Phenolic compounds or their derivatives, as well as methods for producing the same and their uses.

Abstract

This invention provides phenol compounds or derivatives thereof that exhibit high heat resistance (thermal decomposition resistance), as well as methods for producing the same and their applications. [Solution] Prepare a fluorene compound represented by the following formula (1) or a salt thereof. TIFF2026049678000032.tif56153 (In the formula, Z 1a , Z 1b , Z 2a and Z 2 b (Each independently represents an arene ring, m1a, m1b, m3a, and m3b independently represent non-negative integers, and m2a and m2b independently represent integers between 0 and 3.)

Description

[Technical Field]

[0001] This disclosure relates to phenol compounds (bisphenol compounds) having a 9,9-bisarylfluorene skeleton and an arylethynyl skeleton, salts thereof, or derivatives thereof [for example, resins (specifically epoxy resins, epoxy (meth)acrylate resins (or vinyl ester resins), polyfunctional (meth)acrylic resins (or di(meth)acrylate resins), etc.)], as well as methods for producing the same and its uses. [Background technology]

[0002] Compounds containing a 9,9-bisarylfluorene skeleton exhibit excellent optical properties such as high refractive index and high heat resistance, and are therefore effectively utilized as optical components (or their raw materials).

[0003] Japanese Patent Publication No. 2022-042002 (Patent Document 1) discloses fluorene compounds that exhibit high refractive index and heat resistance. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2022-042002 [Overview of the project] [Problems that the invention aims to solve]

[0005] Examples 1 and 2 of Patent Document 1 describe the preparation of phenol compounds such as 9,9-bis(6-hydroxy-2-naphthyl)-2,7-di(2-naphthyl)fluorene (DNBNF) and 9,9-bis(6-hydroxy-2-naphthyl)-2,7-diphenylfluorene (DPBNF), and that these compounds had a higher refractive index compared to other phenol compounds having a 9,9-bisarylfluorene skeleton, and furthermore, that DNBNF had a particularly high 5% weight loss temperature.

[0006] However, there are applications that require higher heat resistance, and further improvement in heat resistance has been demanded.

[0007] Therefore, an object of the present disclosure is to provide a phenol compound or a salt thereof, or a derivative thereof, which exhibits high heat resistance (thermal decomposition resistance), and a method for producing the same and uses thereof.

Means for Solving the Problems

[0008] As a result of intensive studies to achieve the above problems, the present inventors have found that a phenol compound or a salt thereof, or a derivative thereof having an arylethynyl skeleton (i.e., the group [-C≡C-Z 1a -(R 1a ) m1a and [-C≡C-Z 1b -(R 1b ) m1b ) together with a 9,9-bisarylfluorene skeleton in the chemical structure exhibits high heat resistance, and completed the present invention (or the present disclosure). That is, the present disclosure may include the following aspects.

[0009] Aspect [1]: A fluorene compound (phenol compound) represented by the following formula (1) or a salt thereof.

[0010]

Chemical formula

[0011] (In the formula, Z 1a and Z 1b each independently represent an arene ring, R 1a and R 1b each independently represent a substituent, m1a and m1b each independently represent an integer of 0 or more, R 2a and R 2b each independently represent a substituent, m2a and m2b each independently represent an integer of 0 to 3, Z2a and Z 2b These independently show an arene ring, R 3a and R 3b (where m3a and m3b independently represent substituents, and m3a and m3b independently represent non-negative integers.)

[0012] Appearance [2]: In the above formula (1), Z 1a and Z 1b These independently exhibit a benzene ring, R 1a and R 1b m1a and m1b independently represent an alkyl group, and m1a and m1b independently represent an integer from 0 to 4. R 2a and R 2b m2a and m2b independently represent alkyl groups, and m2a and m2b independently represent integers from 0 to 2. Z 2a and Z 2b C is independent 6-12 Showing an arene ring, R 3a and R 3b A fluorene compound represented by formula (1) or a salt thereof according to embodiment [1], wherein m3a and m3b independently represent an alkyl group and m3a and m3b independently represent an integer from 0 to 4.

[0013] Appearance [3]: In the above formula (1), Z 1a and Z 1b These independently exhibit a benzene ring, R 1a and R 1b C is independent 1-4 It represents an alkyl group, and m1a and m1b independently represent integers from 0 to 2. R 2a and R 2b C is independent 1-4 It represents an alkyl group, and m2a and m2b independently represent 0 or 1. Z 2a and Z 2b C is independent 6-10 Showing an arene ring, R 3a and R 3b C is independent 1-4 A fluorene compound represented by formula (1) or a salt thereof according to embodiment [1] or [2], wherein the alkyl group is represented and m3a and m3b independently represent integers from 0 to 2.

[0014] Appearance [4]: A fluorene compound represented by formula (1) or a salt thereof, according to any one of embodiments [1] to [3], wherein the 5% weight loss temperature is 450°C or higher.

[0015] Appearance [5]: A fluorene compound represented by formula (1) or a salt thereof, according to any one of embodiments [1] to [4], wherein the refractive index nD at a temperature of 25°C and a wavelength of 589 nm is 1.74 or greater.

[0016] Appearance [6]: A fluorene compound represented by formula (1) or a salt thereof, as described in any of embodiments [1] to [5], which is soluble in at least one solvent selected from acetone, cyclohexanone, ethyl acetate, γ-butyrolactone, propylene glycol monomethyl ether acetate, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide, at a concentration of 30% by mass and a temperature of 25°C within 1 hour.

[0017] Appearance [7]: A method for producing a fluorene compound represented by formula (1) or a salt thereof, according to any one of embodiments [1] to [6], comprising a coupling step of reacting a fluorene compound represented by formula (2) or a salt thereof with a compound represented by formula (3a) and a compound represented by formula (3b).

[0018] [ka]

[0019] [In the formula, X 1a and X 1bThese independently represent reactive groups that can be coupled with the compound represented by formula (3a) and the compound represented by formula (3b), respectively. Z 1a and Z 1b , R 1a and R 1b , m1a and m1b, R 2a and R 2b , m2a and m2b, Z 2a and Z 2b , R 3a and R 3b m3a and m3b are the same as in formula (1) above.

[0020] Appearance [8]: A mixture comprising a fluorene compound represented by formula (1) or a salt thereof as described in any of embodiments [1] to [6], and at least one solvent selected from ketones, esters, ether esters, amides, and sulfoxides.

[0021] Appearance [9]: A resin comprising a fluorene compound represented by formula (1) or a salt thereof, as described in any of embodiments [1] to [6], as a resin raw material or polymerization component.

[0022] Appearance

[10] : A fluorene compound (curable resin) represented by the following formula (4). This fluorene compound represented by the following formula (4) may be a derivative that can be converted or derived from the fluorene compound (phenol compound) represented by formula (1) or a salt thereof, i.e., a resin (curable resin) according to embodiment [9] that contains the fluorene compound (phenol compound) represented by formula (1) or a salt thereof as described in any of embodiments [1] to [6] as a resin raw material or polymerization component.

[0023] [ka]

[0024] (In the formula, Z 1a and Z 1bThese independently show an arene ring, R 1a and R 1b m1a and m1b independently represent substituents, and m1a and m1b independently represent integers greater than or equal to 0. R 2a and R 2b m2a and m2b independently represent substituents, and m2a and m2b independently represent integers from 0 to 3. Z 2a and Z 2b These independently show an arene ring, R 3a and R 3b m3a and m3b independently represent substituents, and m3a and m3b independently represent integers greater than or equal to 0. Y 1a and Y 1b (This independently represents an epoxy-containing group or a (meth)acryloyl-containing group.)

[0025] Appearance

[11] : The fluorene compound represented by formula (4) according to embodiment

[10] , wherein the epoxy-containing group is a group represented by the following formula (Y1-1).

[0026] [ka]

[0027] (In the formula, R 4 (This represents a hydrogen atom or a methyl group.)

[0028] Appearance

[12] : In the above equation (4), Y 1a and Y 1b These independently represent the epoxy-containing group, The temperature at which the 5% weight loss occurs is 410°C or higher. The refractive index nD at a temperature of 25°C and a wavelength of 589 nm is 1.765 or higher. A fluorene compound represented by formula (4) according to embodiment

[10] or

[11] , which is soluble in at least one solvent selected from acetone, cyclohexanone, ethyl acetate, γ-butyrolactone, propylene glycol monomethyl ether acetate, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide at a concentration of 30% by mass and within 1 hour at a temperature of 25°C.

[0029] Appearance

[13] : The fluorene compound represented by formula (4) according to embodiment

[10] or

[11] , wherein the (meth)acryloyl-containing group is a group represented by the following formula (Y1-2).

[0030] [ka]

[0031] (In the formula, R 4 This indicates a hydrogen atom or a methyl group. p represents 0 or 1. R 5 (This represents a hydrogen atom or a methyl group.)

[0032] Appearance

[14] : In the above equation (4), Y 1a and Y 1b These independently represent the (meth)acryloyl-containing group, The temperature at which the 5% weight loss occurs is 390°C or higher. The refractive index nD at a temperature of 25°C and a wavelength of 589 nm is 1.67 or higher. A fluorene compound represented by formula (4) according to embodiment

[10] or

[13] , which is soluble in at least one solvent selected from acetone, cyclohexanone, ethyl acetate, γ-butyrolactone, propylene glycol monomethyl ether acetate, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide at a concentration of 30% by mass and a temperature of 25°C within 1 hour.

[0033] Appearance

[15] : A fluorene compound (phenol compound) represented by formula (1) as described in any of embodiments [1] to [6], and a hydrogen atom in the hydroxyl group of this fluorene compound Y 1a ,Y 1b A method for producing a fluorene compound (curable resin) represented by formula (4) according to any one of embodiments

[10] to

[14] , comprising the step of reacting with a reactive component that can be converted to or derived from the group represented by .

[0034] Appearance

[16] : A curable composition comprising a fluorene compound (curable resin) represented by formula (4) as described in any of embodiments

[10] to

[14] .

[0035] Appearance

[17] : A curable composition according to embodiment

[16] , comprising at least one solvent selected from ketones, esters, ether esters, amides, and sulfoxides.

[0036] Appearance

[18] : A cured product obtained by curing the curable composition according to embodiment

[16] or

[17] .

[0037] Furthermore, this disclosure may achieve the following secondary objectives (solve the following secondary problems).

[0038] In other words, another object of this disclosure is to provide phenol compounds or salts thereof that exhibit a high refractive index, or derivatives thereof, as well as methods for producing them and their uses.

[0039] Another object of this disclosure is to provide phenol compounds or salts thereof, or derivatives thereof, that can achieve both high heat resistance and / or high refractive index and high solubility, as well as methods for producing them and their uses.

[0040] In this specification and in the claims, the number of carbon atoms in a substituent is defined as C1, C6, C 10These 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.

[0041] Furthermore, in this specification and the claims, “independently” means that the 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.

[0042] In this specification and in the claims, the numerical range indicated by "X~Y" may include the numerical values ​​X and Y. [Effects of the Invention]

[0043] This disclosure provides phenol compounds or salts thereof that exhibit high heat resistance (thermal decomposition resistance), or derivatives thereof, as well as methods for producing them and their applications. [Modes for carrying out the invention]

[0044] [Fluorene compounds (phenol compounds) represented by formula (1)] The fluorene compounds (phenol compounds) represented by the following formula (1) in this disclosure exhibit high heat resistance (thermal decomposition resistance). They can also exhibit a high refractive index. Furthermore, it is possible to achieve both high heat resistance and / or a high refractive index and high solubility.

[0045] [ka]

[0046] (In the formula, Z 1a and Z 1b These independently show an arene ring, R 1a and R 1beach independently represents a substituent, m1a and m1b each independently represent an integer of 0 or more, R 2a and R 2b each independently represents a substituent, m2a and m2b each independently represent an integer of 0 to 3, Z 2a and Z 2b each independently represents an arene ring, R 3a and R 3b each independently represents a substituent, m3a and m3b each independently represent an integer of 0 or more.)

[0047] In the above formula (1), the arene ring (aromatic hydrocarbon ring) represented by Z 1a or Z 1b includes, for example, monocyclic arene rings such as benzene rings; polycyclic arene rings such as condensed polycyclic arene rings (condensed polycyclic aromatic hydrocarbon rings) and ring-fused arene rings (ring-fused aromatic hydrocarbon rings).

[0048] Examples of the condensed polycyclic arene rings include condensed bicyclic to tetracyclic arene rings such as condensed bicyclic arene rings and condensed tricyclic arene rings. Examples of the condensed bicyclic arene rings include condensed bicyclic C 9-16 arene rings such as naphthalene rings and indene rings. Examples of the condensed tricyclic arene rings include condensed tricyclic C 14-20 arene rings such as anthracene rings and phenanthrene rings. Preferred condensed polycyclic arene rings are condensed polycyclic C 10-14 arene rings such as naphthalene rings.

[0049] Examples of the ring-fused arene rings include bi- or ter-arene rings such as biphenyl rings, phenylnaphthalene rings, binaphthyl rings, and terphenyl rings. Preferred ring-fused arene rings are ring-fused C 12-18 arene rings, and more preferably bi- or ter-C 12-18 arene rings such as biphenyl rings.

[0050] In the present specification and the claims, the "ring-aggregated arene ring" means that two or more ring systems (arene ring systems) are directly connected by a single bond or a double bond, and the number of bonds connecting the rings is one less than the number of ring systems. For example, as described above, a phenylnaphthalene ring, a binaphthyl ring, etc. are classified as ring-aggregated arene rings even if they have a condensed polycyclic arene ring skeleton, and are clearly distinguished from "condensed polycyclic arene rings" such as a naphthalene ring (non-ring-aggregated arene ring).

[0051] Z 1a ,Z 1b The preferred arene rings represented by are arene rings such as benzene ring, naphthalene ring, biphenyl ring, etc., and more preferably arene rings, and particularly, benzene ring. 6-12 are arene rings, and more preferably arene rings, and particularly, benzene ring. 6-10 are arene rings, and particularly, benzene ring.

[0052] R 1a Or the substituent represented by R 1b may be a non-reactive group (or non-polymerizable group) that is inert to the reaction. R 1a ,R 1b Examples of the substituent represented by include a halogen atom, a hydrocarbon group, a group [-OR h (wherein R h represents a hydrocarbon group), a group [-SR h (wherein R h represents a hydrocarbon group), an acyl group, a nitro group, a cyano group, a substituted amino group (mono- or di-substituted amino group), etc.

[0053] In the present specification and the claims, the hydrocarbon group represented by R h means an independent hydrocarbon group, and may be the same or different from each other.

[0054] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.

[0055] The 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 constituting the group is not particularly limited, but may be as low as 20, for example, and preferably in the following order: 1-16, 1-12, 1-10, 1-8, 1-6. Typical hydrocarbon group (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 C such as an alkyl group, more preferably a methyl group. 1-4 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. Examples of alkylphenyl groups include mono- or tri-C groups such as methylphenyl (or tolyl) and dimethylphenyl (or xylyl) groups. 1-4 Examples include alkylphenyl groups.

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

[0060] The group [-OR h ] and base [-SRh In ], R h As a hydrocarbon group represented by R 1 ,R 1b Examples of hydrocarbon groups include those similar to the hydrocarbon groups exemplified above, including preferred embodiments, such as alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. The aforementioned group [-OR h ] and base [-SR h For example, the hydrocarbon group (or R h Examples of the corresponding bases are given, and representative bases [-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 Examples include alkoxy groups. Cycloalkyloxy groups include, for example, cyclohexyloxy groups and other C groups. 5-10 Examples include cycloalkyloxy groups. Examples of aryloxy groups include phenoxy groups and other C groups. 6-10 Examples include aryloxy groups. Examples of aralkyloxy groups include the benzyloxy group and other C groups. 6-10 Aryl-C 1-4 Alkyloxy groups are one example.

[0062] Examples of alkylthio groups include methylthio group, ethylthio group, propylthio group, n-butylthio group, t-butylthio group, etc. 1-10 Examples include alkylthio groups. Cycloalkylthio groups include, for example, cyclohexylthio groups and other C groups. 5-10 Examples include cycloalkylthio groups. Examples of arylthio groups include phenylthio groups (or thiophenoxy groups) and C 6-10Examples of arylthio groups include the benzylthio group. 6-10 Aryl-C 1-4 Alkylthio groups are one example.

[0063] Examples of acyl groups include C 1-12 Examples include acyl groups, specifically C groups such as acetyl groups. 1-6 Examples include alkyl-carbonyl groups.

[0064] Examples of mono- or disubstituted amino groups include mono- or dialkylamino groups and mono- or diacylamino groups. Examples of mono- or dialkylamino groups include mono- or diC such as mono- or dimethylamino groups. 1-4 Examples include alkylamino groups. Mono or diacylamino groups include mono or diacetylamino groups, for example. 1-5 Examples include acylamino groups.

[0065] Typical R 1 ,R 1b Examples include halogen atoms, hydrocarbon groups (e.g., alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, etc.), and groups [-OR h Examples include alkoxy groups, acyl groups, and preferably hydrocarbon groups such as alkyl groups (linear or branched alkyl groups) and aryl groups, and more preferably alkyl groups such as methyl groups, ethyl groups, and t-butyl groups. 1-6 This includes alkyl groups, and in particular, C such as methyl groups. 1-4 Alkyl alkyl groups are preferred.

[0066] R 1a or R 1b The number of substitutions m1a or m1b each represents a non-negative integer, and Z 1a ,Z 1bDepending on the type, for example, an integer of about 0 to 5, preferably an integer of 0 to 3, an integer of 0 to 2, more preferably 0 or 1, and especially 0. m1a and m1b may be different from each other, but are preferably the same. If m1a is 2 or more, then R is 2 or more. 1a The types may be the same or different from each other; if m1b is 2 or more, then 2 or more R 1b The types may be the same or different from each other. Also, R 1a and R 1b The types may be different from each other, but it is preferable that they be the same. 1a ,R 1b The substitution position is not particularly restricted.

[0067] Note that the arylethynyl skeleton (i.e., the group in formula (1) [-C≡CZ) 1a -(R 1a ) m1a ] or [-C≡CZ 1b -(R 1b ) m1b The substitution positions (bonding positions) of ]) are not particularly limited as long as they are at positions 1-4 and 5-8 of the fluorene ring, for example, symmetrical positions on the plane of the paper such as positions 1,8-, 2,7-, 3,6-, and 4,8-, with positions 2,7- being preferred.

[0068] R 2a or R 2b The substituent represented by the group [-C≡CZ 1a -(R 1a ) m1a ],[-C≡CZ 1b -(R 1b ) m1b ] may be a different group, and may be an inactive, non-reactive group (or non-polymerizable group) that is inert to the reaction. 2a ,R 2b Examples of substituents represented by R 1a ,R 1b Similar groups, including the substituents exemplified and preferred embodiments, can be mentioned. 2a ,R 2bPreferred substituents represented by are hydrocarbon groups such as alkyl groups, and more preferably C 1-6 Alkyl group (for example, C such as a methyl group) 1-4 It is an alkyl group.

[0069] R 2a or R 2b The number of substitutions m2a or m2b is an integer between 0 and 3, for example, an integer between 0 and 2, preferably 0 or 1, and more preferably 0. m2a and m2b may be different from each other, but are preferably the same. 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 or different from each other. Also, R 2a and R 2b The types may be different from each other, but it is preferable that they be the same. 2a ,R 2b The substitution position is the base [-C≡CZ 1a -(R 1a ) m1a ],[-C≡CZ 1b -(R 1b ) m1b Any position other than the substitution position of ] is acceptable and there are no particular restrictions.

[0070] Z 2a or Z 2b Examples of arene rings represented by Z include monocyclic arene rings such as benzene rings, and polycyclic arene rings. Examples of polycyclic arene rings include fused polycyclic arene rings (fused polycyclic aromatic hydrocarbon rings) and ring aggregated arene rings (ring aggregated aromatic hydrocarbon rings). Examples of these arene rings include the aforementioned Z 1a ,Z 1b Examples include those similar to the arene rings exemplified above.

[0071] Z 2a ,Z 2b Preferred arene rings represented by C are benzene rings, naphthalene rings, biphenyl rings, etc. 6-12It is an arene ring, and more preferably C 6-10 It is an arene ring, and more specifically, a naphthalene ring.

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

[0073] Also, Z 2a and Z 2b The substitution position (bonding position) of the hydroxyl group [-OH] in the arene ring is not particularly restricted; for example, Z 2a ,Z 2b If is a benzene ring, it is preferable to substitute at one of the positions of the phenyl group bonded to the 9-position of the fluorene ring, either the 2-position, 3-position, or 4-position, especially the 3-position or 4-position, particularly the 4-position. Also, Z 2a ,Z 2b 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 2a ,Z 2b If is a ring-assembled arene ring, the substitution position of the hydroxyl group is not particularly limited and may be, for example, substituted on the arene ring bonded to the 9-position of fluorene or on an arene ring adjacent to this arene ring. For example, Z 2a ,Z 2b If it is a biphenyl ring (or Z 2a ,Z2b This is a benzene ring, and one phenyl group is attached to this benzene ring R 3a ,R 3b When bonded as such, 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 hydroxyl group.

[0074] R 3a or R 3b The substituent represented by may be a group different from the hydroxyl group, and may be an inactive (or nonpolymerizable) group that is inert to the reaction. 3a ,R 3b Examples of substituents represented by R 1a ,R 1b Similar groups, including the substituents exemplified and preferred embodiments, can be mentioned. 3a ,R 3b Typical substituents represented include halogen atoms, hydrocarbon groups, and groups [-OR h Examples include alkoxy groups, acyl groups, nitro groups, cyano groups, mono- or disubstituted amino groups, preferably hydrocarbon groups such as alkyl groups (linear or branched alkyl groups), cycloalkyl groups, aryl groups, aralkyl groups, and alkoxy groups (linear or branched alkoxy groups). h ] are examples, and more preferably C 1-6 Alkyl groups such as alkyl groups, aryl groups (such as phenyl groups and C groups) 6-10 (such as aryl groups), and in particular, C 1-6 Alkyl groups such as alkyl groups (C such as methyl group) 1-4 (Alkyl alkyl groups, etc.) Note that R 3a ,R 3b When R is an aryl group, 3a ,R 3b These are Z 2a ,Z 2b They may form a ring-assembled arene ring together.

[0075] R 3a or R 3b The number of substitutions m3a or m3b each represents a non-negative integer, and Z 2a ,Z2b 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, then an integer of 0 to 2, more preferably 0 or 1, and especially preferably 0. m3a and m3b may be different from each other, but are preferably the same. If m3a is 2 or more, then R is 2 or more. 3a The types may be the same or different from each other; if m3b is 2 or more, then 2 or more R 3b The types may be the same or different from each other. Also, R 3a and R 3b The types may be different from each other, but it is preferable that they be the same. 3a ,R 3b The substitution position is not particularly restricted and can be any position other than the substitution position of the hydroxyl group, for example, Z 2a ,Z 2b The hydroxyl group bonded to the carbon atom may be substituted at the ortho position (the carbon atom adjacent to the bonded position of the hydroxyl group).

[0076] Typical fluorene compounds represented by the above formula (1) include: Z 1a and Z 1b The C ring is independently a benzene ring or a polycyclic arene ring (preferably a benzene ring, naphthalene ring, biphenyl ring, etc.). 6-12 (e.g., arene rings) R 1a and R 1b m1a and m1b independently represent an aliphatic hydrocarbon group such as an alkyl group or cycloalkyl group, and m1a and m1b independently represent an integer from 0 to 4. R 2a and R 2b m2a and m2b independently represent an aliphatic hydrocarbon group such as an alkyl group or cycloalkyl group, and m2a and m2b independently represent an integer from 0 to 2. Z 2a and Z 2b These independently represent a benzene ring or a polycyclic arene ring. R 3a and R 3bExamples of compounds where m3a and m3b independently represent a hydrocarbon group, and m3a and m3b independently represent integers from 0 to 6;

[0077] Preferably, Z 1a and Z 1b These are independently C2 rings such as benzene rings and naphthalene rings. 6-10 It shows an arene ring (preferably a benzene ring), R 1a and R 1b C is independent 1-6 It represents an alkyl group such as an alkyl group, and m1a and m1b independently represent integers from 0 to 4. R 2a and R 2b C is independent 1-6 It represents an alkyl group such as an alkyl group, and m2a and m2b independently represent integers from 0 to 2. Z 2a and Z 2b These are independently C2 rings such as benzene rings, naphthalene rings, and biphenyl rings. 6-12 Showing an arene ring, R 3a and R 3b These are independently alkyl groups or aryl groups (preferably C 1-6 Examples of compounds include those exhibiting alkyl groups (such as alkyl groups), where m3a and m3b independently represent integers from 0 to 4;

[0078] More preferably, Z 1a and Z 1b These independently exhibit a benzene ring, R 1a and R 1b These are independently C groups such as methyl groups. 1-4 It represents an alkyl group, and m1a and m1b independently represent integers from 0 to 2. R 2a and R 2b These are independently C groups such as methyl groups. 1-4 It represents an alkyl group, and m2a and m2b independently represent 0 or 1. Z 2a and Z 2b These are independently C2 rings such as benzene rings and naphthalene rings.6-10 It shows an arene ring (preferably a naphthalene ring), R 3a and R 3b C is independent 1-6 Alkyl groups such as alkyl groups (preferably C such as a methyl group) 1-4 Examples of compounds include those exhibiting an alkyl group, where m3a and m3b independently represent integers between 0 and 2.

[0079] Specific fluorene compounds represented by formula (1) include 9,9-bis(hydroxyphenyl)-bis(arylethynyl)fluorene, 9,9-bis(alkyl-hydroxyphenyl)-bis(arylethynyl)fluorene, 9,9-bis(aryl-hydroxyphenyl)-bis(arylethynyl)fluorene, and 9,9-bis(hydroxynaphthyl)-bis(arylethynyl)fluorene.

[0080] Examples of 9,9-bis(hydroxyphenyl)-bis(arylethynyl)fluorene include 9,9-bis(4-hydroxyphenyl)-2,7-bis(phenylethynyl)fluorene and 9,9-bis(4-hydroxyphenyl)-2,7-bis(2-naphthylethynyl)fluorene. 6-10 Examples include arylethynyl fluorene.

[0081] Examples of 9,9-bis(alkyl-hydroxyphenyl)-bis(arylethynyl)fluorene include 9,9-bis(4-hydroxy-3-methylphenyl)-2,7-bis(phenylethynyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)-2,7-bis(phenylethynyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-2,7-bis(2-naphthylethynyl)fluorene, and other 9,9-bis[(mono or di)C 1-4 [Alkyl-hydroxyphenyl]-bis(C 6-10 Examples include arylethynyl fluorene.

[0082] Examples of 9,9-bis(aryl-hydroxyphenyl)-bis(arylethynyl)fluorene include 9,9-bis(4-hydroxy-3-phenylphenyl)-2,7-bis(phenylethynyl)fluorene, 9,9-bis(4-hydroxy-3,5-diphenylphenyl)-2,7-bis(phenylethynyl)fluorene, and 9,9-bis(4-hydroxy-3-phenylphenyl)-2,7-bis(2-naphthylethynyl)fluorene, etc. 6-10 [Aryl-hydroxyphenyl]-bis(C 6-10 Examples include arylethynyl fluorene.

[0083] Examples of 9,9-bis(hydroxynaphthyl)-bis(arylethynyl)fluorene include 9,9-bis(6-hydroxy-2-naphthyl)-2,7-bis(phenylethynyl)fluorene, 9,9-bis(5-hydroxy-1-naphthyl)-2,7-bis(phenylethynyl)fluorene, and 9,9-bis(6-hydroxy-2-naphthyl)-2,7-bis(2-naphthylethynyl)fluorene, etc. 6-10 Examples include arylethynyl fluorene.

[0084] The fluorene compound (phenol compound) represented by formula (1) may also be in the form of a salt. Examples of salts include alkali metal salts (such as sodium salts), metal salts such as alkaline earth metal salts (metal phenoxides), and amine salts (or ammonium salts).

[0085] [Method for producing a fluorene compound represented by formula (1) or a salt thereof] The method for producing the sodium salt of the fluorene compound (phenol compound) represented by formula (1) is not particularly limited, and may include, for example, a coupling step in which the fluorene compound represented by formula (2) below is reacted (coupling reaction) with the compound represented by formula (3a) below and the compound represented by formula (3b) below.

[0086] [ka]

[0087] [In the formula, X 1a and X 1b These independently represent reactive groups that can be coupled with the compound represented by formula (3a) and the compound represented by formula (3b), respectively. Z 1a and Z 1b , R 1a and R 1b , m1a and m1b, R 2a and R 2b , m2a and m2b, Z 2a and Z 2b , R 3a and R 3b m3a and m3b are the same as in formula (1), including preferred embodiments.

[0088] The coupling reaction (cross-coupling reaction) is not particularly limited; for example, the Heck-Cassar-Sonogashira coupling reaction or the Sonogashira-Hagiwara coupling reaction can be used.

[0089] X 1a or X 1b The reactive group represented by formula (3a) or (3b) can be any group capable of forming a carbon-carbon bond through a coupling reaction with the ethynyl group [CH≡C-] of the compound represented by formula (3a) or (3b). For example, halogen atoms (iodine atoms, bromine atoms, chlorine atoms, etc.), fluoride alkanesulfonyloxy groups [for example, trifluoromethanesulfonyloxy group (or group [-OTf]) and other fluoride C 1-4 Examples include alkanesulfonyloxy groups, and preferably halogen atoms such as bromine atoms. 1a and X 1b The types may be different from each other, but it is preferable that they be the same.

[0090] A typical fluorene compound represented by formula (2) or a salt thereof corresponds to a typical (or preferred) fluorene compound represented by formula (1) or a salt thereof, X 1a and X 1b Examples include compounds in which the halogen atom is a bromine atom or other halogen atom. Specifically, 9,9-bis(hydroxy(C))(C) such as 9,9-bis(4-hydroxyphenyl)-2,7-dibromofluorene. 6-12 Examples include aryl-dihalofluorene.

[0091] The fluorene compound represented by formula (2) or its salt may be produced by conventional methods, for example, by reacting dihalo-9-fluorenones (such as 2,7-dibromo-9-fluorenone) with phenols (such as phenol, 2-naphthol, o-hydroxybiphenyl) in the presence of an acid catalyst (such as an inorganic acid such as concentrated sulfuric acid) and a co-catalyst (such as thiols such as 3-mercaptopropionic acid).

[0092] Typical compounds represented by formula (3a) or (3b) include ethynylarene (ethynyl-C such as ethynylbenzene). 6-12 Examples include arenes, etc. It is preferable that the compound represented by formula (3a) and the compound represented by formula (3b) are the same compound.

[0093] The ratio of the fluorene compound represented by formula (2) or its salt to the total amount of the compound represented by formula (3a) or (3b) may be, for example, the former / latter (molar ratio) = 1 / 1 to 1 / 10, and preferably, in stages, 1 / 2 to 1 / 10, 1 / 2.5 to 1 / 5, and 1 / 2.7 to 1 / 3.5.

[0094] The reaction may be carried out in the presence of a catalyst. Examples of catalysts include metal catalysts such as palladium catalysts, and examples of palladium catalysts include palladium(0) catalysts such as tetrakis(triphenylphosphine)palladium(0) [or Pd(PPh3)4], bis(tri-t-butylphosphine)palladium(0) [or Pd(P(t-Bu)3)2], bis(dibenzylideneacetone)palladium(0) [Pd(dba)2], tris(dibenzylideneacetone)dipalladium(0) [Pd2(dba)3], tris(dibenzylideneacetone)dipalladium(0) chloroform complex [or Pd2(dba)3·CHCl3]; palladium(II) chloride, palladium(II) acetate, [1,2-bi Examples of palladium(II) catalysts include palladium(II) compounds such as [s(diphenylphosphino)ethane]palladium(II) dichloride [or PdCl2(dppe)], [1,3-bis(diphenylphosphino)propane]palladium(II) dichloride [or PdCl2(dppp)], [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride [or PdCl2(dppf)], bis(triphenylphosphine)palladium(II) dichloride [or PdCl2(PPh3)2], and bis(tri-o-tolylphosphine)palladium(II) dichloride [or PdCl2(P(o-tolyl)3)2]. These catalysts can be used individually or in combination of two or more.

[0095] The catalyst may be a catalyst that exhibits catalytic activity directly within the reaction system, or it may be a catalytic precursor that is converted into a catalyst within the reaction system. For example, palladium(II) catalysts such as palladium(II) acetate may be reduced to zero valence by reducing compounds such as phosphine, amine, or organometallic reagents within the reaction system and then act as a catalyst.

[0096] Of these catalysts, palladium(II) catalysts such as palladium(II) chloride are preferred. The proportion of the catalyst (palladium catalyst) may be, for example, about 0.001 to 0.5 moles in terms of metal, per mole of the fluorene compound or salt represented by formula (2) above, and preferably in the following increments: 0.005 to 0.15 moles, 0.01 to 0.1 moles, and 0.03 to 0.07 moles.

[0097] The reaction may be carried out in the presence of a ligand, along with a catalyst such as the palladium catalyst, as needed. Examples of ligands include conventional ligands used in coupling reactions, such as phosphines and carbenes, with phosphines being preferred. Examples of phosphines include trialkylphosphines such as tributylphosphine, tricycloalkylphosphines such as tricyclohexylphosphine, triphenylphosphine, diphenyl-biphenylylphosphine, tritlylphosphine, triarylphosphine such as tris(mono- or dimethoxyphenyl)phosphine, tris(fluorophenyl)phosphine, tris[di(trifluoromethyl)phenyl]phosphine, bis(diphenylphosphino)alkanes such as dppe and dppp, phosphines having a ferrocene skeleton such as dppf, and phosphines having a binaphthyl skeleton such as BINAP. These ligands can be used alone or in combination of two or more. Among these ligands, triarylphosphines such as triphenylphosphine and tritlylphosphine are preferred. The ratio of ligands may be, for example, about 1 to 10 moles per mole of catalyst, and preferably in stages, 1.3 to 5 moles, 1.5 to 3 moles, and 1.8 to 2.5 moles.

[0098] The reaction may, if necessary, be carried out in the presence of a copper catalyst as a co-catalyst or co-catalyst, along with a catalyst such as the palladium catalyst. Examples of copper catalysts include copper(I) halides such as copper(I) iodide and copper(I) chloride. The proportion of the co-catalyst may be, for example, about 0.001 to 0.5 moles per mole of the fluorene compound or salt represented by formula (2), and preferably in the following steps: 0.003 to 0.15 moles, 0.005 to 0.1 moles, and 0.01 to 0.05 moles.

[0099] The reaction may be carried out in the presence of a base such as an amine. Examples of amines include mono- or trialkylamines such as n-propylamine, diethylamine, diisopropylamine, triethylamine, and N,N-diisopropylethylamine, as well as mono- or tri-C alkylamines such as triethylamine. 1-4 Alkylamines are preferred. The base can be used alone or in combination of two or more types. The proportion of the base may be, for example, about 10 to 100 moles, preferably 20 to 75 moles, more preferably 30 to 50 moles, and particularly 35 to 45 moles, per mole of the fluorene compound or salt represented by formula (2) above.

[0100] The reaction may be carried out in the absence or presence of a solvent that is inert to the reaction. Examples of solvents include ethers (such as linear ethers like diethyl ether, tetrahydrofuran (THF), and cyclic ethers like dioxane), esters (such as ethyl acetate), nitriles (such as acetonitrile), and amides (such as N,N-dimethylformamide (DMF)). Solvents may be used alone or in combination of two or more.

[0101] The reaction may be carried out under an inert gas atmosphere (e.g., nitrogen gas; noble gases such as helium or argon). The reaction temperature is, for example, 10 to 150°C, preferably in stages, 20 to 130°C, 50 to 120°C, 70 to 110°C, 80 to 100°C, and 85 to 95°C. The reaction may be carried out under reflux or with stirring. The reaction time is not particularly limited, and may be, for example, about 1 to 10 hours, preferably 1 to 3 hours.

[0102] After the reaction is complete, the reaction mixture may be separated and purified as needed by conventional separation and purification methods, such as washing, extraction, filtration, dehydration, concentration, decantation, crystallization or recrystallization, reprecipitation, column chromatography, adsorption, or a combination thereof.

[0103] [Properties and uses of fluorene compounds represented by formula (1) or their salts] (characteristic) The fluorene compound (phenol compound) or salt represented by formula (1) exhibits high heat resistance (thermal decomposition resistance), and its 5% weight loss temperature may be, for example, 400°C or higher (e.g., 430°C to 530°C), preferably 450°C or higher (e.g., 460°C to 525°C), more preferably 470°C to 520°C (e.g., 480°C to 515°C), and particularly 490°C to 510°C (e.g., 495°C to 505°C).

[0104] The refractive index nD of the fluorene compound (phenol compound) or salt represented by formula (1) above may be, for example, 1.74 or more (e.g., 1.76 to 1.85) at a temperature of 25°C and a wavelength of 589 nm, preferably 1.77 or more (e.g., 1.78 to 1.83), more preferably 1.785 or more (e.g., 1.79 to 1.82), and particularly 1.795 or more (e.g., 1.8 to 1.81).

[0105] In this specification and in the claims, the 5% weight loss temperature and refractive index nD can be measured by the method described in the examples below.

[0106] The fluorene compound (phenol compound) represented by the formula (1) or a salt thereof may be crystalline or amorphous.

[0107] When the fluorene compound (phenol compound) represented by the formula (1) or a salt thereof is crystalline, its melting point is, for example, 100 to 170 °C (for example, 110 to 160 °C), preferably 120 to 150 °C (for example, 130 to 140 °C), and more preferably 133 to 139 °C (for example, 135 to 137 °C).

[0108] In the present specification and claims, the melting point can be measured by the method described in the examples below.

[0109] Although the fluorene compound (phenol compound) represented by the formula (1) or a salt thereof contains many rigid or bulky structures such as benzene rings (aromatic rings) in its chemical structure, it surprisingly shows high solubility (or compatibility) with organic compounds (such as organic solvents). Therefore, it is possible to achieve both high solubility, high heat resistance, and high refractive index. The fluorene compound represented by the formula (1) or a salt thereof can be dissolved in at least one solvent selected from acetone, cyclohexanone, ethyl acetate, γ-butyrolactone, propylene glycol monomethyl ether acetate, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide at a concentration of 30% by mass and a temperature of 25 °C within 1 hour.

[0110] In the present specification and claims, the solubility can be measured by the method described in the examples below.

[0111] (Use) The present disclosure includes a mixture or composition (particularly, a liquid composition or solution) containing the fluorene compound (phenol compound) represented by the formula (1) or a salt thereof and a solvent. Since the fluorene compound represented by the formula (1) or a salt thereof surprisingly shows high solubility (or compatibility), it is easy or efficient to easily prepare a uniform mixture or composition (particularly, a liquid composition or solution).

[0112] Solvents contained in mixtures or compositions (especially liquid compositions or solutions) include, for example, hydrocarbons (aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene); alcohols (methanol, ethanol, n-propanol, benzyl alcohol, etc.); ethers (dialkyl ethers such as diethyl ether; aromatic ethers such as anisole, cyclic ethers such as tetrahydrofuran and 1,4-dioxane, etc.); glycol ethers [such as (mono or tetra)alkylene glycols like ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME), ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol diethyl ether (DEDG)]. Examples include: cellulose (mono or di)alkyl ethers, etc.; ketones [such as chain ketones like acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK), and cyclic ketones like cyclohexanone]; esters (such as acetate esters like ethyl acetate, lactate esters like methyl lactate, ethyl lactate, and butyl lactate, and lactones or cyclic esters like γ-butyrolactone); ether esters [such as alkylene glycol monoalkyl ether acetates like methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate (PGMEA), and alkoxycarboxylic acid esters like ethyl 3-ethoxypropionate]; amides (such as chain amides like N,N-dimethylformamide and N,N-dimethylacetamide, and cyclic amides like N-methyl-2-pyrrolidone); and sulfoxides (such as dimethyl sulfoxide).

[0113] The solvent may be used alone or in combination of two or more. Preferred solvents are at least one selected from ketones, esters, ether esters, amides, and sulfoxides; more preferably, at least one selected from linear ketones such as acetone, cyclic ketones such as cyclohexanone, acetate esters such as ethyl acetate, lactones such as γ-butyrolactone, alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, linear amides such as N,N-dimethylformamide, cyclic amides such as N-methyl-2-pyrrolidone, and sulfoxides such as dimethyl sulfoxide, wherein the fluorene compound represented by formula (1) or its salt is readily soluble in these solvents.

[0114] In the mixture or composition (liquid composition or solution), the ratio of the fluorene compound represented by formula (1) or its salt to the total amount of the fluorene compound represented by formula (1) or its salt and the solvent is not particularly limited, and is, for example, 1 to 70% by mass, preferably 10 to 50% by mass, more preferably 20 to 40% by mass, and particularly 25 to 35% by mass.

[0115] The mixture or composition may, for example, be a coating solution for forming a coating film of the fluorene compound represented by formula (1) or a salt thereof; or it may be a reaction solution (reaction mixture) containing other reaction components or catalysts, for example, a reaction solution for solution polymerization of the fluorene compound represented by formula (1) or a salt thereof as a monomer. Furthermore, the mixture or composition may be a homogeneous composition (homogeneous mixture or solution) such as a solution, or a heterogeneous composition (heterogeneous mixture) such as a suspension or colloidal dispersion.

[0116] The fluorene compound (or its salt) or composition represented by formula (1) can satisfy solubility, refractive index, and heat resistance (or heat decomposition resistance) at a high level, and can be easily or efficiently mixed into resins by melt kneading, etc., and can be effectively used not only as a resin additive or resin modifier (refractive index improver, etc.), but also as a resin raw material or polymerization component (monomer component).

[0117] Therefore, this disclosure also includes resins that contain a fluorene compound (phenol compound or bisphenol compound) represented by formula (1) or a salt thereof as a resin raw material or polymerization component (monomer component). Examples of resins formed from resin raw materials or monomer components (polymerization components) include thermoplastic resins such as polyester resins [polyester resins (polyarylate resins, etc.), polycarbonate resins, polyester carbonate resins, etc.], polyether resins, and polyether ketone resins (polyether ketone resins, polyether ether ketone resins, etc.), which utilize the hydroxyl group of the fluorene compound (phenol compound) represented by formula (1); and curable resins (thermally or photocurable resins) such as polyfunctional (meth)acrylic resins [for example, polyfunctional (meth)acrylic resins, vinyl ester resins [or epoxy (meth)acrylate resins], etc.], vinyl ether resins, epoxy resins, and phenol resins. Typical resins include fluorene compounds (curable resins) represented by formula (4), which will be described later.

[0118] Furthermore, since the resin has an ethynylene group [-C≡C-] derived from the fluorene compound (phenol compound) represented by formula (1) or a salt thereof, it may be polymerized or chemically modified (or modified) using this ethynylene group. For example, graft polymerization may be performed using the ethynylene group as a starting point, or the thermoplastic resin may be cured (or crosslinked) as a macromonomer to form a cured product. In particular, the fluorene compound represented by formula (1) or a salt thereof has a high 5% weight loss temperature and exhibits high heat resistance, yet surprisingly has excellent solubility. Therefore, even when used as a monomer component for melt polymerization or solution polymerization of the resin (e.g., thermoplastic resin) or as a resin raw material for preparing (converting or deriving) the resin (e.g., curable resin), thermal decomposition can be effectively suppressed, and the reaction can be carried out at high temperatures and / or high concentrations, making it easy or efficient to prepare the resin.

[0119] Furthermore, the fluorene compound (phenol compound) or salt thereof represented by formula (1) in this disclosure may be used, for example, as an additive (resin additive or resin modifier). Examples of additives (resin additives or resin modifiers) include refractive index improvers and curing agents (such as curing agents for epoxy resins). In particular, since the fluorene compound or salt thereof represented by formula (1) has excellent heat resistance and solubility, a homogeneous composition (resin composition or liquid composition) may be easily or efficiently prepared by melt-kneading it with a resin or by mixing the resin and the fluorene compound or salt thereof in a solvent.

[0120] [Fluorene compound represented by formula (4) (curable resin)] This disclosure includes fluorene compounds (curable resins) represented by the following formula (4), which are derivatives that can be converted or derived from fluorene compounds (phenol compounds) represented by formula (1) or salts thereof.

[0121] [ka]

[0122] (In the formula, Z 1a and Z 1b These independently show an arene ring, R 1a and R 1b m1a and m1b independently represent substituents, and m1a and m1b independently represent integers greater than or equal to 0. R 2a and R 2b m2a and m2b independently represent substituents, and m2a and m2b independently represent integers from 0 to 3. Z 2a and Z 2b These independently show an arene ring, R 3a and R 3b m3a and m3b independently represent substituents, and m3a and m3b independently represent integers greater than or equal to 0. Y 1a and Y 1b (This independently represents an epoxy-containing group or a (meth)acryloyl-containing group.)

[0123] In equation (4) above [and equations (4-1) and (4-2) described later], Z 1a and Z 1b , Z 2a and Z 2b The type of arene ring represented by R 1a and R 1b , R 2a and R 2b , R 3a and R 3b The types of substituents represented by , the numerical ranges of the number of substitutions represented by m1a and m1b, m2a and m2b, m3a and m3b, each substitution position (bonding position), and combinations thereof [for example, a typical fluorene compound represented by formula (4)] are the same as those represented by formula (1), including preferred embodiments.

[0124] In the above equation (4), Y 1a and Y 1b The monovalent group represented by may be either an epoxy-containing group or a (meth)acryloyl-containing group. 1a and Y 1bThe types of the monovalent groups represented by may be different from each other, but are preferably the same.

[0125] The epoxy-containing group is not particularly limited as long as it is a monovalent group having at least an epoxy group (epoxy ring) in its chemical structure, and is preferably a group represented by the following formula (Y1-1).

[0126]

Chemical formula

[0127] (In the formula, R 4 represents a hydrogen atom or a methyl group.)

[0128] In the formula (Y1-1), R 4 may be either a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoints of curability, refractive index, productivity, etc.

[0129] Specific examples of the epoxy-containing group represented by the formula (Y1-1) include a glycidyl group and a (2-methyl) glycidyl group.

[0130] The (meth)acryloyl-containing group is not particularly limited as long as it is a monovalent group having at least a (meth)acryloyl group in its chemical structure, and is preferably a group represented by the following formula (Y1-2).

[0131]

Chemical formula

[0132] (In the formula, R 4 represents a hydrogen atom or a methyl group, p represents 0 or 1, R 5 represents a hydrogen atom or a methyl group.)

[0133] In the formula (Y1-2), R 4This can be either a hydrogen atom or a methyl group, but from the viewpoint of curability, refractive index, productivity, etc., a hydrogen atom is preferred.

[0134] Furthermore, the coefficient p may be either 0 or 1, but it is preferable that it be 1.

[0135] R 5 This can be either a hydrogen atom or a methyl group, but from the viewpoint of curability, refractive index, productivity, etc., a hydrogen atom is preferred.

[0136] Specific examples of (meth)acryloyl-containing groups represented by formula (Y1-2) include the (meth)acryloyl group, the 3-(meth)acryloyloxy-2-hydroxypropyl group, and the 3-(meth)acryloyloxy-2-hydroxy-2-methylpropyl group.

[0137] A typical fluorene compound (curable resin) represented by the above formula (4) is Y 1a and Y 1b Compounds in which is an epoxy-containing group [particularly the group represented by formula (Y1-1)], for example, a fluorene compound (epoxy resin or epoxy compound) represented by the following formula (4-1) or its polymer; Y 1a and Y 1b Compounds in which the group is a (meth)acryloyl-containing group [particularly the group represented by formula (Y1-2)] include, for example, fluorene compounds represented by the following formula (4-2) [polyfunctional (meth)acrylic resins or polyfunctional (meth)acrylic compounds].

[0138] [ka]

[0139] [In the formula, R 4a and R 4b These independently represent a hydrogen atom or a methyl group. p1 and p2 independently represent either 0 or 1. R 5a and R 5bThese independently represent a hydrogen atom or a methyl group. Z 1a and Z 1b , R 1a and R 1b , m1a and m1b, R 2a and R 2b , m2a and m2b, Z 2a and Z 2b , R 3a and R 3b m3a and m3b are the same as in formula (4) (and formula (1)), including preferred embodiments.

[0140] In equations (4-1) and (4-2) above, R 4a and R 4b is the aforementioned R 4 And p1 and p2 are the same as p, R 5a and R 5b is the aforementioned R 5 The same applies to each preferred embodiment. Also, R 4a and R 4b p1 and p2 may be different from each other, but are preferably the same; R 5a and R 5b They may be different from each other, but it is preferable that they be the same.

[0141] The typical fluorene compound (curable resin) represented by formula (4) [in particular, the typical fluorene compound (epoxy resin) represented by formula (4-1), and the typical fluorene compound (polyfunctional (meth)acrylic resin) represented by formula (4-2)] corresponds to the typical fluorene compound represented by formula (1) described above, and is the same including preferred embodiments, and among them, in formulas (4-1) and (4-2), R 4a and R 4b represents a hydrogen atom, p1 and p2 represent 1, R 5a and R 5b Compounds exhibiting a hydrogen atom are preferred.

[0142] Specific examples of fluorene compounds (epoxy resins) represented by formula (4-1) include, for example, epoxy resins (epoxy compounds) in which a glycidyloxy group or a (2-methyl)glycidyloxy group is bonded to the two phenolic hydroxyl groups, corresponding to the representative fluorene compound represented by formula (1) mentioned above, such as 9,9-bis(6-glycidyloxy-2-naphthyl)-2,7-bis(phenylethynyl)fluorene and 9,9-bis(glycidyloxyaryl)-bis(arylethynyl)fluorene.

[0143] Furthermore, specific fluorene compounds (polyfunctional (meth)acrylic resins) represented by formula (4-2) include, for example, polyfunctional (meth)acrylic resins [polyfunctional (meth)acrylic compounds] in which, corresponding to the representative fluorene compound represented by formula (1) above, the two phenolic hydroxyl groups are replaced with (meth)acryloyloxy groups, 3-(meth)acryloyloxy-2-hydroxypropyloxy groups, or 3-(meth)acryloyloxy-2-hydroxy-2-methylpropyloxy groups, such as di(meth)acrylate resins, specifically 9,9-bis Examples include 9,9-bis[(meth)acryloyloxyaryl]-bis(arylethynyl)fluorene, such as [6-(meth)acryloyloxy-2-naphthyl]-2,7-bis(phenylethynyl)fluorene; epoxy (meth)acrylate resins, specifically, 9,9-bis[6-(3-(meth)acryloyloxy-2-hydroxypropyloxy)-2-naphthyl]-2,7-bis(phenylethynyl)fluorene, such as 9,9-bis[(3-(meth)acryloyloxy-2-hydroxypropyloxy)aryl]-bis(arylethynyl)fluorene.

[0144] Furthermore, the fluorene compound represented by formula (4-1) (epoxy resin, or a curable composition containing this epoxy resin, as described later) may be a mixture containing not only the fluorene compound represented by formula (4-1) (monomer), but also its polymers, such as dimers, trimers, tetramers, and other dimers to decamers. The polymers may be included individually or in combination of two or more types.

[0145] In this specification and in the claims, unless otherwise specified, the “multimer” of the epoxy resin means an epoxy resin (epoxy compound) having two or more structures (skeletons) in its chemical structure derived from the raw material compound [the phenol compound represented by formula (1)], and these two or more structures derived from the phenol compound are linked together via linking groups derived from the epihalohydrin component described later (e.g., 2-hydroxypropane-1,3-diyl group). Such a multimer may be inevitably introduced or introduced as an impurity during the manufacturing process of the compound (monomer) represented by formula (4-1) described later, and if necessary, a multimer prepared by a conventional method such as a one-stage method (taffy method or direct method) or a two-stage method (Advanced method, melting method or indirect method) may be intentionally added to the monomer.

[0146] The proportion of the polymer may be, for example, about 0 to 50 mol%, specifically about 0 to 20 mol%, preferably 0 to 10 mol%, and more preferably 0 to 5 mol%, relative to the total number of moles of the monomer [fluorene compound (epoxy resin) represented by formula (4-1)] and its polymer. The proportion may also be, for example, 0.1 to 8 mol%, preferably 0.2 to 3 mol%.

[0147] Furthermore, the fluorene compound represented by formula (4-2) (a polyfunctional (meth)acrylic resin, or a curable composition containing this epoxy resin, as described later) may be a mixture containing not only the fluorene compound [di(meth)acrylate] represented by formula (4-2), but also a mono(meth)acrylate that has only one (meth)acryloyl group-containing group corresponding to the di(meth)acrylate. The mono(meth)acrylate may be, for example, a by-product generated when synthesizing the di(meth)acrylate by a manufacturing method described later [reaction with (meth)acrylic acid component] (for example, a product obtained by the reaction of one molecule of (meth)acrylic acid component with one molecule of the raw material fluorene compound). The mono(meth)acrylate by-product may be removed or isolated from the corresponding di(meth)acrylate [fluorene compound represented by formula (4-2)], but complete removal is often difficult (cumbersome or impractical) from a productivity standpoint, so it may be included together with the di(meth)acrylate without being completely removed by purification.

[0148] Therefore, it is preferable that the di(meth)acrylate is the main component, and the proportion of the mono(meth)acrylate may be, in terms of area ratio in high-performance (or high-performance) liquid chromatography (HPLC), for example, about 30% or less (e.g., 0-20%), preferably 15% or less (e.g., 1-12%), more preferably 10% or less (e.g., 2-8%), and particularly about 5% or less, relative to the total amount of the di(meth)acrylate and the mono(meth)acrylate. In this specification and in the claims, the area ratio can be calculated by measuring it using HPLC under the conditions of mobile phase: acetonitrile / distilled water (volume ratio) = 90 / 10, flow rate: 0.5 mL / min, and detection wavelength: 254 nm.

[0149] [Method for producing the fluorene compound represented by formula (4)] The method for producing the fluorene compound (curable resin) represented by formula (4) [in particular, formulas (4-1) and (4-2)] is not particularly limited, but the method involves using the fluorene compound (phenol compound) represented by formula (1) or a salt thereof, and the hydrogen atoms in the hydroxyl group of this fluorene compound (phenol compound) as Y 1a ,Y 1b It is preferable that the reaction step (conversion step or derivation step) includes reacting a reactive component that can be converted or derived to a group represented by the formula (4-1) with the group represented by the formula (4-2). As a typical manufacturing method, the manufacturing methods for the fluorene compound (epoxy resin) represented by formula (4-1) and the fluorene compound [polyfunctional (meth)acrylic resin] represented by formula (4-2) are described in detail below.

[0150] (Method for producing a fluorene compound (epoxy resin) represented by formula (4-1)) The fluorene compound (epoxy resin) represented by formula (4-1) may be produced, for example, by a method including an epoxidation step in which a fluorene compound (phenol compound) represented by formula (1) is reacted with a compound represented by the following formula (5a) (epihalohydrin component) and a compound represented by the following formula (5b) (epihalohydrin component).

[0151] [ka]

[0152] (In the formula, X 2a and X 2b These independently represent halogen atoms, R 4a and R 4b (The same applies to preferred embodiments.)

[0153] In equations (5a) and (5b) above, X 2a or X 2b Examples of halogen atoms represented by include chlorine atoms, bromine atoms, and iodine atoms, with chlorine atoms being preferred. 2a and X 2bThe types may be different from each other, but it is preferable that they be the same.

[0154] It is preferable that the compound represented by formula (5a) and the compound represented by formula (5b) are the same compound.

[0155] Representative compounds (epihalohydrin components) represented by formula (5a) or formula (5b) include, for example, epihalohydrins (e.g., epichlorohydrin, epibromohydrin, epiiodohydrin, etc.) and β-methylepihalohydrins (e.g., β-methylepichlorohydrin, β-methylepibromohydrin, β-methylepiiodohydrin, etc.). These epihalohydrin components can be used alone or in combination of two or more. Among these epihalohydrin components, epihalohydrins such as epichlorohydrin and β-methylepichlorohydrin are preferred, and epichlorohydrin is even more preferred.

[0156] Furthermore, as the fluorene compound (phenol compound) or salt thereof represented by formula (1) to be subjected to the epoxidation process, for example, the phenol compound or salt thereof described above can be used as a representative or specific fluorene compound represented by formula (1).

[0157] The proportion of the epihalohydrin component may be, for example, 2 moles or more per mole of the fluorene compound (phenol compound) or salt represented by formula (1) above, but it may be in excess of the phenol compound, for example, 3 to 100 moles (for example, about 10 to 50 moles, preferably 15 to 30 moles), preferably 5 to 30 moles, and more preferably 8 to 15 moles.

[0158] Furthermore, the reaction with the epihalohydrin component may be carried out in or without a catalyst, as needed. Examples of catalysts include quaternary ammonium salts, specifically tetramethylammonium chloride, tetramethylammonium bromide, and other tetramethylammonium compounds. 1-20Alkylammonium halides, benzyltrimethylammonium chloride, and other benzyltrimethylammonium chlorides 1-4 Alkylammonium halides, etc.; trimethylamine boranes, etc. 1-4 Examples include alkylamine boranes, crown ethers, phosphonium salts, and pyridinium salts. The catalyst may be used alone or in combination of two or more types.

[0159] When a catalyst is used, the proportion is not particularly limited, but is, for example, 0.001 to 1 mole, preferably 0.01 to 0.2 moles, and more preferably 0.05 to 0.1 moles, per mole of the fluorene compound (phenol compound) or salt represented by formula (1) above.

[0160] Furthermore, the epoxidation process may be carried out in the presence of a base. Examples of bases include inorganic bases such as metal hydroxides, metal carbonates, or bicarbonates; and organic bases such as amines. Examples of metal hydroxides include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides such as calcium hydroxide. Examples of metal carbonates or bicarbonates include alkali metal or alkaline earth metal carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate. Examples of amines include trialkylamines such as triethylamine, aromatic tertiary amines such as benzyldimethylamine, and heterocyclic tertiary amines such as pyridine. The base may be used alone or in combination of two or more types. Of these bases, strong bases (strong alkalis) are preferred, metal hydroxides are more preferred, and alkali metal hydroxides such as sodium hydroxide are particularly preferred.

[0161] The proportion of the base is not particularly limited, but for 1 mole of hydroxyl groups of the fluorene compound (phenol compound) represented by formula (1), it is, for example, 0.01 to 20 moles, preferably in stages, 0.05 to 10 moles, 1 to 5 moles, and 1.1 to 1.5 moles.

[0162] The reaction with the epihalohydrin component may be carried out in a solvent that is inert to the reaction, or without a solvent. Suitable solvents include aprotic solvents, such as hydrocarbons, specifically aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; alcohols (e.g., alkanols such as butanol); esters such as ethyl acetate; ethers, specifically linear ethers (e.g., dialkyl ethers such as diethyl ether), cyclic ethers such as tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); amides such as dimethylformamide (DMF) and dimethylacetamide; and sulfoxides such as dimethyl sulfoxide (DMSO). The solvent may be used alone or in combination of two or more. Of these solvents, protic polar solvents such as alcohols are preferred from the viewpoint of reactivity; aprotic polar solvents such as amides and sulfoxides are preferred; ketones such as MEK and MIBK and ethers such as dioxane are preferred; aprotic polar solvents such as amides (DMF, etc.) and sulfoxides (DMSO, etc.) are even more preferred from the viewpoint of easily reducing impurities and improving purity, and sulfoxides (DMSO, etc.) are particularly preferred.

[0163] The proportion of the solvent is not particularly limited, and is, for example, 0.01 to 100 moles per mole of the fluorene compound (phenol compound) or salt thereof represented by formula (1), preferably in the following increments: 0.1 to 50 moles, 0.5 to 30 moles, 1 to 20 moles, 1.5 to 10 moles, 2 to 5 moles, and 2.5 to 3.5 moles.

[0164] The reaction with the epihalohydrin component may be carried out in air or in an inert atmosphere such as nitrogen gas or a noble gas, and may be carried out with stirring. The reaction may also be carried out under normal pressure, under pressure, or under reduced pressure.

[0165] The reaction temperature and reaction time may be appropriately selected depending on the type of raw materials. The reaction temperature is, for example, 30 to 150°C, preferably in stages, 40 to 130°C, 45 to 100°C, 50 to 90°C, and 60 to 80°C, and the reaction may be carried out under reflux (at reflux temperature). Furthermore, in order to suppress the formation of polymers, the reaction may be carried out at a relatively low temperature within the above temperature range (for example, around 30 to 60°C, preferably 40 to 50°C), and the reaction may be carried out at a low temperature first, and then the temperature may be gradually or stepwise increased. The reaction time may be, for example, 1 to 12 hours, preferably around 2 to 6 hours.

[0166] After the reaction is complete, the reactants may be treated with a base (dehalogenation treatment or ring closure treatment) as needed to promote the formation of epoxy groups by dehalogenation or ring closure. Examples of bases include bases that may be added in the reaction with the epihalohydrin component described above, and may be the same in preferred embodiments, with metal hydroxides (particularly alkali metal hydroxides such as sodium hydroxide) being preferred. The base may be added in the form of an aqueous solution. The base may be the same as the base added in the reaction with the epihalohydrin component described above, or it may be newly added. The amount of base to be added may be, for example, about 0 to 1 mole per mole of hydroxyl groups of the fluorene compound (phenol compound) represented by formula (1), and preferably in the following steps: 0.01 to 0.5 moles, 0.03 to 0.2 moles, and 0.05 to 0.15 moles. The temperature during the treatment (dehydrohalogenation treatment or ring-closing treatment) is, for example, 30 to 150°C, preferably in stages, 40 to 130°C, 45 to 100°C, 50 to 90°C, and 60 to 80°C. The treatment time is not particularly limited and may be, for example, 0.1 to 12 hours, preferably about 0.5 to 3 hours.

[0167] After the reaction is complete, the reaction mixture may be separated and purified as needed by conventional separation and purification methods, such as neutralization, washing, extraction, filtration, dehydration, concentration, decantation, drying, crystallization, reprecipitation, column chromatography, adsorption, or a combination thereof.

[0168] (Method for producing a fluorene compound (polyfunctional (meth)acrylic resin) represented by formula (4-2)) The fluorene compound (di(meth)acrylic resin) represented by formula (4-2) may be produced by a method including a (meth)acryloylation step in which a raw material fluorene compound [such as the fluorene compound (phenol compound) represented by formula (1) or a salt thereof, or the fluorene compound (epoxy compound) represented by formula (4-1)] is reacted with (meth)acrylic acid or a salt thereof or an ester-forming derivative [collectively referred to as the (meth)acrylic acid component] represented by the following formulas (6a) and (6b).

[0169] [ka]

[0170] (In the formula, R 5a and R 5b (The same applies to preferred embodiments.)

[0171] Examples of ester-forming derivatives represented by formula (6a) or formula (6b) include alkyl (meth)acrylates (especially lower alkyl esters, specifically methyl esters, ethyl esters, etc.). 1-4 Examples include alkyl esters, (meth)acrylate halides [such as (meth)acrylate chloride], and (meth)acrylate anhydrides.

[0172] It is preferable that the compound represented by formula (6a) and the compound represented by formula (6b) [(meth)acrylic acid component] are the same compound.

[0173] Furthermore, (a) when a fluorene compound (phenol compound) represented by formula (1) or a salt thereof is used as the raw material fluorene compound, a di(meth)acrylate resin in formula (4-2) where p1=p2=0 can be prepared; and (b) when a fluorene compound (epoxy compound) represented by formula (4-1) is used as the raw material fluorene compound, an epoxy(meth)acrylate resin (vinyl ester resin) in formula (4-2) where p1=p2=1 can be prepared.

[0174] (a) Method for producing a di(meth)acrylate resin where p1=p2=0 As the fluorene compound (phenol compound) represented by formula (1) or its salt, which is a raw material fluorene compound to be used in the (meth)acryloylation process, for example, the phenol compound or its salt described above can be used as a representative or specific fluorene compound represented by formula (1).

[0175] The proportion of the (meth)acrylic acid component is 1 mole or more, for example, 1 to 10 moles (for example, about 1 to 1.25 moles), preferably 1.1 to 5 moles, more preferably 1.5 to 4 moles, even more preferably 2 to 3 moles, and more preferably 2.3 to 2.8 moles, per mole of hydroxyl groups of the fluorene compound (phenol compound) represented by formula (1).

[0176] If the (meth)acrylic acid component is an acid halide, the reaction may be carried out in the presence of a base to trap the hydrogen halides produced during the reaction. Bases can be broadly classified into inorganic bases and organic bases, for example.

[0177] 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.

[0178] 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.

[0179] The bases may be used alone or in combination of two or more. Among these bases, amines, such as trialkylamines like triethylamine, are commonly used. The amount of base used is not particularly limited, but for example, it is 1 to 2 moles, preferably 1.05 to 1.5 moles, and more preferably 1.1 to 1.2 moles per mole of (meth)acrylate halide.

[0180] Furthermore, if the (meth)acrylic acid component is an acid (or its anhydride) or an alkyl ester, the reaction may use a conventional esterification catalyst. Examples of catalysts include acid catalysts, base catalysts, and metal catalysts such as metal alkoxides, specifically titanium(IV) alkoxides such as titanium(IV) tetraisopropoxide. Of these catalysts, acid catalysts can be preferably used.

[0181] The acid catalyst is not particularly limited and includes inorganic acids, organic acids, Lewis acids such as boron trifluoride etherate and tin tetrachloride, and solid acid catalysts such as cation exchange resins. These acid catalysts may be used individually or in combination of two or more. Furthermore, these acid catalysts may be hydrates.

[0182] Examples of the inorganic acids include strong acids, specifically sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid; and homo- or heteropoly acids, specifically tungstric acid, molybdric acid, tungstosilicate, and molybdosilicic acid.

[0183] Examples of the aforementioned organic acids include sulfonic acids, specifically alkanesulfonic acids such as methanesulfonic acid and ethanesulfonic acid, fluorinated alkanesulfonic acids such as trifluoromethanesulfonic acid, and arenesulfonic acids such as p-toluenesulfonic acid. As acid catalysts, arenesulfonic acids such as p-toluenesulfonic acid monohydrate are commonly used.

[0184] The proportion of the catalyst is not particularly limited, but is, for example, 0.001 to 1 mole, preferably 0.01 to 0.5 moles, per mole of the fluorene compound (phenol compound) or salt represented by formula (1) above.

[0185] The reaction may be carried out in the presence of a polymerization inhibitor. Alternatively, a polymerization inhibitor may be added after the reaction is complete. Examples of polymerization inhibitors include benzoquinone; hydroquinone, hydroquinone monomethyl ether (MEHQ, p-methoxyphenol or methoquinone), t-butylhydroquinone, p-benzoquinone and other hydroquinones; catechols such as pt-butylcatechol; amines such as N,N-diethylhydroxylamine; 1,1-diphenyl-2-picrylhydrazyl; tri-p-nitrophenylmethyl; and phenothiazines. Polymerization inhibitors may be used alone or in combination of two or more. Among these polymerization inhibitors, hydroquinones such as p-methoxyphenol (or methoquinone) are commonly used.

[0186] The proportion of the polymerization inhibitor may be, for example, about 0.001 to 10 parts by mass per 100 parts by mass of the (meth)acrylic acid component, or about 0.0001 to 0.1 parts by mass per 100 parts by mass of the fluorene compound represented by formula (4-2) obtained by the reaction.

[0187] The reaction may be carried out in the presence of a solvent. Examples of solvents include hydrocarbons, specifically aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons, specifically methylene chloride, chloroform, 1,2-dichloroethane, and chlorobenzene; ethers, specifically dialkyl ethers such as diethyl ether, and cyclic ethers such as tetrahydrofuran (THF) and 1,4-dioxane; ketones, specifically acetone and methyl ethyl ketone; sulfoxides, specifically dimethyl sulfoxide; amides, specifically N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; and nitriles such as acetonitrile. These solvents may be used alone or in combination of two or more. Among these solvents, aromatic hydrocarbons such as toluene are commonly used. The proportion of the solvent is not particularly limited and may be, for example, about 10 to 1000 parts by mass, preferably 50 to 150 parts by mass, per 100 parts by mass of the total amount of the fluorene compound (phenol compound) or its salt and the (meth)acrylic acid component represented by formula (1).

[0188] The reaction temperature and reaction time can be appropriately selected depending on the type of raw materials used. When the (meth)acrylic acid component is (meth)acrylic acid halide, the reaction temperature is, for example, -10°C to 30°C, preferably 0 to 20°C, and more preferably 2 to 10°C. When the (meth)acrylic acid component is (meth)acrylic acid (or its anhydride) or an alkyl ester of (meth)acrylic acid, the reaction temperature is, for example, 50 to 150°C, preferably 80 to 130°C, and more preferably 100 to 120°C. The reaction may also be carried out at reflux temperature. The reaction time is not particularly limited and may be, for example, 1 to 24 hours.

[0189] The reaction can be carried out in air or in an inert atmosphere such as nitrogen gas or a noble gas, with stirring, and may be carried out under atmospheric pressure, pressurized pressure, or reduced pressure. In addition, to effectively prevent unexpected polymerization during the reaction, air may be blown into the reaction solution.

[0190] After the reaction is complete, the di(meth)acrylate compound represented by formula (4-2) that is produced may be separated and purified by conventional methods, such as neutralization, washing, dehydration, filtration, adsorption, concentration, extraction, crystallization, recrystallization, reprecipitation, centrifugation, column chromatography, or a combination thereof.

[0191] (b) Method for producing epoxy (meth)acrylate resin where p1=p2=1 As the fluorene compound (epoxy compound) represented by formula (4-1) used as a raw material for the (meth)acryloylation process, for example, the epoxy compounds mentioned above can be used as representative or specific fluorene compounds represented by formula (4-1).

[0192] The proportion of the (meth)acrylic acid component is 1 mole or more, for example 1 to 10 moles (for example about 1 to 1.25 moles), per mole of epoxy group (or glycidyl group) of the fluorene compound (epoxy compound) represented by formula (4-1), preferably in stages as follows: 1 to 2 moles, 1.1 to 1.5 moles, and 1.2 to 1.3 moles.

[0193] The reaction may be carried out in the presence of a catalyst. A base catalyst is preferred as the catalyst. The base catalyst may be an inorganic base or an organic base.

[0194] Examples of inorganic bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and alkaline earth metal hydroxides such as calcium hydroxide.

[0195] Examples of organic bases include amines, quaternary ammonium salts, phosphines, and phosphonium salts. Examples of amines include aliphatic tertiary amines such as triethylamine and tributylamine; aromatic tertiary amines such as N,N-dimethylaniline; heterocyclic amines such as pyridine, imidazole, 2-methylimidazole, and 2-ethyl-4-methylimidazole; and amidines [e.g., cyclic amidines such as 1,5-diazabicyclo[4.3.0]-5-nonene and 1,8-diazabicyclo[5.4.0]-7-undecene]. Examples of quaternary ammonium salts include tetramethylammonium chloride, tetramethylammonium bromide, and benzyltrimethylammonium bromide. Examples of phosphines include triphenylphosphine and tributylphosphine. Examples of phosphonium salts include n-butyltriphenylphosphonium bromide.

[0196] These catalysts can be used individually or in combination of two or more. Of these catalysts, quaternary ammonium salts are preferred, such as tetramethylammonium bromide and other tetraC 1-20 Alkylammonium halides are even more preferred.

[0197] The proportion of the catalyst is, for example, 0.01 to 10 moles, preferably 0.1 to 5 moles, more preferably 0.3 to 4 moles, more preferably 0.5 to 3 moles, and most preferably 0.7 to 2 moles, per 100 moles of the fluorene compound (epoxy compound) represented by formula (4-1).

[0198] The reaction may be carried out in the presence of a polymerization inhibitor, if necessary. Examples of polymerization inhibitors include those similar to those exemplified in section (a) above, "Methoquinone," and hydroquinones such as methoquinone are preferred.

[0199] The proportion of the polymerization inhibitor may be, for example, about 0.001 to 10 parts by mass per 100 parts by mass of the (meth)acrylic acid component, preferably 0.005 to 1 part by mass, or for example, about 0.0001 to 1 part by mass per 100 parts by mass of the epoxy (meth)acrylate compound represented by formula (4-2) obtained by the reaction.

[0200] The reaction may be carried out in solvent-free or solvent-based conditions. Suitable solvents include: aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as benzene and toluene; alcohols such as methanol, ethanol, n-propanol, and benzyl alcohol; dialkyl ethers such as diethyl ether; cyclic ethers such as tetrahydrofuran (THF) and 1,4-dioxane; aromatic ethers such as anisole; and glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME), ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol diethyl ether (DEDG). Examples include chain ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); cyclic ketones such as cyclohexanone; acetate esters such as ethyl acetate; lactic acid esters such as methyl lactate, ethyl lactate, and butyl lactate; lactones or cyclic esters such as γ-butyrolactone; ether esters such as alkoxycarboxylic acid esters such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), and ethyl 3-ethoxypropionate; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; and sulfoxides such as dimethyl sulfoxide.

[0201] These solvents can be used individually or in combination of two or more. Of these, ether esters are preferred, and alkylene glycol monoalkyl ether acetates such as PGMEA are particularly preferred.

[0202] The proportion of the solvent is, for example, 1 to 1000 parts by mass, preferably 10 to 500 parts by mass, more preferably 30 to 200 parts by mass, and more preferably 50 to 100 parts by mass, per 100 parts by mass of the epoxy compound represented by formula (4-2).

[0203] The reaction temperature is, for example, 50 to 150°C, preferably 70 to 140°C, more preferably 90 to 130°C, and more preferably 100 to 120°C. The reaction time is not particularly limited, for example, 30 minutes to 100 hours, preferably 1 to 50 hours. The reaction is usually carried out in air or under an inert gas atmosphere, at atmospheric pressure or under pressurized pressure.

[0204] After the reaction is complete, the epoxy (meth)acrylate compound represented by formula (4-2) that is produced may be separated and purified by conventional methods, such as neutralization, washing, dehydration, filtration, adsorption, concentration, extraction, crystallization, recrystallization, reprecipitation, centrifugation, column chromatography, or a combination thereof.

[0205] [Properties of fluorene compounds represented by formula (4)] The fluorene compound (curable resin) represented by formula (4) exhibits high heat resistance (thermal decomposition resistance), and its 5% weight loss temperature may be, for example, 350°C or higher (e.g., 380°C to 470°C), preferably 390°C or higher (e.g., 400°C to 450°C), and more preferably 410°C to 430°C.

[0206] In the above equation (4), Y 1a and Y 1b Compounds in which the epoxy-containing group is [in particular, fluorene compounds (epoxy resins) represented by formula (4-1)] exhibit high heat resistance (thermal decomposition resistance), and their 5% weight loss temperature may be, for example, 400°C or higher (e.g., 430°C to 450°C), preferably 410°C or higher (e.g., 412°C to 440°C), and more preferably 415°C to 430°C.

[0207] In the above equation (4), Y 1a and Y 1b Compounds in which (meth)acryloyl is a (meth)acryloyl-containing group [preferably, fluorene compounds represented by the above formula (4-2) (polyfunctional (meth)acrylic resins), in particular epoxy (meth)acrylate resins in which p1=p2=1] exhibit high heat resistance (thermal decomposition resistance), and their 5% weight loss temperature may be, for example, 385°C or higher (e.g., 390°C to 450°C), preferably 400°C or higher (e.g., 405 to 430°C), and more preferably 410 to 420°C.

[0208] The fluorene compound (curable resin) represented by formula (4) exhibits a high refractive index, and its refractive index nD may be, for example, 1.67 or higher (e.g., 1.68 to 1.83) at a temperature of 25°C and a wavelength of 589 nm, preferably 1.69 or higher (e.g., 1.7 to 1.8), and more preferably 1.71 or higher (e.g., 1.71 to 1.79).

[0209] In the above equation (4), Y 1a and Y 1b Compounds in which the epoxy-containing group is [in particular, fluorene compounds (epoxy resins) represented by the above formula (4-1)] exhibit a high refractive index, and the refractive index nD may be, for example, 1.765 or higher (e.g., 1.77 to 1.81) at a temperature of 25°C and a wavelength of 589 nm, preferably 1.77 or higher (e.g., 1.775 to 1.8), and more preferably 1.78 or higher (e.g., 1.78 to 1.79).

[0210] In the above equation (4), Y 1a and Y 1b Compounds in which (meth)acryloyl is a (meth)acryloyl-containing group [preferably, fluorene compounds represented by the above formula (4-2) (polyfunctional (meth)acrylic resins), in particular epoxy (meth)acrylate resins in which p1=p2=1] exhibit a high refractive index, and the refractive index nD at a temperature of 25°C and a wavelength of 589 nm may be, for example, 1.67 or higher (e.g., 1.68 to 1.73), preferably 1.69 or higher (e.g., 1.7 to 1.725), and more preferably 1.705 or higher (e.g., 1.71 to 1.72).

[0211] In this specification and in the claims, the 5% weight loss temperature and refractive index nD can be measured by the method described in the examples below.

[0212] The fluorene compound (curable resin) represented by formula (4) may be crystalline or amorphous. When the fluorene compound (curable resin) represented by formula (4) is crystalline, its melting point is, for example, 180 to 300°C (for example, 200 to 280°C), preferably 210 to 260°C (for example, 220 to 250°C).

[0213] In the above equation (4), Y 1a and Y 1b The compound in which is an epoxy-containing group [in particular, the fluorene compound (epoxy resin) represented by formula (4-1) above] may be crystalline or amorphous. In formula (4) above, Y 1a and Y 1b When the compound in which is an epoxy-containing group [in particular, the fluorene compound (epoxy resin) represented by formula (4-1) above] is crystalline, its melting point is, for example, 200 to 280°C (e.g., 210 to 260°C), preferably 220 to 250°C (e.g., 230 to 240°C), and more preferably 231 to 237°C (e.g., 232 to 236°C).

[0214] In the above equation (4), Y 1a and Y 1b The compound having a (meth)acryloyl-containing group [preferably, a fluorene compound represented by formula (4-2) (a polyfunctional (meth)acrylic resin), in particular an epoxy (meth)acrylate resin in which p1=p2=1] may be crystalline or amorphous.

[0215] In this specification and in the claims, the melting point can be measured by the method described in the examples below.

[0216] The fluorene compound (curable resin) represented by formula (4) may be soluble in at least one solvent selected from acetone, cyclohexanone, ethyl acetate, γ-butyrolactone, propylene glycol monomethyl ether acetate, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide at a concentration of 30% by mass and a temperature of 25°C within 1 hour.

[0217] In the above equation (4), Y 1a and Y 1b A compound in which is an epoxy-containing group [in particular, a fluorene compound (epoxy resin) represented by formula (4-1)] may be soluble in at least one solvent selected from acetone, cyclohexanone, ethyl acetate, γ-butyrolactone, propylene glycol monomethyl ether acetate, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide (preferably at least one solvent selected from cyclohexanone, γ-butyrolactone, N,N-dimethylformamide, and N-methyl-2-pyrrolidone) at a concentration of 30% by mass and a temperature of 25°C within 1 hour.

[0218] In the above equation (4), Y 1a and Y 1b A compound having a (meth)acryloyl-containing group [preferably, a fluorene compound represented by formula (4-2) (a polyfunctional (meth)acrylic resin), particularly an epoxy (meth)acrylate resin with p1=p2=1] may be soluble in at least one solvent selected from acetone, cyclohexanone, ethyl acetate, γ-butyrolactone, propylene glycol monomethyl ether acetate, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide at a concentration of 30% by mass and a temperature of 25°C within 1 hour.

[0219] In this specification and in the claims, solubility can be measured by the method described in the examples below.

[0220] In addition, in formula (4) above, Y 1a and Y 1b The epoxy equivalent of the compound in which is an epoxy-containing group [in particular, the fluorene compound (epoxy resin) represented by formula (4-1) above] may be selected from a range of, for example, 331 g / eq or more (for example, about 350 to 2000 g / eq), preferably 360 to 1000 g / eq, more preferably 370 to 800 g / eq, and particularly preferably 380 to 450 g / eq (for example, 390 to 430 g / eq, preferably 400 to 420 g / eq).

[0221] In this specification and in the claims, the epoxy equivalent can be measured by the method described in the examples below, in accordance with JIS K 7236:2001.

[0222] [Curable composition containing a fluorene compound represented by formula (4) and its cured product] This disclosure also includes curable compositions and cured products thereof, comprising a fluorene compound (curable resin) represented by formula (4). The curable composition comprises Y in formula (4). 1a and Y 1b The epoxy-based curable composition may also contain at least a compound in which is an epoxy-containing group [in particular, a fluorene compound (epoxy resin) represented by formula (4-1)]; in formula (4), Y 1a and Y 1b The (meth)acrylic curable composition may contain at least a compound having a (meth)acryloyl-containing group [preferably, a fluorene compound represented by the formula (4-2) (a polyfunctional (meth)acrylic resin), particularly an epoxy (meth)acrylate resin in which p1=p2=1].

[0223] (Other polymerization components) The curable composition may or may not contain other polymerization components different from the fluorene compound (curable resin) represented by formula (4), as needed.

[0224] The curable composition is Y in formula (4) above. 1a and Y1b In the case of an epoxy-based curable composition containing at least a compound in which is an epoxy-containing group [in particular, a fluorene compound (epoxy resin) represented by the above formula (4-1)] (hereinafter also referred to as the first epoxy compound), it may or may not contain a second epoxy compound different from the above formula (4).

[0225] Examples of the second epoxy compound (epoxy resin) include glycidyl ether type epoxy resins, specifically bi or bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, bisphenol AD ​​type, bisphenol S type, and biphenol type; novolac type epoxy resins such as phenol novolac type and cresol novolac type; phenol aralkyl type epoxy resins; triphenol alkane type epoxy resins; tetrakisphenol type epoxy resins such as tetrakis(glycidyloxyphenyl)ethane; condensed ring aromatic hydrocarbon modified epoxy resins such as 1,6-bis(glycidyloxy)naphthalene; and diglycidyl ether type epoxy resins (or their hydrogenated counterparts). Examples include glycidyl ester type epoxy resins such as sidyl esters; glycidylamine type epoxy resins such as tetraglycidyldiaminodiphenylmethane, tetraglycidylbisaminomethylcyclohexane, and triglycidylaminophenol; cyclic aliphatic type epoxy resins such as bis(3,4-epoxycyclohexylmethyl)adipate and (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexanecarboxylate; stilbene type epoxy resins; heterocyclic epoxy resins such as isocyanurate type epoxy resins, hydantoin type epoxy resins, and epoxy resins containing xanthene units; and bromine-containing epoxy resins such as tetrabromobisphenol A type epoxy resin.

[0226] Furthermore, a reactive diluent may be included as the second epoxy compound. The reactive diluent may be a monofunctional or polyfunctional epoxy compound with low viscosity, for example, a viscosity of about 200 mPa·s or less at 25°C, preferably 100 mPa·s or less, and more preferably 30 mPa·s or less. Examples of monofunctional epoxy compounds include alkyl glycidyl ethers such as 2-ethylhexyl glycidyl ether, alkenyl glycidyl ethers such as allyl glycidyl ether, aryl glycidyl ethers such as phenyl glycidyl ether and pt-butylphenyl glycidyl ether, and glycidyl ethers of alkylene oxide adducts corresponding to these compounds; and alkene oxides such as octylene oxide, styrene oxide, and 4-vinylcyclohexene monooxide.

[0227] Examples of polyfunctional epoxy compounds include diglycidyl ethers, polyol polyglycidyl ethers, diglycidylaniline, and cycloalkene oxides. Examples of polyol polyglycidyl ethers include (poly)alkanediol diglycidyl ethers such as butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether, as well as cyclohexanedimethanol diglycidyl ether, trimethylolpropane or triglycidyl ether, and glycerin or triglycidyl ether. Examples of cycloalkene oxides include vinylcyclohexene dioxide and methylated vinylcyclohexene dioxide.

[0228] These reactive diluents may be used individually or in combination of two or more. The proportion of the reactive diluent is, for example, 1 to 1000 parts by mass, preferably 5 to 500 parts by mass, and more preferably 10 to 200 parts by mass, per 100 parts by mass of the total amount of epoxy resin components (compounds having epoxy groups) in the epoxy curing agent composition.

[0229] The second epoxy compound may be a monomer, a dimer, a trimer, or other polymer. The second epoxy compound may be used alone or in combination of two or more types. Preferred second epoxy compounds are bi- or bisphenol type epoxy resins, such as bisphenol A type epoxy resins.

[0230] The proportion of the first epoxy compound may be, for example, about 10 to 100% by mass relative to the total epoxy resin in the epoxy-based curable composition, preferably in stages of 30% by mass or more, 50% by mass or more, 70% by mass or more, 90% by mass or more, and particularly 100% by mass.

[0231] The curable composition is Y in formula (4) above. 1a and Y 1b In the case of a (meth)acrylic curable composition containing at least a compound having a (meth)acryloyl-containing group [preferably, a fluorene compound represented by formula (4-2) (a polyfunctional (meth)acrylic resin), particularly an epoxy (meth)acrylate resin in which p1=p2=1] (hereinafter also referred to as a first polyfunctional (meth)acrylate), other polymerization components, such as a second polyfunctional (meth)acrylate different from formula (4), monofunctional polymerization components (or reactive diluents), etc., may or may not be included as needed.

[0232] The second polyfunctional (meth)acrylate is not particularly limited and may be any compound having multiple (two or more) (meth)acryloyl groups. The number of (meth)acryloyl groups per molecule is, for example, 2 to 10, preferably 2 to 6, more preferably 2 to 4, most preferably 2 to 3, and especially preferably 2.

[0233] Examples of the second type of polyfunctional (meth)acrylate include epoxy (meth)acrylates (vinyl ester resins) such as aliphatic epoxy (meth)acrylates, alicyclic epoxy (meth)acrylates, aromatic epoxy (meth)acrylates, and poly(meth)acrylates of novolac-type epoxy resins; urethane (meth)acrylates; polyester (meth)acrylates (poly(meth)acrylates of polyester polyols having two or more hydroxyl groups); alkylene glycol di(meth)acrylates; polyalkylene glycol di(meth)acrylates; di(meth)acrylates of alicyclic diols; di(meth)acrylates of biphenols or bisphenols or their alkylene oxide (alkylene carbonate or haloalkanol) adducts; and poly(meth)acrylates of low molecular weight polyol compounds having about 3 to 6 hydroxyl groups or their alkylene oxide (alkylene carbonate or haloalkanol) adducts. These second polyfunctional (meth)acrylates may be used alone or in combination of two or more. Commercially available products may be used for these second polyfunctional (meth)acrylates.

[0234] Examples of the aliphatic epoxy (meth)acrylate include di(meth)acrylates of (poly)alkylene glycol diglycidyl ethers, such as di(meth)acrylate of 1,6-hexanediol diglycidyl ether and di(meth)acrylate of polypropylene glycol diglycidyl ether.

[0235] Examples of the alicyclic epoxy (meth)acrylate include C1,4-cyclohexanedimethanol diglycidyl ether di(meth)acrylate. 5-10 Examples include di(meth)acrylates of epoxy compounds having an aliphatic ring.

[0236] Examples of the aromatic epoxy (meth)acrylate include di(meth)acrylates of bisphenols or biphenols or their alkylene oxide (alkylene carbonate or haloalkanol) adducts, such as di(meth)acrylate of bisphenol A diglycidyl ether. Examples of bisphenols include bisphenol A, bisphenol F, bisphenol AD, and bisphenol S. Examples of biphenols include p,p'-biphenol, m,m'-biphenol, and o,o'-biphenol.

[0237] Examples of alkylene glycol di(meth)acrylate include ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, and other C 2-10 Examples include alkylene glycol di(meth)acrylate.

[0238] The polyalkylene glycol di(meth)acrylate mentioned above may include, for example, diethylene glycol di(meth)acrylate and other di or hexaC 2-10 Examples include alkylene glycol di(meth)acrylate.

[0239] Examples of di(meth)acrylates of alicyclic diols include C1,4-cyclohexanedimethanol di(meth)acrylate. 5-10 Examples include di(meth)acrylates of diol compounds having an aliphatic ring.

[0240] Examples of poly(meth)acrylates of low molecular weight polyol compounds having approximately 3 to 6 hydroxyl groups or their alkylene oxide (alkylene carbonate or haloalkanol) adducts include glycerin tri(meth)acrylate, diglycerin tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and sorbitol tri or hexa(meth)acrylate.

[0241] The proportion of the first polyfunctional (meth)acrylate can be selected from a range of approximately 30 to 100% by mass, for example, 10% by mass or more, relative to the total amount of the first and second polyfunctional (meth)acrylates, preferably in stages of 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, more preferably 90% by mass or more, and in particular, it is preferable that it be substantially 100% by mass, i.e., that the polyfunctional polymerization component is only the first polyfunctional (meth)acrylate. The proportion may be selected from a range of approximately 60 to 99% by mass, for example, and may be 80 to 97% by mass. When the proportion of the first polyfunctional (meth)acrylate is above the lower limit, the refractive index and heat resistance tend to improve.

[0242] The monofunctional polymerization component (or reactive diluent) can be any compound having one polymerizable group (or polymerizable unsaturated bond), such as a vinyl group, an alkenyl group such as an allyl group, or a (meth)acryloyl group. Specifically, examples include monofunctional vinyl monomers and monofunctional (meth)acrylic monomers. Examples of monofunctional vinyl monomers include α-olefin monomers such as ethylene and propylene; styrene monomers such as styrene, α-methylstyrene, and vinyltoluene; vinyl ester monomers such as vinyl acetate; and N-vinylpyrrolidone. Examples of monofunctional (meth)acrylic monomers include (meth)acrylic acid; (meth)acrylamide; N-substituted (meth)acrylamides such as N-methylol(meth)acrylamide and N,N-dimethyl(meth)acrylamide; (meth)acrylonitrile; and monofunctional (meth)acrylates.

[0243] These monofunctional polymerization components can be used individually or in combination of two or more. Among these monofunctional polymerization components, monofunctional (meth)acrylic monomers, particularly monofunctional (meth)acrylates, are commonly used.

[0244] Examples of monofunctional (meth)acrylates include aliphatic monofunctional (meth)acrylates; alicyclic monofunctional (meth)acrylates; aromatic monofunctional (meth)acrylates; and monofunctional (meth)acrylates containing sulfur atoms. These monofunctional (meth)acrylates can be used individually or in combination of two or more types.

[0245] Examples of aliphatic monofunctional (meth)acrylates include methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and C 1-20 Examples include alkyl (meth)acrylates.

[0246] Examples of alicyclic monofunctional (meth)acrylates include C636 5-10Examples of cross-linked cyclic (meth)acrylates include cycloalkyl (meth)acrylates, dicyclopentenyl (meth)acrylates, and isobornyl (meth)acrylates.

[0247] Examples of aromatic monofunctional (meth)acrylates include aryl (meth)acrylates such as phenyl (meth)acrylate; aralkyl (meth)acrylates such as benzyl (meth)acrylate; and aryloxyalkyl (meth)acrylates, specifically C2-phenoxyethyl (meth)acrylate, 2-(2-naphthoxy)ethyl (meth)acrylate, and 2-(o-phenylphenoxy)ethyl (meth)acrylate. 6-12 Aryloxy C 2-4 Examples include alkyl (meth)acrylates; mono(meth)acrylates of bisphenols or biphenols (or their alkylene oxide adducts), such as mono(meth)acrylates of ethylene oxide adducts of bisphenol A; and (meth)acrylates having a fluorene skeleton, such as 9-(meth)acryloyloxymethylfluorene.

[0248] Examples of monofunctional (meth)acrylates containing sulfur atoms include alkylthio(meth)acrylates, arylthio(meth)acrylates, aralkylthio(meth)acrylates, and arylthioalkyl(meth)acrylates. Examples of alkylthio(meth)acrylates include methylthio(meth)acrylates. 1-6 Examples include alkylthio(meth)acrylates. Examples of arylthio(meth)acrylates include phenylthio(meth)acrylate and other C3 6-10 Examples include arylthio(meth)acrylates. Examples of arylthio(meth)acrylates include benzylthio(meth)acrylate. 6-10 Aryl C 1-6 Examples include alkylthio(meth)acrylates. Examples of arylthioalkyl(meth)acrylates include phenylthioethyl(meth)acrylate. 6-10 Arylthio C2-4 Examples include alkyl (meth)acrylates.

[0249] (Ingredients other than polymerization components) The curable composition may or may not contain, as it is necessary, a curing agent, a curing accelerator, a cationic polymerization initiator, a radical polymerization initiator, a solvent, or additives, in addition to the polymerization component (or monomer component).

[0250] Examples of curing agents include amine-based curing agents, polyaminoamide-based curing agents, acid anhydride-based curing agents, and phenolic resin-based curing agents. These may also be included in the epoxy-based curable composition.

[0251] Examples of amine-based curing agents include primary amines, such as linear aliphatic amines, specifically linear aliphatic polyamines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine; cyclic aliphatic amines, specifically monocyclic, crosslinked, or spirocyclic aliphatic polyamines such as mensendiamine, isophoronediamine, bis(4-amino-3-methylcyclohexyl)methane, norbornanediamine, and 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane; aromatic aliphatic polyamines such as xylylenediamine; and aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, and 4,4'-diaminodiphenylsulfone.

[0252] Examples of polyaminoamide-based curing agents include condensates of polyethylene polyamines such as ethylenediamine, diethylenetriamine, and triethylenehexamine, dimer acid, and, if necessary, fatty acids.

[0253] Examples of acid anhydride-based curing agents include aliphatic acid anhydrides such as dodecenyl succinic anhydride and polyadipic anhydride; alicyclic acid anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, and methylcyclohexendicarboxylic acid anhydride; and aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic acid anhydride.

[0254] Examples of phenolic resin curing agents include novolac resins such as phenol novolac resins and cresol novolac resins, and resol-type phenolic resins.

[0255] These curing agents can be used individually or in combination of two or more. Of these curing agents, phenolic resin-based curing agents are preferred, and novolac resins such as phenol novolac resins are even more preferred.

[0256] The proportion of the curing agent is, for example, 0.1 to 500 parts by mass, preferably 1 to 100 parts by mass, and more preferably 10 to 50 parts by mass, per 100 parts by mass of the total amount of epoxy resin components (compounds having epoxy groups) in the curable composition. The proportion of the functional groups (or active hydrogen) of the curing agent is, for example, 0.1 to 4 equivalents, preferably in the following increments, 0.3 to 2 equivalents, 0.5 to 1.5 equivalents, 0.8 to 1.2 equivalents, and 0.9 to 1.1 equivalents, per equivalent of epoxy groups of the epoxy resin components.

[0257] Curing accelerators may be included in the epoxy-based curable composition. Examples of curing accelerators include amines such as tertiary amines, imidazoles and their derivatives; alkali metal or alkaline earth metal alkoxides; phosphines, specifically triarylphosphines such as triphenylphosphine; amide compounds such as dimer acid polyamides; Lewis acid complex compounds such as boron trifluoride-ethylamine complexes; sulfur compounds such as polysulfides and mercaptan compounds (thiol compounds); boron compounds such as phenyldichloroborane; and condensing organometallic compounds such as organotitanium compounds and organoaluminum compounds. Regarding the amines, examples of tertiary amines include triethylamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo[5.4.0]-7-undecene. Examples of imidazoles include mono- or dialkylimidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, and arylimidazoles such as 2-phenylimidazole. Examples of derivatives include phenol salts, phenol novolac salts, carbonates, formates, and other salts. These curing accelerators may be used individually or in combination of two or more. Among these curing accelerators, phosphines are preferred, and triarylphosphines such as triphenylphosphine are even more preferred.

[0258] The proportion of the curing accelerator is, for example, 0.01 to 30 parts by mass, preferably 0.05 to 20 parts by mass, 0.1 to 10 parts by mass, and 1 to 5 parts by mass, based on 100 parts by mass of the total amount of epoxy resin components (compounds having epoxy groups) in the curable composition. Furthermore, the proportion of the curing accelerator is, for example, 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 2 parts by mass, based on 100 parts by mass of the total amount of epoxy resin components and curing agent in the curable composition.

[0259] The cationic photopolymerization initiator may be included in the epoxy curable composition. The cationic polymerization initiator may also be a cationic photopolymerization initiator such as a photoacid generator. Examples of cationic photopolymerization initiators include onium salts of Brønsted acids such as aromatic diazonium salts, aromatic sulfonium salts, and aromatic iodonium salts.

[0260] Examples of aromatic diazonium salts include benzenediazonium compounds such as benzenediazonium hexafluoroantimonate and benzenediazonium hexafluorophosphate.

[0261] Examples of aromatic sulfonium salts include triphenylsulfonium compounds such as triphenylsulfonium hexafluorophosphate and triphenylsulfonium hexafluoroantimonate, and 4,4'-bis(diphenylsulfonio)diphenyl sulfides such as 4,4'-bis(diphenylsulfonio)diphenyl sulfide bishexafluorophosphate.

[0262] Examples of aromatic iodonium salts include diphenyliodonium compounds such as diphenyliodonium tetrakis(pentafluorophenyl)borate and diphenyliodonium hexafluorophosphate, and di(4-nonylphenyl)iodonium compounds such as di(4-nonylphenyl)iodonium hexafluorophosphate.

[0263] Cationic photopolymerization initiators can be used alone or in combination of two or more. The proportion of cationic photopolymerization initiator may be 0.1 to 10 parts by mass, preferably about 0.5 to 5 parts by mass, per 100 parts by mass of the total amount of epoxy resin components (compounds having epoxy groups) in the curing agent composition.

[0264] Radical polymerization initiators may be included in (meth)acrylic curable compositions. Radical polymerization initiators may be thermal polymerization initiators (thermal radical generators) or photopolymerization initiators (photoradical generators).

[0265] Examples of thermal polymerization initiators include organic peroxides and azo compounds. Examples of organic peroxides include dialkyl peroxides such as di-t-butyl peroxide; diacyl peroxides such as lauroyl peroxide and benzoyl peroxide; peracids (or peracid esters) such as t-butyl hydroperoxide, cumene hydroperoxide, and t-butyl peracetate; ketone peroxides; peroxycarbonates; and peroxyketals. Examples of azo compounds include azonitrile compounds such as 2,2'-azobis(isobutyronitrile), azoamide compounds, and azoamidine compounds. These thermal polymerization initiators can be used alone or in combination of two or more.

[0266] Examples of radical photopolymerization initiators include benzoins, specifically benzoin alkyl ethers such as benzoin and benzoin ethyl ether; acetophenones such as acetophenone; α-hydroxyphenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1-hydroxycyclohexyl-phenyl ketone; aminoacetophenones such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoaminopropanone-1; anthraquinones such as anthraquinone and 2-methylanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; xanthones; and benzoylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. These photopolymerization initiators may be used alone or in combination of two or more.

[0267] The proportion of polymerization initiator (thermal and / or photopolymerization initiator) is, for example, 0.1 to 15 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, and even more preferably 2 to 5 parts by mass, per 100 parts by mass of the total amount of polymerization components.

[0268] Furthermore, the photopolymerization initiator may be combined with a photosensitizer. Typical photosensitizers include tertiary amines, such as trialkylamines; trialcanolamines such as triethanolamine; alkyl dialkylaminobenzoates, specifically N,N-dimethylaminobenzoate ethyl such as p-(dimethylamino)benzoate ethyl, N,N-dimethylaminobenzoate amyl such as p-(dimethylamino)benzoate amyl; bis(dialkylamino)benzophenone such as 4,4-bis(diethylamino)benzophenone; and dialkylaminobenzophenone such as 4-(dimethylamino)benzophenone. These photosensitizers may be used alone or in combination of two or more.

[0269] The proportion of the photosensitizer is, for example, 1 to 200 parts by mass, preferably 5 to 150 parts by mass, and more preferably 10 to 100 parts by mass, per 100 parts by mass of the polymerization initiator.

[0270] The fluorene compound represented by formula (4) may have surprisingly high solubility, and to adjust handling, the curable composition may or may not contain a solvent as needed. The solvent is not particularly limited and includes, for example, solvents similar to those exemplified in the section [Properties and Uses of the Fluorene Compound Represented by Formula (1) or its Salt] (Uses) above, including preferred embodiments. These solvents can be used individually or as mixed solvents in combination of two or more.

[0271] The curable composition may contain at least one solvent selected from ketones, esters, ether esters (such as PGMEA), amides, and sulfoxides.

[0272] The proportion of the solvent is not particularly limited, and the concentration of non-volatile solids (components other than the solvent) may be such that it is approximately 0.1 to 80% by mass (e.g., 10 to 60% by mass) of the total curable composition.

[0273] The curable composition may contain conventional additives, such as colorants, stabilizers, fillers, antistatic agents, flame retardants, surfactants, plasticizers, curing agents, polymerization inhibitors, etc. Examples of stabilizers include heat stabilizers, antioxidants, and ultraviolet absorbers. These additives can be used individually or in combination of two or more.

[0274] The proportion of the additive is, for example, about 50% by mass or less (for example, 30% by mass or less) relative to the entire curable composition (preferably the total solid content in the curable composition), preferably in stages as follows: 20% by mass or less, 10% by mass or less, and 5% by mass or less. The aforementioned proportion may be 0.001 to 15% by mass, specifically 0.01 to 3% by mass.

[0275] (cured product) The curable composition of this disclosure can be easily cured (curing step) by applying active energy (or active energy rays) as needed to produce a cured product. The active energy can be thermal energy and / or light energy, such as ultraviolet rays or X-rays. In the curing step, the curable composition may be partially cured or semi-cured (stage B) before being fully cured.

[0276] When using thermal energy for heat treatment, the heating temperature is, for example, 50 to 300°C, preferably 100 to 250°C, and more preferably 150 to 200°C.

[0277] Furthermore, when using light energy such as ultraviolet light for irradiation, the amount of light irradiation energy can be appropriately selected depending on the application, for example, 50 to 10,000 mJ / cm². 2 Preferably 70-8000 mJ / cm² 2 More preferably 100-5000 mJ / cm² 2More preferably 200-3000 mJ / cm² 2 Most preferably 300-1000 mJ / cm² 2 That is the case.

[0278] The shape of the cured product is not particularly limited and may be a three-dimensional structure such as a lens-shaped or tubular cured product, a two-dimensional structure such as a film-shaped, sheet-shaped, or plate-shaped cured product (or cured film), or a one-dimensional structure such as a linear or fibrous, thread-shaped, or rod-shaped cured product.

[0279] The method for manufacturing the cured product is not particularly limited. For example, depending on the shape of the cured product, the curable composition may be molded or poured into a predetermined mold, and then cured (heated and / or irradiated with light). In the case of a two-dimensional cured product, for example, the curable composition may be applied to a substrate or base material, such as a metal like aluminum; an inorganic material or ceramic like titanium oxide, glass, or quartz; an organic material or plastic like a cyclic olefin resin or polycarbonate resin; or a porous body like wood, to form a film-like coating (or thin film), and then cured.

[0280] Since the cured product of this disclosure is formed from a fluorene compound (curable resin) represented by formula (4), it exhibits a high refractive index. Therefore, the refractive index nD of the cured product at a temperature of 25°C and a wavelength of 589 nm may be, for example, around 1.65 to 1.8.

[0281] Furthermore, since the cured product is formed from a fluorene compound (curable resin) represented by formula (4), it has high heat resistance, and the glass transition temperature Tg of the cured product may be, for example, around 120 to 250°C, and preferably in the following increments: 130 to 250°C, 150 to 220°C, 160 to 200°C, 170 to 190°C, and 175 to 185°C.

[0282] Since the cured product is formed from a fluorene compound (curable resin) represented by formula (4), it has high heat resistance, and the temperature at which the cured product loses 5% of its weight may be, for example, around 300 to 450°C, and preferably in stages below, 330 to 430°C, 350 to 420°C, 360 to 410°C, 370 to 400°C, 375 to 395°C, and 380 to 390°C.

[0283] In this specification and in the claims, the glass transition temperature Tg and 5% weight loss temperature of the cured product can be measured by the method described in the examples below. [Examples]

[0284] 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 materials are described below.

[0285] [Evaluation Method] (HPLC) Using a Shimadzu LC-2030 HPLC (High Performance Liquid Chromatography) instrument and a Tosoh ODS-80TM column, samples were dissolved in acetonitrile and measured to calculate HPLC purity (LC purity) [area %].

[0286] ( 1 (H-NMR) The sample is dissolved in a deuterated 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.

[0287] (LC-MS) Using a Shimadzu Nexera XR HPLC (High Performance Liquid Chromatography) instrument, an LCMS-2020 MS unit, and a Phenomenex Kinetex C-18 column, the samples were dissolved in a mixed solvent of acetonitrile and tetrahydrofuran (THF) (acetonitrile / THF = 90 / 10 (mass ratio)) for measurement.

[0288] (FD-MS) Mass spectrometry (MS) was performed based on the following measuring equipment and conditions. Equipment used: “JMS-T200GC” manufactured by JEOL Ltd. Ionization method: FD (Field Desorption) Emitter: Carbon Emitter current: 0-50mA (25mA / min)

[0289] (5% weight loss temperature) Thermogravimetric analysis—using a differential thermal analyzer (TG-DTA) (TG / DTA6200, manufactured by SII Nanotechnology Co., Ltd.), was performed to measure the temperature at which the mass of the sample decreased by 5% under conditions of a nitrogen atmosphere and a heating rate of 10°C / min.

[0290] (Melting point) A differential scanning calorimeter (Discovery DSC25, manufactured by T.A. Instruments Japan Co., Ltd.) 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 (DSC curve), the temperature at the peak top of the endothermic peak due to melting was read and defined as the melting point.

[0291] (Glass transition temperature Tg) A differential scanning calorimeter (Discovery DSC25, manufactured by T.A. Instruments Japan Co., Ltd.) 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. The glass transition temperature (Tg) of the sample (cured material) was read from the obtained DSC chart (DSC curve).

[0292] (Solubility) The sample (200 mg) and the solvent described below were added to a 30 mL scale test tube to a concentration of 30% 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 at room temperature (25°C), the temperature was gradually increased to 50°C, and if it still did not dissolve at 50°C, the temperature was increased to 80°C. The solubility was confirmed by stirring in the same manner as above at 50°C or 80°C, and the solubility was evaluated according to the following evaluation criteria.

[0293] ◎: Dissolved within 1 hour at 25℃ ○: Did not dissolve within 1 hour at 25℃, but dissolved within 1 hour at 50℃. △: Did not dissolve within 1 hour at 50°C, but dissolved within 1 hour at 80°C. ×: Did not dissolve within 1 hour at 80°C

[0294] (Refractive index nD) The refractive index was measured using a refractometer (ATAGO RX-7000i) at a temperature of 25°C and a wavelength of 589 nm (D-line). The refractive index was calculated by dissolving the sample in dimethyl sulfoxide to prepare solutions with concentrations of 5.0 mass%, 10.0 mass%, and 30.0 mass%, and then extrapolating the concentrations to 100 mass% in a calibration curve (approximate straight line) created by measuring the refractive index of the obtained solutions and 0 mass% (dimethyl sulfoxide only).

[0295] (Epoxy equivalent) In accordance with JIS K 7236:2001, titration was performed using an automatic titrator (Mitsubishi Chemical Corporation "GT-100") with perchloric acid solution (acetic acid).

[0296] [Synthesis Example 1]

[0297] [ka]

[0298] 9,9-bis(6-hydroxy-2-naphthyl)-2,7-dibromofluorene (hereinafter also referred to as DBrBNF), represented by the above formula, was prepared in accordance with Synthesis Example 1 of Japanese Patent Publication No. 2022-042002.

[0299] [Example 1]

[0300] [ka]

[0301] In a three-necked flask, 36.5 g (60 mmol) of DBrBNF, 18.4 g (180 mmol, 3.0 eq) of ethynylbenzene, 0.34 g (1.8 mmol, 0.03 eq) of copper(I) iodide, and 243 g (2.4 mol, 40 eq) of triethylamine were added. The system was then subjected to a nitrogen atmosphere, and 0.53 g (3 mmol, 0.05 eq) of palladium chloride and 1.57 g (6 mmol, 0.1 eq) of triphenylphosphine were added. The mixture was stirred and reacted for 2 hours under reflux of triethylamine. After the reaction was complete, methyl isobutyl ketone (MIBK) was added, and the mixture was filtered by Celite to remove insoluble matter. The resulting filtrate was washed with deionized water four times. The resulting organic layer was concentrated under reduced pressure to obtain a concentrate (a paste-like liquid composition containing a small amount of MIBK), to which n-hexane was added and crystallization was performed. The obtained solid was heated and dissolved in toluene, n-hexane was added, and after cooling, the precipitated crystals were filtered to obtain 12 g (yield 33%, LC purity 95%) of the target product, 9,9-bis(6-hydroxy-2-naphthyl)-2,7-bis(phenylethynyl)fluorene [hereinafter also referred to as bisethynylbenzene BNF or BEBBNF], as a brownish powder. The melting point of the obtained BEBBNF was 136°C. 1 The results of the H-NMR spectrum are shown below.

[0302] 1H NMR (300MHz, CDCl3): δ(ppm)=7.0(2H,d), 7.1(2H,s), 7.3(2H,d), 7.4-7.5(6H,m), 7.5-7.6(6H,m), 7.6-7.7(8H,m), 8.1(2H,d)

[0303] [Comparative Example 1]

[0304] [ka]

[0305] 9,9-bis(6-hydroxy-2-naphthyl)-2,7-di(2-naphthyl)fluorene (hereinafter also referred to as DNBNF), represented by the above formula, was prepared in accordance with Example 1C of Japanese Patent Publication No. 2022-042002.

[0306] [Comparative Example 2] Various evaluations were performed using 9,9-bis(6-hydroxy-2-naphthyl)fluorene (hereinafter also referred to as BNF), which is represented by the following formula.

[0307] [ka]

[0308] Tables 1 and 2 below show the physical properties (5% weight loss temperature, refractive index) and solubility evaluation results of the fluorene compounds obtained in Example 1 and Comparative Examples 1 and 2. In Table 2, PGMEA represents propylene glycol monomethyl ether acetate, DMF represents N,N-dimethylformamide, NMP represents N-methyl-2-pyrrolidone, and DMSO represents dimethyl sulfoxide.

[0309] [Table 1]

[0310] [Table 2]

[0311] As is clear from the results in Table 1, Example 1, a phenolic compound, exhibited extremely high heat resistance, with a 5% higher weight loss temperature compared to Comparative Examples 1 and 2. In particular, compared to Comparative Example 1 (DNBNF), in which naphthalene rings with a higher proportion of benzene ring skeletons were bonded to the 2,7-positions of the fluorene skeleton, Example 1 showed a 5% higher weight loss temperature of approximately 40°C, which was an unexpected result.

[0312] Furthermore, Example 1 also had a higher refractive index compared to Comparative Examples 1 and 2. In the field of optical materials, even an improvement of around 0.01 in nD is considered advantageous, so the improvement in refractive index in Example 1 can be said to be remarkable.

[0313] Furthermore, as is clear from the results in Table 2, Example 1 exhibited unexpectedly high solubility in various solvents compared to Comparative Example 1. Therefore, Example 1 achieved an even higher level of balance between heat resistance, refractive index, and solubility.

[0314] [Example 2]

[0315] [ka]

[0316] In a 300 mL round-necked flask, 19.48 g (0.030 mol) of BEBBNF obtained in Example 1, 27.61 g (0.300 mol, 10 eq), and 6.89 g (0.088 mol) of dimethyl sulfoxide (DMSO) were placed, and the container was purged with nitrogen. 2.81 g (0.070 mol, 2.34 eq) of sodium hydroxide (granules) was added, and the mixture was stirred at 45°C for 1 hour and then at 70°C for 2 hours. The epichlorohydrin was then concentrated and removed. After dissolving with 100 g (0.975 mol, 32.5 eq) of methyl isobutyl ketone (MIBK), 0.80 g of 30% by mass NaOH aqueous solution was added, and the mixture was stirred at 70°C for 1 hour. Insoluble matter was filtered through Celite filtration, and after draining, the organic layer was washed with 43.3 mL of distilled water. This process was repeated four times. MIBK was concentrated and adjusted to a solid content of 60% by mass. The organic layer was then reprecipitated with 65 g of methanol, and the resulting solid was dried at 80°C to obtain 7.64 g of 9,9-bis(6-glycidyloxy-2-naphthyl)-2,7-bis(phenylethynyl)fluorene [hereinafter also referred to as BEBBNFG] as a pale yellow solid. The melting point of the obtained BEBBNFG was 234°C, and its epoxy equivalent was 410.5371 g / eq. 1 The results of the H-NMR spectrum are shown below.

[0317] 1 H NMR (300MHz, CDCl3): δ(ppm)=2.8(2H,d), 2.9(2H,d), 3.4(2H,m), 4.1(2H,d), 4.3(2H,d), 7.1-7.8(28H,m)

[0318] (Preparation of curable compositions containing BEBBNFG and their cured products) In a sample bottle, 2.0 g of BEBBNFG and 0.5 g of phenol novolac resin (PSM-4261, manufactured by Gun-ei Chemical Industry Co., Ltd., with a hydroxyl group equivalent of 105 g / eq) were added (i.e., mixed so that the epoxy group / hydroxyl group (molar ratio) was approximately 1 / 1). The mixture was melted at 250°C using a multi-stirrer, stirred with a spatula, and 0.025 g of triphenylphosphine was added as a curing accelerator. Once homogenized, the resulting curable composition (or partially cured curable composition) was removed to a curing dish and heated in a drying oven at 175°C for 5 hours to fully cure. The glass transition temperature (Tg) of the resulting cured product was 180.5°C, and the 5% weight loss temperature of the cured product was 380.05°C.

[0319] [Comparative Example 3]

[0320] [ka]

[0321] 9,9-bis(6-glycidyloxy-2-naphthyl)-2,7-di(2-naphthyl)fluorene (hereinafter also referred to as DNBNFG), represented by the above formula, was prepared in accordance with Example 3A of Japanese Patent Publication No. 2022-042002.

[0322] Tables 3 and 4 below show the physical properties (5% weight loss temperature, refractive index) and solubility evaluation results of the fluorene compounds obtained in Example 2 and Comparative Example 3. In Table 4, DMF represents N,N-dimethylformamide and NMP represents N-methyl-2-pyrrolidone.

[0323] [Table 3]

[0324] [Table 4]

[0325] As is clear from the results in Tables 3-4, Example 2, an epoxy resin derived from a phenol compound, also exhibited higher heat resistance (5% weight loss temperature) and refractive index compared to Comparative Example 3, and its solubility was equally superior. Therefore, in Example 2, it was possible to improve heat resistance and refractive index without significantly reducing solubility.

[0326] [Example 3]

[0327] [ka]

[0328] In a 50 mL flask, 5.30 g (0.007 mol) of BEBBNFG obtained in Example 2, 1.27 g (0.018 mol) of acrylic acid, 4.23 g of propylene glycol monomethyl ether acetate (PGMEA), 0.0142 g (0.1 mmol) of tetramethylammonium bromide, and 0.0203 g (0.1 mmol) of 4-methoxyphenol were added. The mixture was stirred at 110°C for 27 hours, and 3.62 g of PGMEA was added to adjust the solid content. 14.5 g of 9,9-bis[6-(3-acryloyloxy-2-hydroxypropyloxy)-2-naphthyl]-2,7-bis(phenylethynyl)fluorene (hereinafter also referred to as BEBBNFGA) was obtained as a PGMEA solution with a solid content of 47.3% by mass (6.86 g). In the obtained LC-MS spectrum of BEBBNFGA, a peak was confirmed at m / z=907, which corresponds to BEBBNFGA. 1 The results of the H-NMR spectrum are shown below.

[0329] 1 H NMR (300MHz, CDCl3): δ(ppm)=3.4(2H,d), 4.2(4H,d), 4.3(2H,m), 4.4(4H,d), 5.9(2H,m), 6.1-6.2(2H,m), 6.4-6.5(2H,m), 7.1-7.8(28H,m)

[0330] [Comparative Example 4]

[0331] [ka]

[0332] In a 100 mL flask, 48.9 g (0.06 mol) of DNBNFG obtained in Comparative Example 3, 10.8 g (0.15 mol) of acrylic acid, 7.5 g of PGMEA, 0.09 g (0.6 mmol) of tetramethylammonium bromide, and 0.13 g (1.0 mmol) of 4-methoxyphenol were added, and the mixture was stirred at 110°C for 10 hours to obtain 9,9-bis[6-(3-acryloyloxy-2-hydroxypropyloxy)-2-naphthyl]-2,7-di(2-naphthyl)fluorene (hereinafter also referred to as DNBNFGA). The FD-MS spectrum of the obtained DNBNFGA was measured, and a peak at m / z=958, which corresponds to DNBNFGA, was confirmed. 1 The results of the H-NMR spectrum are shown below.

[0333] 1 H NMR (DMSO-d6,300MHz): δ(ppm)=4.04-4.28(m,10H), 5.44(OH,2H), 6.12(dd,4H), 6.12-6.22(m,2H), 7.09(d, 2H), 7.29(s,2H), 7.47-7.57(m,6H), 7.70(d,4H), 7.81(t,4H), 7.89-8.01(m,10H), 8.18(d,2H), 8.23(s,2H)

[0334] Table 5 below shows the evaluation results of the physical properties (5% weight loss temperature, refractive index) of the fluorene compounds obtained in Example 3 and Comparative Example 4.

[0335] [Table 5]

[0336] As is clear from the results in Table 5, Example 3, which is an epoxy (meth)acrylate resin derived from a phenol compound, also showed higher heat resistance (5% weight loss temperature) and refractive index compared to Comparative Example 4. [Industrial applicability]

[0337] The fluorene compound (phenol compound) represented by formula (1) in this disclosure may be used, for example, as a resin raw material or monomer component (polymerization component), or as an additive (resin additive).

[0338] The fluorene compound (phenol compound) represented by formula (1) of this disclosure, a resin using the fluorene compound (phenol compound) as a resin raw material or monomer component (polymerization component) [for example, epoxy resin, epoxy (meth)acrylate resin, or polyfunctional (meth)acrylic resin, etc.], and a composition containing the fluorene compound (phenol compound) as an additive, as well as a curable composition containing an epoxy resin, epoxy (meth)acrylate resin, and / or di(meth)acrylate resin represented by formula (4) and its cured product, can be suitably used as optical components (optical materials or transparent materials) or their raw materials, semiconductor manufacturing materials (or reagents), and the like.

[0339] Examples of the optical components include optical lenses such as reflow lenses, pickup lenses, and microlenses; optical films such as polarizing films, anti-reflective films, touch panel films, flexible substrate films, and display films; films for fuel cells; optical fibers; optical waveguides; and holograms.

[0340] Examples of the semiconductor manufacturing materials (or reagents) include resist materials for forming resist films, underlayer films, upper layers, intermediate layers, anti-reflective films, protective films, and the like.

Claims

1. A fluorene compound represented by the following formula (1) or a salt thereof. 【Chemistry 1】 (In the formula, Z １ａ and Z １ｂ These independently show an arene ring, R １ａ and R １ｂ m1a and m1b independently represent substituents, and m1a and m1b independently represent integers greater than or equal to 0. R ２ａ and R ２ｂ m2a and m2b independently represent substituents, and m2a and m2b independently represent integers from 0 to 3. Z ２ａ and Z ２ｂ These independently show an arene ring, R ３ａ and R ３ｂ each independently represents a substituent, and m3a and m3b each independently represent an integer of 0 or more.)

2. In the above formula (1), Z １ａ and Z １ｂ These independently exhibit a benzene ring, R １ａ and R １ｂ m1a and m1b independently represent an alkyl group, and m1a and m1b independently represent an integer from 0 to 4. R ２ａ and R ２ｂ m2a and m2b independently represent an alkyl group, and m2a and m2b independently represent an integer between 0 and 2. Z ２ａ and Z ２ｂ C is independent ６－１２ Showing an arene ring, R ３ａ and R ３ｂ The fluorene compound represented by formula (1) or a salt thereof according to claim 1, wherein m3a and m3b independently represent an alkyl group, and m3a and m3b independently represent an integer from 0 to 4.

3. In the above formula (1), Z １ａ and Z １ｂ These independently exhibit a benzene ring, R １ａ and R １ｂ C is independent １－４ It represents an alkyl group, and m1a and m1b independently represent integers from 0 to 2. R ２ａ and R ２ｂ C is independent １－４ It represents an alkyl group, and m2a and m2b independently represent 0 or 1. Z ２ａ and Z ２ｂ C is independent ６－１０ Showing an arene ring, R ３ａ and R ３ｂ C is independent １－４ A fluorene compound represented by formula (1) or a salt thereof according to claim 1, wherein the alkyl group is represented and m3a and m3b independently represent integers from 0 to 2.

4. A fluorene compound represented by formula (1) or a salt thereof according to any one of claims 1 to 3, wherein the 5% weight loss temperature is 450°C or higher.

5. A fluorene compound represented by formula (1) or a salt thereof according to any one of claims 1 to 3, wherein the refractive index nD at a temperature of 25°C and a wavelength of 589 nm is 1.74 or more.

6. A fluorene compound represented by formula (1) or a salt thereof according to any one of claims 1 to 3, which is soluble in at least one solvent selected from acetone, cyclohexanone, ethyl acetate, γ-butyrolactone, propylene glycol monomethyl ether acetate, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide at a concentration of 30% by mass and a temperature of 25°C within 1 hour.

7. A method for producing a fluorene compound represented by formula (1) or a salt thereof, according to any one of claims 1 to 3, comprising a coupling step of reacting a fluorene compound represented by formula (2) or a salt thereof with a compound represented by formula (3a) and a compound represented by formula (3b). 【Chemistry 2】 [In the formula, X １ａ and X １ｂ These independently represent reactive groups that can be coupled with the compound represented by formula (3a) and the compound represented by formula (3b), respectively. Z １ａ and Z １ｂ , R １ａ and R １ｂ , m1a and m1b, R ２ａ and R ２ｂ , m2a and m2b, Z ２ａ and Z ２ｂ , R ３ａ and R ３ｂ m3a and m3b are the same as in formula (1) above.

8. A mixture comprising a fluorene compound represented by formula (1) or a salt thereof as described in any one of claims 1 to 3, and at least one solvent selected from ketones, esters, ether esters, amides, and sulfoxides.

9. A resin comprising a fluorene compound represented by formula (1) or a salt thereof as described in any one of claims 1 to 3, as a resin raw material or polymerization component.

10. A fluorene compound represented by the following formula (4). 【Transformation 3】 (In the formula, Z １ａ and Z １ｂ These independently show an arene ring, R １ａ and R １ｂ m1a and m1b independently represent substituents, and m1a and m1b independently represent integers greater than or equal to 0. R ２ａ and R ２ｂ m2a and m2b independently represent substituents, and m2a and m2b independently represent integers from 0 to 3. Z ２ａ and Z ２ｂ These independently show an arene ring, R ３ａ and R ３ｂ m3a and m3b independently represent substituents, and m3a and m3b independently represent integers greater than or equal to 0. Y １ａ and Y １ｂ (This independently represents an epoxy-containing group or a (meth)acryloyl-containing group.)

11. The fluorene compound represented by formula (4) according to claim 10, wherein the epoxy-containing group is a group represented by the following formula (Y1-1). 【Chemistry 4】 (In the formula, R ４ (This represents a hydrogen atom or a methyl group.)

12. In the above formula (4), Y １ａ and Y １ｂ These independently represent the epoxy-containing group, The temperature at which the 5% weight loss occurs is 410°C or higher. The refractive index nD at a temperature of 25°C and a wavelength of 589 nm is 1.765 or higher. A fluorene compound represented by formula (4) according to claim 10 or 11, which is soluble in at least one solvent selected from acetone, cyclohexanone, ethyl acetate, γ-butyrolactone, propylene glycol monomethyl ether acetate, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide at a concentration of 30% by mass and a temperature of 25°C within 1 hour.

13. The fluorene compound represented by formula (4) according to claim 10, wherein the (meth)acryloyl-containing group is a group represented by the following formula (Y1-2). 【Transformation 5】 (In the formula, R ４ This indicates a hydrogen atom or a methyl group. p represents 0 or 1. R ５ (This represents a hydrogen atom or a methyl group.)

14. In the above formula (4), Y １ａ and Y １ｂ These independently represent the (meth)acryloyl-containing group, The temperature at which the 5% weight loss occurs is 390°C or higher. The refractive index nD at a temperature of 25°C and a wavelength of 589 nm is 1.67 or higher. A fluorene compound represented by formula (4) according to claim 10 or 13, which is soluble in at least one solvent selected from acetone, cyclohexanone, ethyl acetate, γ-butyrolactone, propylene glycol monomethyl ether acetate, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide at a concentration of 30% by mass and a temperature of 25°C within 1 hour.

15. A fluorene compound represented by formula (1) according to any one of claims 1 to 3, and a hydrogen atom in the hydroxyl group of this fluorene compound Y １ａ , Y １ｂ A method for producing a fluorene compound represented by formula (4) according to any one of claims 10, 11, and 13, comprising a reaction step of reacting with a reactive component that can be converted to or derived from the group represented by .

16. A curable composition comprising a fluorene compound represented by formula (4) according to any one of claims 10, 11, and 13.

17. The curable composition according to claim 16, comprising at least one solvent selected from ketones, esters, ether esters, amides, and sulfoxides.

18. A cured product obtained by curing the curable composition according to claim 16.

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