additives and a resin (the resin of this disclosure and / or a conventional resin).

[0250] Examples of resins include curable resins (thermo-curable or photocurable resins) and thermoplastic resins.

[0251] Examples of curable resins (thermal or photocurable resins) include phenolic resins (resol type, novolac type, etc.); amino resins (urea resin, melamine resin, guanamine resin, etc.); furan resins; unsaturated polyester resins; diallyl phthalate resins; vinyl ester resins [or epoxy (meth)acrylate resins]; polyfunctional (meth)acrylate resins; epoxy resins; urethane resins; polyimide resins; and silicone resins.

[0252] Examples of thermoplastic resins include polyolefin resins (such as chain or cyclic olefin resins); styrene resins [polystyrene (PS) or styrene copolymers (including high-impact polystyrene (HIPS), rubber-containing styrene resins such as ABS resin (or rubber-grafted styrene copolymers))]; (meth)acrylic resins [such as (meth)acrylic monomers alone or copolymers]; vinyl acetate resins [including polyvinyl alcohol (PVA) and polyvinyl acetal]; vinyl chloride resins (such as vinyl chloride and / or vinylidene chloride alone or copolymers); fluororesins; polyester resins [such as polyalkylene arylate resins, polyarylate resins, and liquid crystalline polyesters]; and polycarbonate resins (PC), specifically bisphenol A Examples include bisphenol-type polycarbonate resins such as molds; polyamide resins (PA) [aliphatic polyamide resins, aromatic polyamide resins (aramid resins), etc.]; polyacetal resins (POM); polyphenylene ether resins (PPE); polyphenylene sulfide resins (PPS); polysulfone resins [polysulfone resins (PSF), polyethersulfone (PES), etc.]; polyetherketone resins [polyetherketone resins (PEK), polyetheretherketone resins (PEEK), polyetherketone etherketone ketone (PEKEKK), etc.]; phenoxy resins; polyketone resins; cellulose derivatives (cellulose esters, cellulose ethers, etc.); thermoplastic polyimide resins; polyethernitrile resins; thermoplastic elastomers (TPE), etc.

[0253] These resins may be included individually or in combination of two or more types.

[0254] Furthermore, when the fluorene-based amine compound (1) and / or the fluorene-based azide compound (2) are included as resin additives, they may, for example, act as a refractive index modifier (refractive index improver) of the resin; they may act as a curing agent or curing accelerator in combination with epoxy resins, etc.; or they may act as a crosslinking agent or chain extender (or chain lengthening agent) in combination with polyurethane resins, polyurea resins, etc. When the fluorene-based amine compound (1) and / or the fluorene-based azide compound (2) act as a curing agent or curing accelerator, crosslinking agent, chain extender (or chain lengthening agent), etc., the resin composition may be a curable composition or its cured product.

[0255] When a fluorene-based amine compound (1) and / or a fluorene-based azide compound (2) are included as resin additives, the proportion of the fluorene-based amine compound (1) and / or fluorene-based azide compound (2) [especially the fluorene-based amine compound (1)] in the resin composition can be appropriately selected depending on the application, and may be, for example, about 80% by mass or less of the total amount of the resin and the fluorene-based amine compound (1) and / or fluorene-based azide compound (2). Preferably, it may be in stages as follows: 70% by mass or less, 50% by mass or less, 30% by mass or less, 15% by mass or less, and 10% by mass or less (for example, 0.1 to 5% by mass).

[0256] The resin composition may optionally contain various conventional additives, such as fillers or reinforcing agents, colorants such as dyes and pigments, conductive agents, flame retardants, flame retardant aids, plasticizers, lubricants, stabilizers (antioxidants, UV absorbers, heat stabilizers, etc.), mold release agents, antistatic agents, dispersants, compatibilizers, flow regulators, leveling agents, defoamers, surface modifiers, stress reducers, carbon materials, etc. These additives may be used individually or in combination of two or more.

[0257] The total proportion of these additives is, for example, 50 parts by mass or less, preferably 30 parts by mass or less, 0 to 10 parts by mass, and may be about 0.1 to 5 parts by mass, based on 100 parts by mass of resin in the resin composition.

[0258] The resin composition may be prepared by mixing a resin with a fluorene-based amine compound (1) and / or a fluorene-based azide compound (2) and other components as needed, for example by conventional methods such as dry mixing or melt kneading, and the resin composition may be in the form of pellets or the like.

[0259] (Molded body) This disclosure includes molded articles comprising at least the resins and / or resin compositions of the disclosure. The shape of the molded articles is not particularly limited and may be selected depending on the application, and may be, for example, pellets, one-dimensional structures such as linear (fibrous or thread-like) or rod-like structures, two-dimensional structures such as film-like, sheet-like, or plate-like structures, three-dimensional structures such as block-like, lens-like (concave or convex lens-like, etc.), or hollow (tubular or tubular) structures, or composite or complex shapes combining these shapes.

[0260] Molded articles can be manufactured using conventional molding methods depending on the type of resin, the shape and application of the molded article, and can be produced using methods such as injection molding, compression molding, transfer molding, lamination molding, FRP molding, casting, powder molding, extrusion molding, blow molding, lamination, casting, calendering, foam molding, and 3D printing.

[0261] Furthermore, the molded article may be a composite molded article comprising the resin composition of the present disclosure and other components. The proportion of the resin composition of the present disclosure in the molded article is not particularly limited and may be, for example, 10 to 100% by mass or 20 to 80% by mass.

[0262] When the molded product has a two-dimensional structure such as a film or sheet, it can be manufactured by forming (or molding) the film using conventional film formation methods, such as casting (solvent casting), melt extrusion, or calendering.

[0263] The average thickness of the film may be selected from a range of approximately 1 to 1000 μm (e.g., 5 to 300 μm) depending on the application, and preferably approximately 10 to 250 μm.

[0264] The film may be unstretched or stretched, and the stretched film may be either uniaxially oriented or biaxially oriented.

[0265] The stretching ratio is, for example, 1.1 to 10 times, preferably 1.2 to 8 times, and more preferably 1.5 to 6 times, in each direction for uniaxial or biaxial stretching. In the case of biaxial stretching, equal stretching, for example, 1.5 to 5 times in both the longitudinal and transverse directions, is also possible, as is eccentric stretching, for example, 1.1 to 4 times in the longitudinal direction and 2 to 6 times in the transverse direction. In the case of uniaxial stretching, longitudinal stretching, for example, 2.5 to 8 times in the longitudinal direction, is also possible, as is transverse stretching, for example, 1.2 to 5 times in the transverse direction.

[0266] 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.

[0267] Furthermore, the stretched film may be prepared by subjecting the film (or unstretched film) after film formation to a stretching treatment. The stretching method is not particularly limited; in the case of uniaxial stretching, either wet stretching or dry stretching may be used, and in the case of biaxial stretching, either the tenter method (flat method) or the tube method may be used.

[0268] The molded body may be in the form of a plate, such as a circuit board. The average thickness of the molded body (especially the circuit board) may be appropriately selected depending on the application, for example, about 10 to 120 μm, preferably about 15 to 100 μm (for example, about 20 to 50 μm). [Examples]

[0269] The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples. The evaluation items and raw material details are shown below.

[0270] [Evaluation Method] (HPLC and LC-MS) Using a Shimadzu LCMS-2020 HPLC (High Performance Liquid Chromatography) instrument and a Shimadzu KINTEX XB-C18 column, the mobile phase (acetonitrile / water, volume ratio) was changed from 50 / 50 to 95 / 5 over 10 minutes, followed by a 5-minute retention period at 95 / 5. HPLC purity (LC purity) [area %] was calculated based on the area ratio in the resulting UV chromatogram. Mass spectra were also measured.

[0271] The HPLC purity [area %] of BPEF-NH2 obtained in Examples 2 and 3, and BNEF-NH2 obtained in Example 5, was measured using the following measuring instrument equipped with an amine column under the following measurement conditions.

[0272] Equipment: Shimadzu Corporation "LC-2060C" Detector: UV detector (LC-2060 UV Detector) Column (amine column): Waters "X Bridge C18 5μm 4.6×250mm" Mobile phase: Acetonitrile / Water (volume ratio) = 20 / 80 (5 min) → 95 / 5 (7 min) → 95 / 5 (12 min) → 80 / 20 (13 min) → 80 / 20 (23 min) → 20 / 80 (25 min) → 20 / 80 (35 min) Flow rate: 1.0000mL / min Measurement temperature: 40℃

[0273] ( 1 (H-NMR) The sample was dissolved in a deuterated chloroform solvent containing tetramethylsilane as an internal standard, and then analyzed using a nuclear magnetic resonance spectrometer (BRUKER AVANCE III HD).1 The 1H-NMR spectrum was measured.

[0274] (Melting point, glass transition temperature) A differential scanning calorimeter (DSC) (TA Instruments "Discovery DSC25") was used to perform measurements under a nitrogen atmosphere, with a measurement temperature of 30-250°C and a heating rate of 10°C / min. From the obtained DSC chart, the peak top temperature of the endothermic peak was read as the melting point.

[0275] For BNEF-NH2 obtained in Example 5, the glass transition temperature Tg was read from the DSC chart obtained using the same method.

[0276] (5% weight loss temperature) Using a thermogravimetric analyzer (TG / DTA6200, manufactured by SII Nanotechnology Co., Ltd.), the temperature at which the mass of the sample decreased by 5% (5% weight loss temperature Td5) was measured under conditions of a nitrogen atmosphere, a heating rate of 10°C / min, and a temperature range of 30 to 500°C.

[0277] (Solid content) The amount of solids was measured under the following conditions using the following measuring equipment. Equipment: AND heating dryer moisture meter “MX-50” Settings: Auto-shutdown mode Sample quantity: 1g Heating temperature: 180℃ End point: Automatic measurement ends when the weight loss rate falls below 0.10% weight / minute.

[0278] (X-ray diffraction (XRD)) Measurements were taken using a powder X-ray diffractometer (Rigaku Corporation's "Smart Lab" fully automatic multi-purpose horizontal X-ray diffractometer) under the following conditions: output power of 3kW, radiation source (Cu tube), and measurement angle of 5-90°.

[0279] (Refractive index nD) The refractive index nD was measured using a refractometer (ATAGO RX-7000i) at a temperature of 25°C and a wavelength of 589 nm (D line). The refractive index nD of BPEF-NH2 obtained in Example 2, which was a liquid, was measured directly without preparing a solution. For BPEF-NH2 obtained in Example 3, which was a solid, the refractive index nD was determined by dissolving the sample in cyclohexanone to prepare solutions at concentrations of 10% by mass, 15% by mass, and 20% by mass. The refractive index of the resulting solutions and a solution at 0% by mass (cyclohexanone only) was measured, and the refractive index was extrapolated to 100% by mass in a calibration curve (approximate straight line). The refractive index nD of BNEF-NH2 obtained in Example 5 was determined using a calibration curve prepared in the same manner, except that N,N-dimethylformamide (DMF) was used at concentrations of 0%, 1%, 5%, and 10% by mass.

[0280] (Solubility Test 1) In a 30 mL test tube, the sample (200 mg) and the solvent described below were added to a concentration of 20% by mass or 10% by mass. The solubility of the sample in each solvent was confirmed by stirring at 300 rpm for 1 hour at room temperature (25°C) using a magnetic stirrer. If complete dissolution was not achieved at room temperature (25°C), the temperature was raised to 60°C, and the solubility was confirmed by stirring in the same manner as above. The solubility was then evaluated according to the following criteria.

[0281] ◎: Dissolved at 25℃ ○: Dissolved at 60°C and did not precipitate even after cooling to 25°C. △: Dissolved at 60°C, then precipitated when cooled to 25°C. ×: Did not dissolve at 60°C

[0282] (Solubility Test 2) The sample (200 mg) and the solvent described below were added to a 30 mL test tube to a concentration of 10% by mass. The solubility of the sample in each solvent was confirmed by stirring at 300 rpm for 1 hour at room temperature (25°C) using a magnetic stirrer. If the sample did not dissolve completely at room temperature (25°C), the temperature was raised to 50°C, and the solubility was confirmed by stirring in the same manner as above. The solubility was then evaluated according to the following criteria.

[0283] ◎: Dissolved at 25℃ ○: Dissolved at 50℃ ×: Did not dissolve at 50°C

[0284] (Weight average molecular weight Mw) The weight-average molecular weight (Mw) was measured using the following measuring equipment under the following measurement conditions. GPC equipment: Tosoh Corporation's "8320GPC" Column: TSKgel GMH manufactured by Tosoh Corporation XL 」×2 + TSKgel G2000H manufactured by Tosoh Corporation XL " × 1 (i.e., these three columns are connected in series in this order for measurement) Column temperature: 50℃ Eluent: N-methyl-2-pyrrolidone (NMP) [with lithium bromide (30 mmol / L) and phosphoric acid (10.5 mmol / L)] Standard material: Polystyrene Flow rate: 0.8mL / min Pretreatment: The sample, adjusted to a concentration of 0.2 w / v%, is pretreated using a membrane filter.

[0285] (viscosity) A TV-22 viscometer (cone plate type, "TVE-22L" manufactured by Toki Sangyo Co., Ltd.) was used, and the optional rotor (01: 1°34′ × R24, 07: 3° × R7.7) and rotation speed (0.5~20 rpm) were selected according to the viscosity to be measured, and measurements were taken at a temperature of 25°C.

[0286] (Film moldability) The obtained film was folded at an angle of 180°, and its flexibility was evaluated according to the following evaluation criteria.

[0287] ○: Flexible; the film does not tear even when bent. △: Lacks flexibility; the film breaks when bent. ×: Unable to produce film

[0288] [Example 1] Synthesis of BPEF-N3 (Mesylation of BPEF)

[0289] [ka]

[0290] A stirring bar, thermometer, and septum were attached to the reaction vessel, and the vessel was purged with nitrogen. 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene [Osaka Gas Chemical Co., Ltd. "BPEF", 13.1 g (29.9 mmol)] and 140 mL of tetrahydrofuran (THF) were added and dissolved. Then 12.5 mL (3.0 eq) of triethylamine was added, and the mixture was cooled to 0°C and stirred. 5.6 mL (2.5 eq) of mesyl chloride was slowly added dropwise at a temperature below 10°C, and the mixture was stirred at 0°C for 30 minutes, followed by stirring at room temperature for 3 hours. After confirming the disappearance of the starting materials and intermediates by HPLC, the mixture was diluted with 300 mL of dichloromethane, neutralized with 1N HClAq, and the organic layer was extracted using a separatory funnel. The resulting organic layer was further washed with water, dried over sodium sulfate, filtered, concentrated under reduced pressure, and dried to obtain 17.6 g of white powdered 9,9-bis[4-(2-mesyloxyethoxy)phenyl]fluorene (also known as BPEF-Ms) [yield 98.9%, LC purity 98% (detected by UV absorption at 234 nm)].

[0291] (Azidization of BPEF-Ms)

[0292] [ka]

[0293] A stirring bar and thermometer were attached to a three-necked flask, and 17.6 g (29.6 mmol) of BPEF-Ms and 200 mL of N,N-dimethylformamide (DMF) were added and dissolved. 39.62 g (5.0 eq) of NaN was then added, and the reaction was carried out under a nitrogen atmosphere at an internal temperature of 80°C for 3 hours. After confirming the progress of the reaction, 200 mL of deionized water was added to stop the reaction, and 400 mL of ethyl acetate was added to extract the organic layer using a separatory funnel. The organic layer was further washed with water, dried over sodium sulfate, filtered, concentrated under reduced pressure, and dried to obtain 14.8 g of viscous solid 9,9-bis[4-(2-azidoethoxy)phenyl]fluorene (also known as BPEF-N3) (LC purity 98.2% (detected by UV absorption at 234 nm)).

[0294] BPEF-N3 1 The results of the H-NMR spectrum are shown below.

[0295] 1 H-NMR(300MHz,CDCl3);δ(ppm) 7.84(d, 2H), 7.49-7.28(m, 6H), 7.21(t, 4H), 6.85(d, 4H), 4.20(t, 4H), 2.25(t, 4H)

[0296] [Example 2] Synthesis of BPEF-NH2 (Reduction of BPEF-N3)

[0297] [ka]

[0298] A stirring bar was placed in the reaction vessel, and 14.8 g (30.3 mmol) of BPEF-N3 and 220 mL of THF were added and dissolved. Then, 1.64 mL (3.0 eq) of deionized water was added and the mixture was stirred. 17.5 g (2.2 eq) of triphenylphosphine was slowly added, and the mixture was stirred at room temperature under air for 10 minutes. After stirring under reflux at 80°C for 3 hours, another 1.64 mL (3.0 eq) of deionized water was added, and the mixture was stirred under reflux for another 3 hours. After confirming the disappearance of the starting materials by HPLC, the mixture was cooled to 0°C, diluted with 200 mL of ethyl acetate, acidified with 4N-HCl / ethyl acetate solution, filtered, and washed with 300 mL of ethyl acetate. The obtained powder crystals were dried to obtain 16.3 g of 9,9-bis[4-(2-aminoethoxy)phenyl]fluorene [or bis(phenoxyethylamine)fluorene] hydrochloride (also known as BPEF-NH2·HCl) (LC purity 98.3% (detected by UV absorption at 234 nm)).

[0299] (Desalting of BPEF-NH2·HCl)

[0300] [ka]

[0301] A stirring bar was placed in a reaction vessel, and 10 g (19.7 mmol) of BPEF-NH2·HCl, 100 g of THF, and 30 g of deionized water were added and dissolved. Then, 30 g (0.36 mol, 18 eq) of 48% by mass sodium hydroxide aqueous solution was added, and the mixture was stirred at room temperature for 24 hours. After that, 30 g of toluene was added, and the mixture was concentrated to convert the solvent to toluene. Next, 20 g of deionized water was added and liquid-liquid extraction was performed. This washing operation was repeated twice, and the resulting organic layer was concentrated under reduced pressure to remove the solvent, yielding 9.0 g (LC purity 100%, solid content approximately 90% by mass) of 9,9-bis[4-(2-aminoethoxy)phenyl]fluorene [or bis(phenoxyethylamine)fluorene] (also called BPEF-NH2) as a yellow, viscous liquid. Note that the solvent (toluene) could not be completely removed by reduced pressure concentration (reduced pressure drying), and it appears that about 10% by mass remained. 1The 1H-NMR spectra are shown below and in Figure 1, and the LC-MS results are shown below.

[0302] 1 H-NMR(300MHz,CDCl3);δ(ppm) 7.74(d, 2H), 7.38-7.28(m, 6H), 7.11(t, 4H), 6.75(d, 4H), 3.92(t, 4H), 3.03(t, 4H), 1.59(s, 4H) LC-MS: m / z = 437 [M + H] + ,873[2M+H] +

[0303] The 5% weight loss temperature of the obtained BPEF-NH2 was 280°C, and the refractive index (25°C, nD) was 1.64.

[0304] Initially, the obtained BPEF-NH2 was a viscous liquid, but after standing for more than a day, crystals (pale yellow, viscous crystals) gradually precipitated. LC purity of these precipitated crystals was measured using an amine column, revealing a purity of 96.4%, a melting point of 127°C, and a 5% weight loss temperature of 329°C. The higher 5% weight loss temperature in the crystals compared to the yellow viscous liquid is presumed to be due to the lower amount of residual solvent in the crystals. Furthermore, the precipitated crystals were not only extremely hard (too hard to break even when a spatula was pressed against them), but also highly viscous, causing them to adhere to the glass sample tube, resulting in poor handling.

[0305] [Example 3] Crystallization of BPEF-NH2

[0306] (Example 3-1) 40g of yellow viscous liquid BPEF-NH2 (approximately 90% by mass solids, i.e., containing approximately 10% by mass solvent (toluene)) obtained in the same manner as in Example 2 was diluted with ethyl acetate, then concentrated, and the solvent was converted back to ethyl acetate. When the resulting concentrate was cooled to 5°C in an ice bath, it became a white slurry, possibly due to the precipitation of crystals. Heptane was added to this slurry to induce crystallization, and after filtration and drying, 12.0g of powdered BPEF-NH2 crystals were obtained [recovery rate 30%, pale yellowish-white, LC purity 94.8% (amine column), solids content 96.5% by mass].

[0307] (Example 3-2) A white slurry was obtained in the same manner as in Example 3-1, except that the ethyl acetate solution of BPEF-NH2 was cooled from 75°C to room temperature (approximately 25°C) without the addition of heptane. The obtained white slurry was filtered and dried to obtain powdered BPEF-NH2 crystals similar to those in Example 3-1.

[0308] The powdered BPEF-NH2 crystals obtained in Example 3 (3-1) showed significantly improved handling properties compared to those obtained in Example 2. The solvent content was reduced from approximately 10% by mass to 3.5%, and viscosity was absent. The melting point of the obtained powdered BPEF-NH2 was 125°C, the 5% weight loss temperature was 314°C, and the refractive index (25°C, nD) was 1.64. The slightly lower 5% weight loss temperature compared to Example 2 is presumed to be because, unlike Example 2, crystallization in Example 3 was promoted by external stimuli, resulting in a polycrystalline state.

[0309] Figure 2 shows the powder X-ray diffraction pattern of the BPEF-NH2 crystal obtained in Example 2, and Figure 3 shows the powder X-ray diffraction pattern of the BPEF-NH2 crystal obtained in Example 3 (3-1). The diffraction peaks are summarized in Tables 1 to 3 below. As is clear from Figures 2 to 3 and Tables 1 to 3, the diffraction patterns are almost the same, and as mentioned above, the melting points are also almost the same, suggesting that the crystals obtained in Examples 2 and 3 are the same crystal.

[0310] [Table 1]

[0311] [Table 2]

[0312] [Table 3]

[0313] [Comparative Example 1] Various evaluations were performed using 9,9-bis(4-aminophenyl)fluorene (BAF, manufactured by Osaka Gas Chemical Co., Ltd.), represented by the following formula. The melting point of BAF was 241°C, and the 5% weight loss temperature was 334°C.

[0314] [ka]

[0315] Table 4 below shows the evaluation results of Solubility Test 1 for the fluorene compounds (fluorene-based amine compounds) obtained in Example 2 and Comparative Example 1, and Table 5 below shows the evaluation results of Solubility Test 2 for the fluorene compounds obtained in Example 3 and Comparative Example 1. In Tables 4 and 5, THF represents tetrahydrofuran, MEK represents methyl ethyl ketone, MIBK represents methyl isobutyl ketone, PGMEA represents propylene glycol monomethyl ether acetate, and NMP represents N-methyl-2-pyrrolidone.

[0316] [Table 4]

[0317] [Table 5]

[0318] The fluorene compounds (BPEF-NH2) obtained in Examples 2 and 3 exhibited excellent heat resistance and refractive index, and, as is clear from the results in Tables 4 and 5, also showed better solubility compared to Comparative Example 1 (BAF).

[0319] Furthermore, BPEF-NH2 (Examples 2 and 3) exhibits a high 5% weight loss temperature and, like BAF (Comparative Example 1), has excellent heat resistance, yet its melting point is about half that of BAF (Comparative Example 1). Therefore, in applications such as forming compositions by heating and mixing with other components (for example, when BPEF-NH2 is mixed with epoxy resin as an amine-based curing agent to form a curable composition), it can be melted and mixed at a lower temperature than BAF (Comparative Example 1) while maintaining high heat resistance, making it easy or efficient to form homogeneous compositions and offering excellent handling advantages.

[0320] [Example 4] Synthesis of BNEF-N3 (Mesylation of BNEF)

[0321] [ka]

[0322] A stirring bar, thermometer, and septum were attached to the reaction vessel, and the vessel was purged with nitrogen. 25.0 g (46.4 mmol) of 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene [BNEF, manufactured by Osaka Gas Chemical Co., Ltd.] and 250 mL of THF were added and dissolved. Then 19.3 mL (3.0 eq) of triethylamine was added, and the mixture was cooled to 0°C and stirred. 13.3 g / 9.0 mL (2.5 eq) of mesyl chloride was slowly added dropwise at a temperature below 10°C, and the mixture was stirred at 0°C for 30 minutes, followed by stirring at room temperature for 40 hours. After confirming the disappearance of the starting materials and intermediates by HPLC, the THF was removed by distillation under reduced pressure with heating. The mixture was diluted with 300 mL of dichloromethane, placed in a separatory funnel, and washed with water. The resulting organic layer was dried over sodium sulfate, then filtered, concentrated under reduced pressure, and dried to obtain 33.1 g of 9,9-bis[6-(2-mesyloxyethoxy)-2-naphthyl]fluorene (also known as BNEF-Ms) as a light brown solid.

[0323] (Azidization of BNEF-Ms)

[0324] [ka]

[0325] A stirring bar and thermometer were attached to a three-necked flask, and 33.1 g (46.4 mmol) of BNEF-Ms and 300 mL of DMF were added and dissolved. Then 15.1 g (5.0 eq) of NaN3 was added, and the reaction was carried out under a nitrogen stream at an internal temperature of 80°C for 6 hours. After confirming that the reaction was progressing, 2000 mL of deionized water was added to stop the reaction, and 500 mL of ethyl acetate was added, and the organic layer was extracted using a separatory funnel. The organic layer was further washed with water, dried over sodium sulfate, filtered, concentrated under reduced pressure, and dried to obtain 25.1 g (yield 91.9%) of 9,9-bis[6-(2-azidoethoxy)-2-naphthyl]fluorene (also known as BNEF-N3) as a light brown solid.

[0326] BNEF-N3 1 The results of the H-NMR spectrum are shown below.

[0327] 1 H-NMR (300MHz, CDCl3); δ (ppm) 7.85 (d, 2H), 7.65-7.08 (m, 18H), 4.22 (t, 4H), 3.63 (t, 4H)

[0328] [Example 5] Synthesis of BNEF-NH2 (Reduction of BNEF-N3)

[0329] [ka]

[0330] A stirring bar was placed in the reaction vessel, and 25.1 g (42.6 mmol) of BNEF-N3 and 450 mL of THF were added and dissolved. Then, 2.31 mL (3.0 eq) of deionized water was added and the mixture was stirred. 36.9 g (3.3 eq) of triphenylphosphine was slowly added, and the mixture was stirred at room temperature under a nitrogen atmosphere for 10 minutes. After stirring under reflux at 75°C for 3 hours, 6.94 mL (9.0 eq) of deionized water was added, and the mixture was stirred under reflux for another 9 hours. After confirming the disappearance of the starting materials by HPLC, the mixture was cooled to 0°C, diluted with 500 mL of ethyl acetate, acidified with 4N-HClaq, and the precipitated white solid was filtered. This white solid was then washed with 150 mL of ethyl acetate. The resulting white solid was dried to obtain 25.5 g (yield 98.8%) of 9,9-bis[6-(2-aminoethoxy)-2-naphthyl]fluorene hydrochloride (also known as BNEF-NH2·HCl).

[0331] (Desalting of BNEF-NH2·HCl)

[0332] [ka]

[0333] A stirring bar was placed in the reaction vessel, and 5.0 g (8.2 mmol) of BNEF-NH2·HCl, 51.3 g of THF, and 15.1 g of deionized water were added and dissolved. Then, 20.5 g (153.8 mmol, 18.8 eq) of 30% by mass sodium hydroxide aqueous solution was added, and the mixture was stirred at room temperature for 24 hours. After that, 30.6 g of toluene was added, and the mixture was concentrated to convert the solvent to toluene. Next, 20 g of deionized water was added and liquid-liquid extraction was performed. This procedure was repeated twice, and the resulting organic layer was concentrated under reduced pressure to remove the solvent, yielding 3.9 g of 9,9-bis[6-(2-aminoethoxy)-2-naphthyl]fluorene (also known as BNEF-NH2) as a yellow amorphous solid (yield 88.0%, LC purity 96.6% (amine column)). 1 The results of the H-NMR spectrum are shown below.

[0334] 1H NMR(300MHz, CDCl3)δ(ppm)=1.5(4H,b), 3.1(4H,t), 4.1(4H,t), 7.1(4H,m), 7.3-7.4(6H,m), 7.5(6H,t), 7.6(2H,d), 7.8(2H,d)

[0335] The obtained BNEF-NH2 had a 5% weight loss temperature of 194°C, a refractive index (25°C, nD) of 1.64, no melting point, and a glass transition temperature (Tg) of 109°C. The results of solubility test 2 were good, as shown in the table below.

[0336] [Table 6]

[0337] [Example 6] Synthesis of polyamic acid and polyimide resins using BPEF-NH2 as a polymerization component

[0338] [ka]

[0339] Under a nitrogen gas atmosphere, a stirring bar was placed in the reaction vessel, and 2.8 g of powdered BPEF-NH2 (96.5% solids, 6.3 mmol) obtained in Example 3 and 20.0 g of N-methyl-2-pyrrolidone (NMP) were added and dissolved. Then, 1.9 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) (6.3 mmol, 1.0 eq) was added, and the mixture was stirred at 60°C for 20 hours to obtain an NMP solution of polyamic acid 1 represented by the above formula (yellow viscous liquid, viscosity 1441.0 mPa·s). The weight-average molecular weight Mw of the obtained polyamic acid 1 was 45286.

[0340] The obtained NMP solution of polyamic acid 1 was cast onto a TAC (triacetylcellulose) film using a doctor blade (film thickness: 250 μm), and dried (pre-baked) in a hot air dryer at 80°C for 30 minutes to produce a polyamic acid 1 film. When the film's moldability was evaluated, the obtained film showed high flexibility without breaking even when folded at 180°, indicating good film moldability, and was colorless and transparent with suppressed discoloration. The obtained polyamic acid 1 film was placed on a heat-resistant Kapton film and fired in a vacuum film deposition machine (300°C, 1 hour) to obtain polyimide 1.

[0341] [Comparative Example 2] Synthesis of polyamic acid using BAF as a polymerization component

[0342] [ka]

[0343] Under a nitrogen gas atmosphere, a stirring bar was placed in the reaction vessel, and 10.0 g (28.7 mmol) of BAF and 77.1 g of NMP were added and dissolved. Then, 8.4 g (28.7 mmol, 1.0 eq) of BPDA was added, and the mixture was stirred at 20°C for 24 hours to obtain an NMP solution of polyamic acid 2 represented by the above formula (yellow viscous liquid, viscosity 670.0 mPa·s). The weight-average molecular weight Mw of the obtained polyamic acid 2 was 50885.

[0344] The obtained polyamic acid 2 NMP solution was cast onto a TAC (triacetylcellulose) film using a doctor blade (film thickness: 250 μm), and dried (pre-baked) in a hot air dryer at 80°C for 30 minutes to produce a polyamic acid 2 film. When the film's moldability was evaluated, the resulting film was found to be brittle enough to break when folded at 180°, and was discolored pale yellow. The obtained polyamic acid 2 film was placed on a heat-resistant Kapton film and fired in a vacuum film deposition machine (300°C, 1 hour) to obtain polyimide 2.

[0345] [Example 7] Synthesis of polyamic acid using BPEF-NH2 as the polymerization component

[0346] The procedure was carried out in the same manner as in Comparative Example 2, except that viscous liquid BPEF-NH2 obtained in Example 2 was used instead of BAF. The weight-average molecular weight Mw of the obtained polyamic acid (with the same chemical structure as polyamic acid 1 in Example 6) was 31405, and the viscosity in NMP solution was 107.6 mPa·s.

[0347] [Example 8] Synthesis of polyamic acid using BPEF-NH2 as the polymerization component

[0348] Except for using powdered BPEF-NH2 obtained in Example 3 instead of BAF, the procedure was carried out in the same manner as in Comparative Example 2. The weight-average molecular weight Mw of the obtained polyamic acid (with the same chemical structure as polyamic acid 1 in Example 6) was 38782, and the viscosity in NMP solution was 445.3 mPa·s. Perhaps due to the good handling properties of BPEF-NH2, a higher molecular weight polyamic acid was obtained compared to Example 7, which was prepared under the same conditions.

[0349] [Comparative Example 3] Synthesis of polyamic acid using PDA as a polymerization component

[0350] [ka]

[0351] Under a nitrogen gas atmosphere, a stirring bar was placed in the reaction vessel, and 5.3 g (48.7 mmol) of p-phenylenediamine (PDA) and 81.5 g of NMP were added and dissolved. Then, 14.3 g (48.7 mmol, 1.0 eq) of BPDA was added, and the mixture was stirred at 20°C for 24 hours. To adjust the viscosity, 36.5 g of NMP was added to obtain an NMP solution of polyamic acid 3 represented by the above formula (a dark brown viscous liquid, viscosity 14240.0 mPa·s). The weight-average molecular weight Mw of the obtained polyamic acid 3 was 70059.

[0352] The obtained polyamic acid 3 NMP solution was cast onto a TAC (triacetylcellulose) film using a doctor blade (film thickness: 250 μm), and dried (pre-baked) in a hot air dryer at 80°C for 30 minutes to produce a polyamic acid 3 film. When the film's moldability was evaluated, the obtained film showed high flexibility without breaking even when folded at 180°, indicating good film moldability, but it was severely discolored to a brownish color. The obtained polyamic acid 3 film was placed on a heat-resistant Kapton film and fired in a vacuum film deposition machine (300°C, 1 hour) to obtain polyimide 3.

[0353] The color of each polyamic acid film obtained in Example 6 and Comparative Examples 2-3 was visually inspected, and the film moldability was evaluated. The results are shown below.

[0354] [Table 7]

[0355] The film obtained in Comparative Example 2 was a pale yellow film that was so brittle it broke when bent and had poor moldability. The film obtained in Comparative Example 3, although flexible enough not to break when bent, was heavily discolored to a reddish-brown. In contrast, the film obtained in Example 6 was not only highly flexible and had good moldability, but also had suppressed discoloration, achieving both film moldability and colorless transparency. [Industrial applicability]

[0356] The fluorene compounds of this disclosure (fluorene-based amine compounds and / or fluorene-based azide compounds) can be effectively used as resin raw materials (or polymerization components) for forming resins; as resin additives for modifying resins, such as refractive index improvers, curing agents or curing accelerators (e.g., curing agents for epoxy resins), crosslinking agents, chain extenders (or chain lengthening agents), etc.

[0357] Furthermore, resins using the fluorene compounds of this disclosure as resin raw materials (polymerization components), and / or resin compositions containing the fluorene compounds of this disclosure as resin additives, can be used in a variety of applications, such as coating agents or coating films, specifically paints, inks, protective films for electronic equipment and liquid crystal components; adhesives; resin fillers; electrical and electronic materials or electrical and electronic components (electrical and electronic equipment), specifically antistatic agents, carrier transport agents, light emitters, organic photoreceptors, thermal recording materials, photochromic materials, holographic recording materials, antistatic trays, conductive sheets, and optical data It may be used in discs, inkjet printers, digital paper, color filters, organic EL elements, organic semiconductor lasers, dye-sensitized solar cells, sensors, EMI shielding films, etc.; mechanical materials or mechanical parts (equipment), specifically automotive materials or parts, aerospace-related materials or parts, sliding members, etc.; optical materials or optical components, specifically optical films (optical sheets) such as liquid crystal display films and organic EL display films; optical lenses such as eyeglass lenses and camera lenses; prisms, holograms, optical fibers, etc.

[0358] In particular, polyimide resins using the fluorene compound (fluorene-based amine compound) of this disclosure as a polymerization component can be used for electrical laminates, insulating varnishes, insulating films (interlayer insulating films, anisotropic conductive films, etc.), circuit boards [printed circuit boards such as flexible printed circuit boards (FPCs) or printed wiring boards, etc.], electrical and electronic materials or components such as base station antenna materials, transparent plastic substrates, optical materials or components such as optical waveguides, resin modifiers, sealants, adhesives, etc. Among these, they are particularly useful as electrical and electronic materials or components such as semiconductor-related components, specifically as circuit boards such as printed wiring board materials for Wi-Fi communication and 5G or 6G communication applications.

Claims

1. An amine compound represented by the following formula (1) or a salt thereof. 【Chemistry 1】 (In the formula, R １ represents a substituent, and m1 represents an integer from 0 to 8. Z １ａ and Z １ｂ These independently exhibit an arene ring, A １ａ and A １ｂ n1a and n1b independently represent an alkylene group, and n1a and n1b independently represent an integer of 1 or more. R ２ａ and R ２ｂ (where m2a and m2b independently represent substituents, and m2a and m2b independently represent integers greater than or equal to 0.)

2. In the above formula (1), R １ represents a hydrocarbon group, and m1 represents an integer from 0 to 4. Z １ａ and Z １ｂ each independently represents a C ６－１４ arene ring, A １ａ and A １ｂ C is independent ２－６ It represents an alkylene group, and n1a and n1b independently represent integers from 1 to 10. R ２ａ and R ２ｂ The amine compound or salt thereof according to claim 1, wherein m2a and m2b independently represent an integer from 0 to 4.

3. In the above formula (1), R １ m1 represents an alkyl group, cycloalkyl group, aryl group, or aralkyl group, and m1 represents an integer from 0 to 2. Z １ａ and Z １ｂ C is independent ６－１２ Showing an arene ring, A １ａ and A １ｂ C is independent ２－４ It represents an alkylene group, and n1a and n1b independently represent integers from 1 to 6. R ２ａ and R ２ｂ The amine compound or salt thereof according to claim 1, wherein m2a and m2b independently represent an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and m2a and m2b independently represent an integer from 0 to 2.

4. An amine compound or salt thereof according to any one of claims 1 to 3, wherein the 5% weight loss temperature is 230 to 350°C.

5. An amine compound or salt thereof according to any one of claims 1 to 3, wherein the refractive index at a temperature of 25°C and a wavelength of 589 nm is 1.6 to 1.

68.

6. An amine compound or salt thereof according to any one of claims 1 to 3, which is soluble in at least one solvent selected from aromatic hydrocarbons, alcohols, ethers, ketones, esters, ether esters, and amides at a concentration of 10% by mass or more at a temperature of 25°C.

7. A crystalline amine compound or salt thereof according to any one of claims 1 to 3.

8. An amine compound or salt thereof according to any one of claims 1 to 3, wherein the amount of residual solvent is 5% by mass or less.

9. A method for producing an amine compound or a salt thereof according to any one of claims 1 to 3, comprising a reduction step of reducing an azide compound represented by the following formula (2). 【Chemistry 2】 (In the formula, R １ represents a substituent, and m1 represents an integer from 0 to 8. Z １ａ and Z １ｂ These independently exhibit an arene ring, A １ａ and A １ｂ n1a and n1b independently represent an alkylene group, and n1a and n1b independently represent an integer of 1 or more. R ２ａ and R ２ｂ (where m2a and m2b independently represent substituents, and m2a and m2b independently represent integers greater than or equal to 0.)

10. The manufacturing method according to claim 9, further comprising a crystallization step of precipitating the amine compound or a salt thereof according to any one of claims 1 to 3 obtained in the reduction step from a solvent containing at least esters.

11. The azide compound represented by formula (2) according to claim 9.

12. A method for producing an azide compound according to claim 11, comprising an azidation step of reacting a compound represented by the following formula (3) with an azidating agent. 【Transformation 3】 (In the formula, R １ represents a substituent, and m1 represents an integer from 0 to 8. Z １ａ and Z １ｂ These independently exhibit an arene ring, A １ａ and A １ｂ n1a and n1b independently represent an alkylene group, and n1a and n1b independently represent an integer of 1 or more. R ２ａ and R ２ｂ m2a and m2b independently represent substituents, and m2a and m2b independently represent integers of 0 or greater. L １ａ and L １ｂ (It independently exhibits a leaving group.)

13. A liquid composition comprising an amine compound represented by formula (1) or a salt thereof according to any one of claims 1 to 3, and a solvent.

14. The liquid composition according to claim 13, wherein the solvent comprises at least one selected from aromatic hydrocarbons, alcohols, ethers, ketones, esters, ether esters, and amides.

15. A resin comprising, as a resin raw material, an amine compound or a salt thereof as described in any one of claims 1 to 3, and / or an azide compound as described in claim 11.

16. The resin according to claim 15, which is a polyamic acid or polyimide resin and comprises, as polymerization components, a diamine component containing an amine compound or a salt thereof as described in any one of claims 1 to 3, and a tetracarboxylic acid component.

17. A resin composition comprising, as an additive, an amine compound or a salt thereof as described in any one of claims 1 to 3, and / or an azide compound as described in claim 11.

18. A molded article comprising the resin according to claim 15 and / or the resin composition according to claim 17.

19. The molded article according to claim 18, which is in the form of a film.

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