Fluorene compound, manufacturing method therefor, and use thereof

Abstract

Provided is a fluorene compound capable of achieving both a high refractive index and high solubility. A fluorene compound according to the present disclosure is represented by formula (1). [In the formula, Y1a and Y1b denote groups represented by formula (Y1), R2a and R2b denote substituents, m2a and m2b denote integers of 0 to 3, and Y2a and Y2b denote groups represented by formula (Y2). (In these formulas, Z1 denotes an arene ring, R1 denotes a substituent, m1 denotes an integer of 0 or 1 or greater, R3, R4, and R5 denote substituents, m3 denotes an integer of 0 to 5, m4 denotes an integer of 0 to 5, m5 denotes an integer of 0 to 2, A1 and A2 denote alkylene groups, and n1 denotes an integer of 0 or 1 or greater).]

Description

Fluorene compound, its production method and use

[0001] The present disclosure relates to a compound having a fluorene skeleton, and a method for producing and using the same.

[0002] Compounds having a fluorene skeleton have excellent optical properties due to their chemical structure, and are used as resin materials (optical materials) for forming optical components.

[0003] Japanese Patent Laid-Open No. 2020-75866 (Patent Document 1) discloses a crystal of a compound represented by the following formula (A), which has a maximum melting endothermic temperature of 201 to 205 ° C. by differential scanning calorimetry, and describes that the crystal has a high bulk density.

[0004]

[0005] In addition, Japanese Patent Laid-Open No. 2018-90560 (Patent Document 2) discloses a compound having the following general formula (B):

[0006]

[0007] (In the formula, R １ ~R ４ are the same or different and each represents an alkyl group, an aryl group, or a halogen atom; n １ and n ２ are the same or different and represent an integer of 1 to 4; k １ ~k ４ are the same or different and each represents an integer of 0 or 1 to 4. １ ~k ４ If at least one of these is 2 or more, the corresponding R １ ~R ４ may be the same or different)

[0008] and it is described that resins made from the bisphenols as raw materials are excellent in refractive index and heat resistance, and further, are excellent in fluidity when melted and solvent solubility.

[0009] JP 2020-75866 A JP 2018-90560 A

[0010] The compound represented by formula (A) in Patent Document 1 is included in the bisphenols represented by formula (B) in Patent Document 2, and Patent Document 2 describes the properties of resins made from the bisphenols.

[0011] However, Patent Documents 1 and 2 do not disclose or suggest anything about a compound in which an aryl group (particularly, a plurality of aryl groups, such as two aryl groups) is bonded to the 1- to 8-positions of a fluorene ring, or about the optical properties thereof.

[0012] Generally, when a fluorene compound contains a benzene ring (aromatic ring) in its chemical structure, its heat resistance (boiling point, 5% weight loss temperature, etc.) and refractive index increase, but its solubility tends to decrease. Therefore, the applications of the fluorene compound containing a benzene ring are significantly restricted.

[0013] Therefore, an object of the present disclosure is to provide a fluorene compound that can achieve both a high refractive index and high solubility even when it contains many benzene rings in its chemical structure, as well as a production method and use thereof.

[0014] The present inventors have discovered that a fluorene compound having a specific chemical structure satisfies the requirements of a high refractive index and high solubility, and have completed the present invention (present disclosure).

[0015] That is, the present disclosure may include the following aspects.

[0016] Aspect [1]: A fluorene compound (diol compound) represented by the following formula (1).

[0017]

[0018] [In the formula, Y １ａ and Y １ｂ are independently represented by the following formula (Y1):

[0019]

[0020] (In the formula, Z １ represents an arene ring, and R １ represents a substituent, and m1 represents an integer of 0 or 1 or more), R ２ａ and R ２ｂeach independently represents a substituent, m2a and m2b each independently represents an integer of 0 to 3, and Y ２ａ and Y ２ｂ are independently represented by the following formula (Y2):

[0021]

[0022] (In the formula, A １ represents an alkylene group, n1 represents 0 or an integer of 1 or more, R ３ represents a substituent, m3 represents an integer of 0 to 5, ２ represents an alkylene group, R ４ represents a substituent, m4 represents an integer of 0 to 5, R ５ represents a substituent, and m5 represents an integer of 0 to 2),

[0023] Aspect [2]: In the formula (1) [and the formulas (Y1) and (Y2)], Z １ is C ６－１２ m1 represents an integer of 0 to 2; m2a and m2b independently represent an integer of 0 to 2; m3, m4, and m5 independently represent an integer of 0 to 2; R １ ~R ５ (i.e., R １ , R ２ａ , R ２ｂ , R ３ , R ４ and R ５ ) independently represent a hydrocarbon group; A １ is C ２－６ represents an alkylene group, n1 represents 0 or an integer of 1 to 6, and A ２ is C １－４ The fluorene compound according to embodiment [1], wherein the fluorene compound represents an alkylene group.

[0024] Aspect [3]: In the formula (1), Y １ａ and Y １ｂ Z in formula (Y1) represents １ The fluorene compound according to embodiment [1] or [2], wherein R represents a benzene ring or a naphthalene ring.

[0025] Aspect [4]: ​​The fluorene compound according to any one of aspects [1] to [3], which is a crystal and has a melting point of 195 to 210°C.

[0026] Aspect [5]: The fluorene compound according to any one of aspects [1] to [4], which is at least one selected from the group consisting of a monomer for melt polymerization or solution polymerization and a resin additive for modifying a resin.

[0027] Aspect [6]: A method for producing a fluorene compound according to any one of Aspects [1] to [5], comprising the reaction steps (i) and (ii) below:

[0028] (i) a step of reacting a compound represented by the following formula (2) with a compound represented by the following formula (3a) and a compound represented by the following formula (3b); and (ii) a step of coupling a compound represented by the following formula (4) with a compound represented by the following formula (5a) and a compound represented by the following formula (5b).

[0029]

[0030] [In the formula, X １ａ and X ２ａ and X １ｂ and X ２ｂ independently represent a pair of reactive groups capable of forming a carbon-carbon bond by a coupling reaction; Y １ａ and Y １ｂ , R ２ａ and R ２ｂ , m2a and m2b, and Y ２ａ and Y ２ｂ is the same as formula (1) above.

[0031] Aspect [7]: A resin made from a fluorene compound represented by formula (1) according to any one of aspects [1] to [5].

[0032] Aspect [8]: An optical member comprising the resin according to aspect [7].

[0033] Aspect [9]: A (meth)acrylate compound [(meth)acrylic resin] represented by the following formula (7):

[0034] [In the formula, Y １ａ and Y １ｂ are independently represented by the following formula (Y1):

[0035]

[0036] (In the formula, Z １ represents an arene ring, and R １ represents a substituent, and m1 represents an integer of 0 or 1 or more), R ２ａ and R ２ｂ each independently represents a substituent, m2a and m2b each independently represents an integer of 0 to 3, and Y ３ａ and Y ３ｂ are independently represented by the following formula (Y3):

[0037]

[0038] (In the formula, A １ represents an alkylene group, n1 represents 0 or an integer of 1 or more, R ３ represents a substituent, m3 represents an integer of 0 to 5, ２ represents an alkylene group, R ４ represents a substituent, m4 represents an integer of 0 to 5, R ５ represents a substituent, m5 represents an integer of 0 to 2, R ６ represents a hydrogen atom or a methyl group),

[0039] Aspect

[10] : In the formula (7) [and the formulas (Y1) and (Y3)], Z １ is C ６－１２ m1 represents an integer of 0 to 2; m2a and m2b independently represent an integer of 0 to 2; m3, m4, and m5 independently represent an integer of 0 to 2; R １ ~R ５ (i.e., R １ , R ２ａ , R ２ｂ , R ３ , R ４ and R ５ ) independently represent a hydrocarbon group; A １ is C ２－６ represents an alkylene group, n1 represents 0 or an integer of 1 to 6, and A ２ is C １－４ The (meth)acrylate compound according to embodiment [9], wherein the (meth)acrylate compound represents an alkylene group.

[0040] Aspect

[11] : A method for producing the (meth)acrylate compound according to aspect [9] or

[10] , comprising a step of reacting the fluorene compound represented by formula (1) according to any one of aspects [1] to [5] with (meth)acrylic acid or an ester-forming derivative thereof.

[0041] Aspect

[12] : An epoxy compound (epoxy resin) represented by the following formula (8):

[0042]

[0043] [In the formula, Y １ａ and Y １ｂ are independently represented by the following formula (Y1):

[0044]

[0045] (In the formula, Z １ represents an arene ring, and R １ represents a substituent, and m1 represents an integer of 0 or 1 or more), R ２ａ and R ２ｂ each independently represents a substituent, m2a and m2b each independently represents an integer of 0 to 3, and Y ４ａ and Y ４ｂ are independently represented by the following formula (Y4):

[0046]

[0047] (In the formula, A １ represents an alkylene group, n1 represents 0 or an integer of 1 or more, R ３ represents a substituent, m3 represents an integer of 0 to 5, ２ represents an alkylene group, R ４ represents a substituent, m4 represents an integer of 0 to 5, R ５ represents a substituent, m5 represents an integer of 0 to 2, R ７ represents a hydrogen atom or a methyl group),

[0048] Aspect

[13] : In the formula (8) [and the formulas (Y1) and (Y4)], Z １ is C ６－１２m1 represents an integer of 0 to 2; m2a and m2b independently represent an integer of 0 to 2; m3, m4, and m5 independently represent an integer of 0 to 2; R １ ~R ５ (i.e., R １ , R ２ａ , R ２ｂ , R ３ , R ４ and R ５ ) independently represent a hydrocarbon group; A １ is C ２－６ represents an alkylene group, n1 represents 0 or an integer of 1 to 6, and A ２ is C １－４ The epoxy compound according to embodiment

[12] , wherein the epoxy compound represents an alkylene group.

[0049] Aspect

[14] : A method for producing an epoxy compound according to aspect

[12] or

[13] , comprising a step of reacting a fluorene compound represented by formula (1) according to any one of aspects [1] to [5] with an epihalohydrin component.

[0050] Aspect

[15] : An epoxy (meth)acrylate compound [vinyl ester resin (or epoxy (meth)acrylate resin)] represented by the following formula (9):

[0051]

[0052] [In the formula, Y １ａ and Y １ｂ are independently represented by the following formula (Y1):

[0053]

[0054] (In the formula, Z １ represents an arene ring, and R １ represents a substituent, and m1 represents an integer of 0 or 1 or more), R ２ａ and R ２ｂ each independently represents a substituent, m2a and m2b each independently represents an integer of 0 to 3, and Y ５ａ and Y ５ｂ are independently represented by the following formula (Y5):

[0055]

[0056] (In the formula, A １represents an alkylene group, n1 represents 0 or an integer of 1 or more, R ３ represents a substituent, m3 represents an integer of 0 to 5, ２ represents an alkylene group, R ４ represents a substituent, m4 represents an integer of 0 to 5, R ５ represents a substituent, m5 represents an integer of 0 to 2, R ７ represents a hydrogen atom or a methyl group, R ８ represents a hydrogen atom or a methyl group),

[0057] Aspect

[16] : In the formula (9) [and the formulas (Y1) and (Y5)], Z １ is C ６－１２ m1 represents an integer of 0 to 2; m2a and m2b independently represent an integer of 0 to 2; m3, m4, and m5 independently represent an integer of 0 to 2; R １ ~R ５ (i.e., R １ , R ２ａ , R ２ｂ , R ３ , R ４ and R ５ ) independently represent a hydrocarbon group; A １ is C ２－６ represents an alkylene group, n1 represents 0 or an integer of 1 to 6, and A ２ is C １－４ The epoxy (meth)acrylate compound according to embodiment

[15] , which represents an alkylene group.

[0058] Aspect

[17] : A method for producing the epoxy (meth)acrylate compound according to aspect

[15] or

[16] , comprising a step of reacting the epoxy compound represented by formula (8) according to aspect

[12] or

[13] with (meth)acrylic acid or an ester-forming derivative thereof.

[0059] Aspect

[18] : A curable composition comprising at least one selected from the group consisting of the (meth)acrylate compound represented by formula (7) according to aspect [9] or

[10] , the epoxy compound represented by formula (8) according to aspect

[12] or

[13] , and the epoxy (meth)acrylate compound represented by formula (9) according to aspect

[15] or

[16] [vinyl ester resin (or epoxy (meth)acrylate resin)].

[0060] Aspect

[19] : A cured product obtained by curing the curable composition according to aspect

[18] .

[0061] Aspect

[20] : An optical component comprising the cured product according to aspect

[19] .

[0062] Aspect

[21] : A composition (liquid composition or solution, or liquid mixture) comprising at least one selected from the group consisting of the fluorene compound (diol compound) represented by formula (1) according to any one of aspects [1] to [5], the (meth)acrylate compound [(meth)acrylic resin] represented by formula (7) according to aspect [9] or

[10] , the epoxy compound (epoxy resin) represented by formula (8) according to aspect

[12] or

[13] , and the epoxy (meth)acrylate compound [vinyl ester resin (or epoxy (meth)acrylate resin)] represented by formula (9) according to aspect

[15] or

[16] , and a solvent.

[0063] Aspect

[22] : The composition according to aspect

[21] , wherein the solvent is at least one selected from the group consisting of ketones, esters, ethers, ether esters, amides, and aromatic hydrocarbons.

[0064] In addition, the present disclosure may achieve the following secondary objectives (solve the problems).

[0065] Another object of the present disclosure is to provide a fluorene compound exhibiting high heat resistance (or resistance to thermal decomposition), a method for producing the same, and a composition (or mixture) containing the compound.

[0066] In this specification and claims, the number of carbon atoms in a substituent is represented by C １ , C ６ , C １０ For example, an alkyl group with one carbon atom is represented by "C１ An aryl group having 6 to 10 carbon atoms is indicated by "C ６－１０ The aryl group is shown as "aryl group".

[0067] In the present specification and claims, the term "independently" means that two components are independent components, for example, a group Y １ａ and Y １ｂ In the case of １ａ and Group Y １ｂ and do not have to be the same group, but may be different groups.

[0068] Furthermore, in this specification and claims, when a numerical range is indicated using "X to Y", the numerical values ​​X and Y at both ends may be included.

[0069] According to the present disclosure, it is possible to provide a fluorene compound that can achieve both a high refractive index and high solubility, a method for producing the same, and a composition (liquid composition) containing the compound.

[0070] FIG. 1 shows the fluorene derivative of 9,9-bis[(3-benzyl-4-(2-acroyloxyethoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene obtained in Example 3. １ 2 is a H-NMR spectrum of 9,9-bis[(3-benzyl-4-(2-acroyloxyethoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene obtained in Example 3. １３ 3 shows the C-NMR spectrum of 9,9-bis[(3-benzyl-4-glycidyloxy-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene obtained in Example 5. １ 4 is a H-NMR spectrum of 9,9-bis[(3-benzyl-4-glycidyloxy-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene obtained in Example 5. １３FIG. 5 is an IR spectrum of 9,9-bis[(3-benzyl-4-hydroxy-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene obtained in Example 2. FIG. 6 is an IR spectrum of 9,9-bis[(3-benzyl-4-glycidyloxy-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene obtained in Example 5. FIG. 7 is an IR spectrum of 9,9-bis[(3-benzyl-4-(3-acryloyloxy-2-hydroxypropoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene obtained in Example 6. １ 8 is a H-NMR spectrum of 9,9-bis[(3-benzyl-4-(3-acryloyloxy-2-hydroxypropoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene obtained in Example 6. １３ 9 is a C-NMR spectrum of 9,9-bis[(3-benzyl-4-(3-acryloyloxy-2-hydroxypropoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene obtained in Example 6.

[0071] [Fluorene compound (or diol compound) represented by formula (1)] In the formula (1), １ａ and Y １ｂ Z in the formula (Y1) represents １ Examples of the arene ring (aromatic hydrocarbon ring) represented by the formula (I) include a monocyclic arene ring such as a benzene ring, a polycyclic arene ring, etc. Examples of the polycyclic arene ring include a fused polycyclic arene ring (fused polycyclic aromatic hydrocarbon ring) and a ring-assembled arene ring (ring-assembled polycyclic aromatic hydrocarbon ring).

[0072] Examples of the fused polycyclic arene ring include fused bicyclic arene rings, fused tricyclic arene rings, and other fused bicyclic to tetracyclic arene rings. Examples of the fused bicyclic arene ring include fused bicyclic C rings such as naphthalene rings and indene rings. １０－１６ Examples of the fused tricyclic arene ring include fused tricyclic C arenes such as an anthracene ring and a phenanthrene ring. １４－２０Preferred fused polycyclic arene rings include fused polycyclic C arene rings such as naphthalene rings. １０－１４ It is an arene ring.

[0073] Examples of the ring-assembled arene ring include biarene rings such as biphenyl ring, phenylnaphthalene ring, and binaphthyl ring; and terarene rings such as terphenyl ring. Preferred ring-assembled arene rings include C １２－１８ It is a biarene ring.

[0074] In this specification and claims, the term "ring assembly arene ring" refers to two or more ring systems (arene ring systems) directly linked by single bonds or double bonds, and the number of bonds directly linking the rings is one less than the number of ring systems. For example, as described above, phenylnaphthalene rings and binaphthyl rings are classified as ring assembly arene rings even though they have a fused polycyclic arene ring skeleton, and are clearly distinguished from "fused polycyclic arene rings" such as naphthalene rings (non-ring assembly arene rings).

[0075] Preferred ring Z １ As for C ６－１４ arene rings, and more preferably C rings such as benzene rings, naphthalene rings, and biphenyl rings. ６－１２ C arene rings (e.g., naphthalene rings, biphenyl rings, etc.) １０－１２ arene ring, and more preferably a benzene ring, a naphthalene ring, and the like ６－１０ arene rings, particularly benzene rings and naphthalene rings. １ is a benzene ring, which is preferable because it not only effectively improves solubility (compatibility) but also exhibits a high refractive index and heat resistance. １ is a polycyclic arene ring, for example, a C ring such as a naphthalene ring or a biphenyl ring １０－１２ Polycyclic arene rings, particularly condensed polycyclic arene rings such as naphthalene rings, are preferred because they not only effectively improve the refractive index and heat resistance but also may exhibit high solubility (compatibility).

[0076] Also, the monovalent group Y １ａ and Y １ｂ Ring Z in １may be substituted at any of the 1- to 4-positions and the 5- to 8-positions of the fluorene skeleton, but examples thereof include the 2-position, the 3-position, and / or the 7-position. Preferred substitution positions (or bonding positions) are positions that are symmetrical on the paper in formula (1), such as the 1,8-position, the 2,7-position, the 3,6-position, and the 4,5-position, and the 2,7-position is particularly preferred.

[0077] In addition, the ring Z relative to the fluorene skeleton １ The bonding position above is ring Z １ When is a naphthalene ring, it may be at either the 1-position or the 2-position of the naphthalene ring, and is preferably at the 2-position of the naphthalene ring.

[0078] R １ Examples of the substituent (non-reactive substituent or non-polymerizable substituent) represented by the formula (I) include a halogen atom, a hydrocarbon group (or a group [—R ｈ ]), 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 mono- or di-substituted amino group, and the like.

[0079] In this specification and claims, R ｈ are independent hydrocarbon groups, and two or more R ｈ The types may be the same or different from each other.

[0080] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0081] The R ｈ The hydrocarbon group represented by may be a saturated or unsaturated hydrocarbon group, an aliphatic (including alicyclic) or aromatic hydrocarbon group, and may be a chain (straight chain or branched chain) or cyclic hydrocarbon group, or a hydrocarbon group having a structure in which a chain and a cyclic structure are combined. ｈ The number of carbon atoms constituting the hydrocarbon group (or R) is not particularly limited, but may be, for example, about 20 or less, and preferably is 1 to 16, 1 to 12, 1 to 10, 1 to 8, and 1 to 6 in the following stepwise order. ｈ) includes, for example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and the like.

[0082] Examples of the alkyl group (linear or branched alkyl group) include C alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl group. １－１０ alkyl group, preferably C １－６ alkyl group, more preferably C １－４ It is an alkyl group.

[0083] Examples of the cycloalkyl group include a C cyclopentyl group, a cyclohexyl group, and the like. ５－１０ Cycloalkyl groups are exemplified.

[0084] Examples of the aryl group include a C aryl group such as a phenyl group, an alkylphenyl group, a biphenylyl group, and a naphthyl group. ６－１２ Examples of the alkylphenyl group include mono- to tri-C alkylphenyl groups such as methylphenyl group (or tolyl group) and dimethylphenyl group (or xylyl group). １－４ Examples include alkyl-phenyl groups.

[0085] Examples of the aralkyl group include C aryl groups such as benzyl and phenethyl groups. ６－１０ Aryl-C １－４ Examples of suitable alkyl groups include:

[0086] The group [-OR ｈ ] includes, for example, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, etc., and specifically, the hydrocarbon group R ｈ Examples of the alkoxy group (linear or branched alkoxy group) include C alkoxy groups such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, and t-butoxy group. １－１０ Examples of the cycloalkyloxy group include a C alkoxy group such as a cyclohexyloxy group. ５－１０ Examples of the aryloxy group include a C aryloxy group such as a phenoxy group. ６－１０Examples of the aralkyloxy group include a C aryloxy group such as a benzyloxy group. ６－１０ Aryl-C １－４ An example is an alkyloxy group.

[0087] The group [—SR ｈ ] includes, for example, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, etc., and specifically, the hydrocarbon group R ｈ Examples of the alkylthio group include a C methylthio group, an ethylthio group, a propylthio group, an n-butylthio group, a t-butylthio group, etc. １－１０ Examples of the cycloalkylthio group include a C alkylthio group such as a cyclohexylthio group. ５－１０ Examples of the arylthio group include a C thiophenoxy group (phenylthio group) and the like. ６－１０ Examples of the aralkylthio group include a C arylthio group such as a benzylthio group. ６－１０ Aryl-C １－４ Examples include alkylthio groups.

[0088] Examples of the acyl group include C groups such as an acetyl group. １－６ Examples include an alkyl-carbonyl group.

[0089] Examples of the mono- or di-substituted amino group include a dialkylamino group and a bis(alkylcarbonyl)amino group. Examples of the dialkylamino group include a di-C group such as a dimethylamino group. １－４ Examples of the bis(alkylcarbonyl)amino group include a bis(C １－４ alkyl-carbonyl)amino groups.

[0090] Representative group R １ Examples of the group R include a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, and a substituted amino group. １ The alkyl group is a linear or branched alkyl group or a linear or branched alkoxy group, and specifically, a C１－６ C such as alkyl group, methoxy group １－４ Alkoxy groups are exemplified, among which alkyl groups, particularly C such as methyl groups. １－４ Alkyl groups are preferred.

[0091] The number of substitutions m1 is 0 or an integer of 1 or more, and the number of substitutions m2 is 0 or an integer of 1 or more. １ The number of substitutions m1 can be selected, for example, from integers of about 0 to 7, preferably from integers of 0 to 6, from integers of 0 to 5, from integers of 0 to 4, from integers of 0 to 3, from integers of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0092] When the number of substitutions m1 is 2 or more, the ring Z １ Two or more groups R １ The types of groups R may be the same or different. １ The substitution position of ring Z is not particularly limited. １ The selection may be made depending on the type of

[0093] Representative monovalent groups Y represented by the formula (Y1) １ａ and Y １ｂ Examples of the alkyl group include a phenyl group, a naphthyl group such as a 1-naphthyl group or a 2-naphthyl group, and a biphenylyl group. A phenyl group or a naphthyl group is preferred, a phenyl group or a 2-naphthyl group is more preferred, and a naphthyl group such as a 2-naphthyl group is particularly preferred.

[0094] In addition, the group Y １ａ and Y １ｂ The types may be different from each other, but are preferably the same.

[0095] R ２ａ or R ２ｂ The substituent represented by the formula (non-reactive substituent or non-polymerizable substituent) is １ａ , Y １ｂ Representative examples of the alkyl group include hydrocarbon groups such as alkyl groups (excluding aryl groups), halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms, and cyano groups. Examples of the alkyl group (linear or branched chain alkyl group) include C groups such as methyl groups, ethyl groups, and t-butyl groups. １－６When the number of substitutions m2a and m2b is 1 or more, preferred R ２ａ , R ２ｂ is a C such as a methyl group １－４ It is an alkyl group.

[0096] R ２ａ and R ２ｂ The numbers of substitutions m2a and m2b are each, for example, an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0. m2a and m2b may be different from each other, but are preferably the same. When m2a and m2b are each 1 or more, R ２ａ and R ２ｂ In addition, when m2a and m2b are two or more, two or more R substituted on the same benzene ring among the two benzene rings forming the fluorene skeleton may be different from each other, but are preferably the same. ２ａ , 2 or more R ２ｂ The types of R may be the same or different. ２ａ and R ２ｂ The substitution position of the group Y １ａ , Y １ｂ It is sufficient that the substitution is made at a position other than the substitution position of the above.

[0097] In the formula (1), the monovalent group (or hydroxyl group-containing group) Y bonded to the 9,9-position of the fluorene skeleton ２ａ and Y ２ｂ A in the formula (Y2) １ The alkylene group represented by the formula (I) is a linear or branched alkylene group, for example, an ethylene group, a propylene group (1,2-propanediyl group), a trimethylene group, a 1,2-butanediyl group, a tetramethylene group, or the like. ２－６ When the repeating number n1 is 1 or more, preferably C ２－４ C alkylene group, more preferably ethylene group, propylene group, etc. ２－３ An alkylene group is preferred, with an ethylene group being particularly preferred.

[0098] Oxyalkylene group (-A １The repeat number (number of added moles) n1 of the aryloxy group (O-) may be 0 or an integer of 1 or more, and can be selected, for example, from a range of integers of about 0 to 15, preferably in the following stepwise order: 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, 0 to 1, and particularly 0. Furthermore, in order to improve polymerization reactivity and the like, the repeat number n1 may be 1 or more, and can be selected, for example, from a range of integers of about 1 to 15, preferably in the following stepwise order: 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, 1 to 2, and particularly 1. In this specification and claims, the "repeat number (number of added moles)" may be an average value (arithmetic mean value, arithmetic mean value) or an average number of added moles, and preferred embodiments are the same as those of the preferred ranges (range of integers) described above. When the repeat number n1 is equal to or less than the upper limit, the refractive index and heat resistance are easily improved.

[0099] When n1 is 2 or more, two or more oxyalkylene groups (-A １ The types of O-) may be different from each other, but are preferably the same.

[0100] The group [—O—(A １ O) ｎ１ The substitution position of [—H] on the benzene ring may be any of the 2- to 6-positions of the phenyl group bonded to the 9-position of the fluorene ring, and for example, the 2-, 4-, or 6-position of the phenyl group is preferred, with the 4-position being particularly preferred.

[0101] A monovalent group (or a hydroxyl group-containing group) Y bonded to the 9,9-position of the fluorene skeleton ２ａ and Y ２ｂ R in the formula (Y2) ３ Examples of the substituent represented by the formula (Y1) (non-reactive substituent or non-polymerizable substituent) include R １ When the number of substitutions m3 is 1 or more, preferred substituents R ３Examples of the alkyl group include a halogen atom; a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group; an alkoxy group; an acyl group; a nitro group; a cyano group; and a substituted amino group. More preferred examples include an alkyl group (a linear or branched alkyl group), a cycloalkyl group, and an alkoxy group (a linear or branched alkoxy group), and even more preferred examples include a C １－６ C such as alkyl group and cyclohexyl group ５－８ C such as cycloalkyl group, methoxy group １－４ Among these, alkyl groups are preferred, and C alkoxy groups such as methyl groups are particularly preferred. １－４ Alkyl groups are preferred.

[0102] group R ３ The number of substitutions m3 is an integer of 0 to 5, preferably an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0. When m3 is 2 or more, two or more groups R ３ The types of groups R may be the same or different. ３ The substitution position of the group R ３ In the benzene ring bonded to ２ It is often substituted at the ortho or para position.

[0103] Alkylene Group A ２ As the alkylene group A １ Specifically, it may be a linear or branched alkylene group, for example, a C alkylene group such as a methylene group, an ethylene group, a propylene group (1,2-propanediyl group), a trimethylene group, a 1,2-butanediyl group, or a tetramethylene group. １－６ Alkylene group, preferably C １－４ C alkylene group, more preferably methylene group, ethylene group, etc. １－３ An alkylene group is preferred, with a methylene group being particularly preferred.

[0104] Group [-A ２ -Ph-(R ３ ) ｍ３] (wherein Ph represents a benzene ring (phenyl group or phenylene group)) is not particularly limited in substitution position, and the group [—O—(A １ O) ｎ１ —H] and the group [—Ph-(R ４ ) ｍ４ ] (wherein Ph is the same as above) is substituted at a position other than the bonding position of the group [—O—(A １ O) ｎ１ -H] (group [-O-(A １ O) ｎ１ It is often substituted on the carbon atom adjacent to the bonding position of the —H.

[0105] A monovalent group (or a hydroxyl group-containing group) Y bonded to the 9,9-position of the fluorene skeleton ２ａ and Y ２ｂ R in the formula (Y2) ４ Examples of the substituent represented by the formula (Y1) (non-reactive substituent or non-polymerizable substituent) include R １ When the number of substitutions m4 is 1 or more, preferred substituents R ４ Examples of the alkyl group include a halogen atom; a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group; an alkoxy group; an acyl group; a nitro group; a cyano group; and a substituted amino group. More preferred examples include an alkyl group (a linear or branched alkyl group), a cycloalkyl group, and an alkoxy group (a linear or branched alkoxy group), and even more preferred examples include a C １－６ C such as alkyl group and cyclohexyl group ５－８ C such as cycloalkyl group, methoxy group １－４ Among these, alkyl groups are preferred, and C alkoxy groups such as methyl groups are particularly preferred. １－４ Alkyl groups are preferred.

[0106] group R ４ The number of substitutions m4 is an integer of 0 to 5, preferably an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0. When m4 is 2 or more, two or more groups R ４ The types of groups R may be the same or different. ４The substitution position is not particularly limited and can be selected appropriately.

[0107] group R ４ The substitution position of the benzene ring bonded to the group [—O—(A １ O) ｎ１ —H] and the group [—A ２ -Ph-(R ３ ) ｍ３ ] (wherein Ph is the same as above) is substituted at a position other than the bonding position of the group [—O—(A １ O) ｎ１ -H] (group [-O-(A １ O) ｎ１ It is often substituted on the carbon atom adjacent to the bonding position of the —H.

[0108] A monovalent group (or a hydroxyl group-containing group) Y bonded to the 9,9-position of the fluorene skeleton ２ａ and Y ２ｂ R in the formula (Y2) ５ Examples of the substituent represented by the formula (Y1) (non-reactive substituent or non-polymerizable substituent) include R １ When the number of substitutions m5 is 1 or more, preferred substituents R ５ Examples of the alkyl group include a halogen atom; a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group; an alkoxy group; an acyl group; a nitro group; a cyano group; and a substituted amino group. More preferred examples include an alkyl group (a linear or branched alkyl group), a cycloalkyl group, and an alkoxy group (a linear or branched alkoxy group), and even more preferred examples include a C １－６ C such as alkyl group and cyclohexyl group ５－８ C such as cycloalkyl group, methoxy group １－４ Among these, alkyl groups are preferred, and C alkoxy groups such as methyl groups are particularly preferred. １－４ Alkyl groups are preferred.

[0109] group R ５ The number of substitutions m5 is an integer of 0 to 2, preferably 0 or 1, and more preferably 0. When m5 is 2, the number of substitutions m5 is ... ５ The types may be the same or different from each other.

[0110] group R ５ The substitution position of is not particularly limited, and may be a group [—O—(A １ O) ｎ１ -H], group [-A ２ -Ph-(R ３ ) ｍ３ ] (wherein Ph is the same as above) and a group [-Ph-(R ４ ) ｍ４ ] (wherein Ph is the same as above) may be substituted at a position other than the bonding position.

[0111] For example, a group R ４ and the benzene ring bonded to the 9-position of the fluorene ring is substituted, and the benzene ring bonded to the 9-position of the fluorene ring is substituted with a group [-A ２ -Ph-(R ３ ) ｍ３ ] (wherein Ph is the same as above), and a group [—O—(A １ O) ｎ１ -H] is preferably substituted.

[0112] The monovalent group (or hydroxyl group-containing group) Y represented by the formula (Y2) ２ａ and Y ２ｂ Representative examples of the group include a (phenylalkyl-hydroxy-phenyl)phenyl group in which n1 is 0 and which may have a substituent, and a (phenylalkyl-hydroxy(poly)alkoxy-phenyl)phenyl group in which n1 is 1 or more and which may have a substituent. In this specification and claims, the term "(poly)alkoxy" is used to include both an alkoxy group and a polyalkoxy group.

[0113] Examples of the (phenylalkyl-hydroxy-phenyl)phenyl group (or phenylalkyl-hydroxy-biphenylyl group or (hydroxy-phenylalkyl-phenyl)phenyl group) include (phenyl C groups) such as (3-phenylmethyl-4-hydroxy-5-phenyl)phenyl group (or 5-phenylmethyl-6-hydroxy-3-biphenylyl group or 5-benzyl-6-hydroxy-3-biphenylyl group), (3-phenylethyl-4-hydroxy-5-phenyl)phenyl group, etc. １－６ alkyl-hydroxy-phenyl)phenyl group, preferably (phenyl C １－４ alkyl-hydroxy-phenyl)phenyl group.

[0114] Examples of the (phenylalkyl-hydroxy(poly)alkoxy-phenyl)phenyl group include (phenyl C) groups such as a (3-phenylmethyl-4-hydroxy(poly)alkoxy-5-phenyl)phenyl group [or a 5-phenylmethyl-6-(2-hydroxyethoxy)-3-biphenylyl group or a 5-benzyl-6-(2-hydroxyethoxy)-3-biphenylyl group], a (3-phenylethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl group, and a (3-phenylmethyl-4-(2-hydroxypropoxy)-5-phenyl)phenyl group. １－６ Alkyl-hydroxy (mono to deca) C ２－４ alkoxy-phenyl)phenyl group, preferably (phenyl C １－４ Alkyl-hydroxy (mono to deca) C ２－４ alkoxy-phenyl)phenyl group and the like.

[0115] These monovalent groups (or hydroxyl group-containing groups) Y ２ａ and Y ２ｂAmong these, n1 is 0 or an integer of 1 to 6 (especially 0 or 1, particularly 0), and an optionally substituted (phenylalkyl-hydroxy-phenyl)phenyl group or (phenylalkyl-hydroxy(poly)alkoxy-phenyl)phenyl group is preferred, and a (3-phenylmethyl-4-hydroxy-5-phenyl)phenyl group (or a (3-benzyl-4-hydroxy-5-phenyl)phenyl group) or a (3-phenylmethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl group is particularly preferred, with a (3-phenylmethyl-4-hydroxy-5-phenyl)phenyl group being more preferred.

[0116] The substituents that the (phenylalkyl-hydroxy-phenyl)phenyl group and the (phenylalkyl-hydroxy(poly)alkoxy-phenyl)phenyl group may have are groups R ３ , group R ４ and group R ５ The same applies to the substituents and preferred embodiments exemplified above.

[0117] Y ２ａ and Y ２ｂ The types of Y may be the same or different. ２ａ and Y ２ｂ If the types of Y are different from each other, ２ａ and Y ２ｂ m3, m4 and m5 in the formula (I) and group A １ , group R ３ , group R ４ , group R ５ , group A ２ The types and substitution positions of these may be the same, with only the number of repetitions n1 being different. ２ａ and Y ２ｂ The types are the same.

[0118] Representative fluorene compounds represented by the formula (1) include Y １ａ and Y １ｂ Ring Z in １ Examples of such fluorene compounds include compounds in which Y １ａ and Y １ｂ Ring Z in １is a benzene ring, a naphthalene ring, or a biphenyl ring, preferably a benzene ring or a naphthalene ring. In such a fluorene compound, m1, m2a, m2b, m3, m4, and m5 may be 0, and A １ is an ethylene group, a propylene group, etc. ２－３ may be an alkylene group, n1 may be 0 or 1 or more, A ２ is a C such as a methylene group or an ethylene group. １－３ Among such fluorene compounds, Z １ is a benzene ring or a naphthalene ring, and Z １ is a benzene ring or a naphthalene ring, m1, m2a, m2b, m3, m4 and m5 are 0, A １ is an ethylene group or a propylene group, n1 is 0 or 1, and A ２ More preferred are compounds in which is a methylene group or an ethylene group.

[0119] Said Z １ is a benzene ring, and m1, m2a, m2b, m3, m4, and m5 are 0, for example, 9,9-bis[(phenylalkyl-hydroxy-phenyl)phenyl]-diphenylfluorene (a compound corresponding to n1=0), 9,9-bis[(phenylalkyl-hydroxy(poly)alkoxy-biphenylyl]-diphenylfluorene (a compound corresponding to n1≧1), etc.

[0120] Examples of 9,9-bis[(phenylalkyl-hydroxy-phenyl)phenyl]-diphenylfluorene include 9,9-bis[(phenyl C such as 9,9-bis[(3-phenylmethyl-4-hydroxy-5-phenyl)phenyl]-2,7-diphenylfluorene [or 9,9-bis(5-phenylmethyl-6-hydroxy-3-biphenylyl-2,7-diphenylfluorene or 9,9-bis(5-benzyl-6-hydroxy-3-biphenylyl)-2,7-diphenylfluorene], 9,9-bis[(3-phenylethyl-4-hydroxy-5-phenyl)phenyl]-2,7-diphenylfluorene, 9,9-bis[(3-phenylmethyl-4-hydroxy-5-phenyl)phenyl]-3,6-diphenylfluorene, and 9,9-bis[(5-phenylethyl-6-hydroxy-3-biphenylyl)-3,6-diphenylfluorene]. １－４ alkyl-hydroxy-phenyl)phenyl]-diphenylfluorene, and the like.

[0121] Examples of 9,9-bis[(phenylalkyl-hydroxy(poly)alkoxy-phenyl)phenyl]-diphenylfluorene include 9,9-bis[(phenyl C such as 9,9-bis[(3-phenylmethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-2,7-diphenylfluorene, 9,9-bis[(3-phenylethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-2,7-diphenylfluorene, 9,9-bis[(3-phenylmethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-3,6-diphenylfluorene, and 9,9-bis[(3-phenylethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-3,6-diphenylfluorene. １－４ Alkyl-hydroxy (mono to deca) C ２－４ alkoxy-phenyl)phenyl]-diphenylfluorene, and the like.

[0122] Said Z １is a naphthalene ring, and m1, m2a, m2b, m3, m4, and m5 are 0, for example, 9,9-bis[(phenylalkyl-hydroxy-phenyl)phenyl]-dinaphthylfluorene, 9,9-bis[(phenylalkyl-hydroxy(poly)alkoxy-phenyl)phenyl]-dinaphthylfluorene, etc.

[0123] Examples of 9,9-bis[(phenylalkyl-hydroxy-phenyl)phenyl]-dinaphthylfluorene include 9,9-bis[(3-phenylmethyl-4-hydroxy-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene [or 9,9-bis(5-phenylmethyl-6-hydroxy-3-biphenylyl)-2,7-di(2-naphthyl)fluorene or 9,9-bis(5-benzyl-6-hydroxy-3-biphenylyl)-2,7-di(2-naphthyl)fluorene], 9,9-bis[(3-phenylethyl-4-hydroxy-5-phenyl)phenyl]- 9,9-bis[(phenyl C] such as 2,7-di(2-naphthyl)fluorene, 9,9-bis[(3-phenylmethyl-4-hydroxy-5-phenyl)phenyl]-2,7-di(1-naphthyl)fluorene, 9,9-bis[(3-phenylethyl-4-hydroxy-5-phenyl)-2,7-di(1-naphthyl)fluorene, 9,9-bis[(3-phenylmethyl-4-hydroxy-5-phenyl)phenyl]-3,6-di(2-naphthyl)fluorene, and 9,9-bis[(3-phenylethyl-4-hydroxy-5-phenyl)phenyl]-3,6-di(2-naphthyl)fluorene. １－４ alkyl-hydroxy-phenyl)phenyl]-dinaphthylfluorene, and the like.

[0124] Examples of 9,9-bis[phenylalkyl-hydroxy(poly)alkoxy-phenyl]-dinaphthylfluorene include 9,9-bis[(3-phenylmethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene {or 9,9-bis[5-phenylmethyl-6-(2-hydroxyethoxy)-3-biphenylyl]-2,7-di(2-naphthyl)fluorene or 9,9-bis[5-benzyl-6-(2-hydroxyethoxy)-3-biphenylyl]-2,7-di(2-naphthyl)fluorene}, 9,9-bis[(3-phenylethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-2 9,9-bis[(phenyl C] such as 9,9-bis[(3-phenylmethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-2,7-di(1-naphthyl)fluorene, 9,9-bis[(3-phenylethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-2,7-di(1-naphthyl)fluorene, 9,9-bis[(3-phenylmethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-3,6-di(2-naphthyl)fluorene, and 9,9-bis[(3-phenylethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-3,6-di(2-naphthyl)fluorene. １－４ Alkyl-hydroxy (mono to deca) C ２－４ and dinaphthylfluorene.

[0125] Of the fluorene compounds, 9,9-bis[(3-phenylmethyl-4-hydroxy-5-phenyl)phenyl]-2,7-diphenylfluorene; 9,9-bis[3-phenylmethyl-4-(2-hydroxyethoxy)-5-phenyl]phenyl-2,7-diphenylfluorene; 9,9-bis[(3-phenylmethyl-4-hydroxy-5-phenyl)phenyl]-2,7-di(2-naphthyl)phenylfluorene; and 9,9-bis[(3-phenylmethyl-4-(2-hydroxyethoxy)-5-phenyl]phenyl-2,7-di(2-naphthyl)fluorene are preferred, and 9,9-bis[(3-phenylmethyl-4-hydroxy-5-phenyl)phenyl]-2,7-diphenylfluorene; and 9,9-bis[(3-phenylmethyl-4-hydroxy-5-phenyl)phenyl]-2,7-di(2-naphthyl)phenylfluorene are more preferred.

[0126] The fluorene compound represented by the formula (1) may be crystalline, or may be non-crystalline or amorphous.

[0127] When the fluorene compound is a crystal, the melting point of the fluorene compound is about 195 to 210° C., preferably 196 to 209° C., and more preferably 197 to 208° C. Therefore, the fluorene compound can be effectively used as a monomer for melt polymerization.

[0128] The fluorene compound has high heat resistance, and the 5% weight loss temperature of the fluorene compound may be, for example, about 350 to 500°C, and preferably the following stepwise temperatures: 355 to 480°C, 360 to 460°C, 365 to 450°C, 370 to 440°C, 380 to 430°C, 390 to 420°C, and 400 to 415°C.

[0129] The fluorene compound represented by formula (1) has a specific chemical structure having an aromatic ring (benzene ring), and therefore has a high refractive index. The refractive index of the fluorene compound may be, for example, about 1.65 to 1.78 at a temperature of 25°C and a wavelength of 589 nm, and preferably ranges in the following stepwise order: 1.66 to 1.75, 1.665 to 1.74, 1.67 to 1.73, 1.675 to 1.72, 1.68 to 1.72, 1.69 to 1.72, 1.7 to 1.72, and 1.71 to 1.72.

[0130] In this specification and claims, the melting point, 5% weight loss temperature and refractive index of the fluorene compound represented by formula (1) can be measured by the method described in the examples below.

[0131] [Method for producing fluorene compound (diol compound) represented by formula (1)] (Reaction step) The fluorene compound represented by formula (1) may be prepared according to the following reaction scheme (first reaction scheme), i.e., a production method including the reaction steps described in the following (i) and (ii).

[0132] (i) a step of reacting a compound represented by the following formula (2) with a compound represented by the following formula (3a) and a compound represented by the following formula (3b); and (ii) a step of coupling a compound represented by the following formula (4) with a compound represented by the following formula (5a) and a compound represented by the following formula (5b).

[0133]

[0134] (In the formula, X １ａ and X ２ａ and X １ｂ and X ２ｂ independently represent a pair of reactive groups capable of forming a carbon-carbon bond by a coupling reaction; Y １ａ and Y １ｂ , R ２ａ and R ２ｂ , m2a and m2b, and Y ２ａ and Y ２ｂ is the same as formula (1) above, including preferred embodiments.

[0135] (Preparation of compound represented by formula (4) in first reaction scheme (reaction step (i))) The compound represented by formula (4) can be prepared by reacting the compound represented by formula (2) with the compound represented by formula (3a) and the compound represented by formula (3b) in reaction step (i), and may be prepared in accordance with the methods described in, for example, JP-A-2011-68624 and JP-A-2020-75904.

[0136] In the formula (2), X １ａ and X １ｂ Examples of the reactive group include the reactive groups described in the section on the reaction of the compound represented by formula (4) with the compound represented by formula (5a) and the compound represented by formula (5b) in the coupling reaction "(Preparation of the compound represented by formula (1) in the first reaction scheme (reaction step (ii)))" described below.

[0137] Examples of the compound represented by formula (2) include dihalo-9-fluorenones such as 2,7-dibromo-9-fluorenone. The compounds represented by formula (2) may be used alone or in combination of two or more, but are preferably used alone. A preferred compound represented by formula (2) is 2,7-dihalo-9-fluorenones such as 2,7-dibromo-9-fluorenone.

[0138] The compound represented by the formula (3a) and the compound represented by the formula (3b) are each a compound represented by the formula (3a) and a compound represented by the formula (3b) ２ａ and Y ２ｂ and a preferred embodiment is a phenylalkyl-hydroxybiphenyl (a compound corresponding to n1=0) or a phenylalkyl-hydroxy(poly)alkoxybiphenyl (a compound corresponding to n1≧1) which may have a substituent corresponding to the above Y ２ａ and Y ２ｂ The same applies to

[0139] Specific phenylalkyl-hydroxy-biphenyls include phenyl C groups such as 3-phenylmethyl-2-hydroxy-biphenyl (3-benzyl-2-hydroxy-biphenyl) and 3-phenylethyl-2-hydroxy-biphenyl.１－４ Alkyl-hydroxy-biphenyl and the like.

[0140] Specific phenylalkyl-hydroxy(poly)alkoxy-biphenyls include phenyl C such as 3-phenylmethyl-2-(2-hydroxyethoxy)-biphenyl, 3-phenylethyl-2-(2-hydroxyethoxy)-biphenyl, and 3-phenylmethyl-2-(2-hydroxypropoxy)-biphenyl. １－４ Alkyl-hydroxy (mono to deca) C ２－４ Alkoxy-biphenyl and the like.

[0141] The substituents which the phenylalkyl-hydroxy-biphenyls and phenylalkyl-hydroxy(poly)alkoxy-biphenyls may have are groups R ３ , group R ４ and group R ５ The same applies to the substituents exemplified as above, including preferred embodiments thereof, and the group R ３ , group R ４ and group R ５ The same applies to the numbers of substitutions m3, m4 and m5, including preferred embodiments.

[0142] These compounds represented by formula (3a) and (3b) may be used alone or in combination of two or more, but are preferably used alone. It is preferable that the compound represented by formula (3a) and the compound represented by formula (3b) are the same compound. Among these compounds represented by formula (3a) and formula (3b), phenylmethyl-hydroxy-biphenyl, such as 3-phenylmethyl-2-hydroxy-biphenyl, is preferred.

[0143] The ratio of the compound represented by formula (2) to the total amount of the compound represented by formula (3a) and the compound represented by formula (3b) may be, for example, the former / latter (molar ratio) = 1 / 2 to 1 / 10, particularly about 1 / 2 to 1 / 1.25, and preferably the following stepwise ratios: 1 / 2.1 to 1 / 7, 1 / 2.2 to 1 / 5, 1 / 2.5 to 1 / 4, and 1 / 2.7 to 1 / 3.3.

[0144] In the formula (1), Y２ａ and Y ２ｂ The oxyalkylene group (-A １ When the repeating number n1 of the fluorene skeleton of the compound represented by the formula (2) is 1 or more, the compound represented by the formula (2) may be provided with a group Y ２ａ and Y ２ｂ As a method for bonding, instead of the method of directly reacting the compound represented by the formula (3a) and the compound represented by the formula (3b) at the 9,9-position of the fluorene skeleton with each other, a method of reacting the compound represented by the formula (3a) and the compound represented by the formula (3b) at the 9,9-position of the fluorene skeleton with a compound in which n1 is 0 in the formulas (3a) and (3b) to obtain a precursor to which no alkylene oxide is added, and then, A is added to this precursor. １ In this method, the ratio between the compound represented by formula (2) and the total amount of the compounds represented by formulas (3a) and (3b) in which n1 is 0 is the same as the ratio between the compound represented by formula (2) and the total amount of the compound represented by formula (3a) and the compound represented by formula (3b), including preferred embodiments.

[0145] The addition reaction of alkylene oxide (alkylene carbonate or haloalkanol) may be carried out by a conventional method, for example, a method according to the method described in WO 2013 / 022065, specifically, a method in which an A alkylene oxide such as ethylene oxide is added in the presence of a base catalyst such as potassium carbonate or potassium hydroxide. １ and a method of reacting the corresponding alkylene oxide with the

[0146] The reaction of the compound represented by formula (2) with the compound represented by formula (3a) and the compound represented by formula (3b) may be carried out in the presence of an acid catalyst. Examples of the acid catalyst include inorganic acids, organic acids, and solid acids. These acid catalysts may be in the form of hydrates, etc. Examples of the inorganic acid include sulfuric acid, hydrogen chloride, and phosphoric acid. The inorganic acid may be in the form of an aqueous solution, for example, hydrochloric acid.

[0147] When sulfuric acid is used as the acid catalyst, the sulfuric acid includes, for example, dilute sulfuric acid having a concentration of about 30 to 90 mass %, concentrated sulfuric acid having a concentration of 90 mass % or more, fuming sulfuric acid, etc., and sulfur trioxide may be used as a sulfuric acid precursor as long as it can be converted into sulfuric acid in the reaction system.

[0148] Examples of the organic acid include sulfonic acids, and examples of the sulfonic acids include (halo)alkanesulfonic acids such as methanesulfonic acid and trifluoromethanesulfonic acid, and arenesulfonic acids such as p-toluenesulfonic acid.

[0149] The solid acids are roughly classified into inorganic solid acids and organic solid acids. Examples of inorganic solid acids include metal compounds such as metal oxides, composite metal oxides, metal sulfides, metal sulfates, and metal-containing polyacids; ４ ) ２ SO ４ non-metallic sulfates such as acid clay and montmorillonite; clay minerals such as Y-type, X-type, A-type, ZSM5, mordenite, and VIPI, which have acidic OH groups; ５ , AlPO ４ -5, AlPO ４ Zeolites such as -11; kaolin, etc.

[0150] Examples of the metal oxide include SiO ２ , Al ２ O ３ , TiO ２ , Fe ２ O ３ , ZrO ２ , SnO ２ , V ２ O ５ Examples of the composite metal oxide include SiO ２ -Al ２ O ３ , SiO ２ -TiO ２ , TiO ２ -ZrO ２ , SiO ２ -ZrO ２ Examples of the metal sulfides include ZnS, etc. Examples of the metal sulfates include CaSO ４ , Fe２ (SO ４ ) ３ , CuSO ４ , NiSO ４ , Al ２ (SO ４ ) ３ , MnSO ４ , BaSO ４ , CoSO ４ , ZnSO ４ Examples of the metal-containing polyacid include polyacids containing elements such as P, Mo, V, W, and Si, and specific examples thereof include phosphates such as AlPO ４ phosphates of Ti, phosphates of W such as tungsto(VI) phosphate n-hydrate, etc.

[0151] Examples of organic solid acids include cation exchange resins such as strong acid cation exchange resins, weak acid cation exchange resins, etc. The solid acid may be porous or non-porous depending on the type of solid acid.

[0152] These acid catalysts can be used alone or in combination of two or more. Preferred acid catalysts are organic acids, more preferably sulfonic acids, and particularly preferably arenesulfonic acids such as p-toluenesulfonic acid, from the viewpoint of improving purity and yield.

[0153] The proportion of the acid catalyst is, for example, 0.01 to 10 moles relative to 1 mole of the compound represented by formula (2), and from the viewpoint of allowing the reaction to proceed efficiently, it is preferably 0.05 to 5 moles, more preferably 0.1 to 2 moles, even more preferably 0.3 to 1 mole, and most preferably 0.5 to 0.8 moles. When the proportion of the acid catalyst is equal to or greater than the lower limit, the reaction tends to proceed efficiently.

[0154] The reaction may also be carried out in the presence of a thiol, such as a mercaptocarboxylic acid, an aminoalkanethiol, a thiocarboxylic acid, an alkyl mercaptan, an aralkyl mercaptan, or a salt thereof.

[0155] Examples of mercaptocarboxylic acids include 3-mercaptoalkanoic acids such as 3-mercaptopropionic acid (or β-mercaptopropionic acid), 2-mercaptoalkanoic acids, mercaptosuccinic acid, mercaptobenzoic acid, etc. Examples of 2-mercaptoalkanoic acids include 2-mercaptoalkanoic acids such as thioglycolic acid (mercaptoacetic acid or mercaptoethanoic acid), thiolactic acid (or α-mercaptopropionic acid), 2-mercaptobutyric acid (or 2-mercapto-n-butanoic acid), and 2-mercaptoisobutyric acid (or 2-mercapto-isobutanoic acid). ２－６ Alkanoic acids are included.

[0156] Examples of aminoalkanethiols include amino C alkanethiols such as 2-aminoethanethiol (or cysteamine), 2-aminopropanethiol, 3-aminopropanethiol, 2-aminobutanethiol, 3-aminobutanethiol, 4-aminobutanethiol, 6-aminohexanethiol, 8-aminooctanethiol, 11-aminoundecanethiol, and 16-aminohexadecanethiol. ２－２０ Alkanethiols and the like are included.

[0157] Examples of thiocarboxylic acids include thioacetic acid and thiooxalic acid.

[0158] Examples of alkyl mercaptans include C mercaptans such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, and dodecyl mercaptan (1-dodecanethiol). １－１６ alkyl mercaptans, etc.

[0159] Examples of aralkyl mercaptans include benzyl mercaptan.

[0160] Representative salts of these include, for example, inorganic acid salts such as hydrochlorides and sulfates, organic acid salts such as acetates, alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as calcium salts and magnesium salts, tetraalkylammonium salts such as ammonium salts and tetramethylammonium salts, and double salts thereof. Preferably, alkali metal salts such as sodium salts are used, and specific examples of such compounds include methyl mercaptan sodium and ethyl mercaptan sodium.

[0161] These thiols can be used alone or in combination of two or more. Among these thiols, mercaptoalkanoic acids such as 3-mercaptopropionic acid, thioglycolic acid, and thiolactic acid, aminoalkanethiols such as cysteamine, and alkyl mercaptans such as dodecyl mercaptan are preferred.

[0162] The proportion of the thiol may be selected from the range of, for example, about 0.01 to 50 parts by mass relative to 100 parts by mass of the compound represented by formula (2), preferably in the following stepwise manner: 0.05 to 20 parts by mass, 0.1 to 10 parts by mass, or 0.15 to 6 parts by mass. The proportion of the thiol may be selected from the range of, for example, about 0.001 to 0.5 moles relative to 1 mole of the compound represented by formula (2), preferably in the following stepwise manner: 0.003 to 0.4 moles, 0.005 to 0.3 moles, or 0.0075 to 0.2 moles. The proportion of the thiol may be selected from the range of, for example, about 0.001 to 50 parts by mass relative to 100 parts by mass of the acid catalyst, preferably in the following stepwise manner: 0.01 to 30 parts by mass, 0.05 to 15 parts by mass, or 0.1 to 10 parts by mass. When the proportion of thiols is equal to or greater than the lower limit, the reaction proceeds efficiently, and when it is equal to or less than the upper limit, the thiols can be effectively prevented from remaining as impurities such as sulfur components.

[0163] The reaction may be carried out in a solvent. Examples of the solvent include ethers, specifically, chain ethers such as diethyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether, and cyclic ethers such as tetrahydrofuran (THF) and 1,4-dioxane; ketones, specifically, chain ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and cyclic ketones such as cyclohexanone; esters, specifically, chain esters such as methyl acetate, ethyl acetate, and butyl acetate, γ-butyrolactone, γ-butyl ketone, and γ-butyl ketone; Cyclic esters (lactones) such as valerolactone and γ-caprolactone (or γ-hexanolactone); carbonates, specifically, linear carbonates such as dimethyl carbonate (or dimethyl carbonate) and diethyl carbonate (or diethyl carbonate), cyclic carbonates such as ethylene carbonate (or ethylene carbonate) and propylene carbonate (or propylene carbonate); amides, specifically, N,N-dimethylformamide (DMF), N,N-diethylformamide, N,N-dimethylacetone chain amides such as N-methyl-2-pyrrolidone (DMAc), and cyclic amides such as N-methyl-2-pyrrolidone (NMP); ureas, specifically, chain ureas such as tetramethylurea and tetraethylurea, and cyclic ureas such as 1,3-dimethyl-2-imidazolidinone (DMI or N,N'-dimethylethyleneurea) and N,N'-dimethyl-N,N'-trimethyleneurea (or N,N'-propyleneurea); nitriles, specifically, cyanide hydrocarbons such as acetonitrile, propiononitrile, and benzonitrile; nitromethane, Nitrated hydrocarbons such as nitroethane, nitropropane, nitrobenzene, etc.; phosphoramides such as hexamethylphosphoramide; sulfones, specifically, chain sulfones such as ethylmethylsulfone, cyclic sulfones such as sulfolane, etc.; sulfoxides such as dimethyl sulfoxide (DMSO); hydrocarbons, specifically, aliphatic hydrocarbons such as hexane, heptane, octane, decane, etc., alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, etc.;Halogenated hydrocarbons, specifically, haloalkanes such as methylene chloride, chloroform, carbon tetrachloride, and 1,2-dichloroethane, and halobenzenes such as chlorobenzene and dichlorobenzene;

[0164] These solvents may be used alone or in combination of two or more. Among these solvents, it is preferable to include at least one selected from ethers, carbonates, sulfones, and hydrocarbons, and it is more preferable to include at least one selected from carbonates such as ethylene carbonate (or ethylene carbonate) and aromatic hydrocarbons such as toluene, and it is particularly preferable to include at least an aromatic hydrocarbon such as toluene.

[0165] The proportion of the solvent (total proportion) may be selected from the range of, for example, about 50 to 10,000 parts by mass relative to 100 parts by mass of the compound represented by formula (2), and is preferably 75 to 2,000 parts by mass, 100 to 1,500 parts by mass, and 150 to 1,000 parts by mass in the following stepwise manner. When the proportion of the solvent is equal to or less than the upper limit, the concentration of the raw materials can be adjusted to an appropriate range, and reactivity can be improved. When the proportion of the solvent is equal to or greater than the lower limit, the viscosity of the raw materials can be adjusted to an appropriate range, and reactivity can be easily improved.

[0166] The reaction temperature can be selected from the range of about 0 to 200° C., and may be 150° C. or lower, but from the viewpoint of improving the yield and purity, it may be 130° C. or lower, preferably 125° C. or lower, more preferably 120° C. or lower, for example, 100 to 120° C., more preferably 105 to 120° C., and most preferably 110 to 120° C. The reaction time can be selected from the range of about 30 minutes to 48 hours, and is preferably 1 to 24 hours, more preferably 3 to 18 hours, and more preferably 6 to 12 hours.

[0167] The reaction may be carried out under normal pressure, elevated pressure, or reduced pressure.

[0168] The reaction may be carried out with stirring, in air, or in an inert atmosphere such as nitrogen gas or a rare gas. The reaction may also be carried out while dehydrating.

[0169] After completion of the reaction, the reaction mixture (reaction solution or reaction mixture) may be separated (or purified) by a conventional method, for example, filtration, concentration, extraction, neutralization, washing, drying, crystallization, column chromatography, or a combination of these methods.

[0170] (Preparation of Compound Represented by Formula (1) in First Reaction Scheme (Reaction Step (ii))) The fluorene compound (diol compound) represented by the formula (1) can be prepared by subjecting the compound represented by the formula (4) to a coupling reaction (or cross-coupling reaction) with the compound represented by the formula (5a) and the compound represented by the formula (5b).

[0171] Examples of the coupling reaction include conventional coupling reactions, such as palladium-catalyzed (or palladium(0)-catalyzed) coupling reactions, such as the Suzuki-Miyaura coupling reaction, the Migita-Kosugi-Stille coupling reaction, the Negishi coupling reaction, and the Hiyama coupling reaction, and nickel-catalyzed (or nickel(0)-catalyzed) coupling reactions, such as the Kumada-Tamao-Corriu coupling reaction. Of these coupling reactions, the Suzuki-Miyaura coupling reaction is preferred.

[0172] In the formula (4) (or formula (2)), X １ａ and X １ｂ each independently represents a reactive group capable of forming a carbon-carbon bond (or a direct bond) by a coupling reaction; in the formulas (5a) and (5b), X ２ａ is the reactive group X １ａ And, X ２ｂ is the reactive group X １ｂ and each represent a reactive group capable of forming a carbon-carbon bond by a coupling reaction. １ａ and X １ｂ and X ２ａ and X ２ｂ When the synthesis is carried out by Suzuki-Miyaura coupling reaction, one of the reactive groups, for example, group X １ａ and X １ｂExamples of the fluorinated alkanesulfonyloxy group include a halogen atom and a fluorinated alkanesulfonyloxy group. Examples of the halogen atom include an iodine atom, a bromine atom, and a chlorine atom. Examples of the fluorinated alkanesulfonyloxy group include a fluorinated C such as a trifluoromethanesulfonyloxy group (or a group [-OTf]). １－４ Examples of the reactive groups include an alkanesulfonyloxy group. These reactive groups may be used alone or in combination of two or more. Among these reactive groups, a halogen atom is preferred, an iodine atom or a bromine atom is more preferred, and a bromine atom is even more preferred.

[0173] One of the reactive groups X in the Suzuki-Miyaura coupling reaction １ａ and X １ｂ Another reactive group X capable of coupling with ２ａ and X ２ｂ Examples of the boronic acid group include a boronic acid group (a dihydroxyboryl group or a group [—B(OH) ２ ]), boronate ester groups, etc. Examples of the boronate ester group include dialkoxyboryl groups such as dimethoxyboryl group, diisopropoxyboryl group, and dibutoxyboryl group; and cyclic boronate ester groups such as pinacolatoboryl group (or group [-Bpin]), 1,3,2-dioxaborinan-2-yl group, and 5,5-dimethyl-1,3,2-dioxaborinan-2-yl group. These other reactive groups may be used alone or in combination of two or more. Of the other reactive groups, the group [-B(OH) ２ ] is preferred.

[0174] In addition, the group X １ａ and X １ｂ and group X ２ａ and X ２ｂ The group X may be any reactive group as long as it is a pair of reactive groups capable of coupling reaction with each other. １ａ and X １ｂ is the other reactive group such as a boronic acid group, and group X ２ａ and X ２ｂ may be one of the reactive groups such as a halogen atom, but the group X １ａ and X １ｂis one of the reactive groups such as a halogen atom, and the group X ２ａ and X ２ｂ is preferably the other reactive group such as a boronic acid group.

[0175] The compound represented by the formula (4) is a compound corresponding to a preferred embodiment of the fluorene compound represented by the formula (1), for example, 9,9-bis(phenyl C) such as 9,9-bis(5-phenylmethyl-6-hydroxy-3-biphenylyl)-2,7-dibromofluorene. １－４ 9,9-bis[phenyl C] such as 9,9-bis[5-phenylmethyl-6-(2-hydroxyethoxy)-3-biphenylyl]-2,7-dibromofluorene; １－４ Alkyl-hydroxy(poly)C ２－４ alkoxy-biphenylyl]-dihalofluorene, and the like.

[0176] The compounds represented by the formula (5a) and the compounds represented by the formula (5b) include compounds corresponding to preferred embodiments of the fluorene compounds represented by the formula (1), such as C boronic acids such as phenylboronic acid, 1-naphthylboronic acid, and 2-naphthylboronic acid. ６－１０ Examples of suitable boronic acids include arylboronic acids. The compound represented by formula (5a) and the compound represented by formula (5b) are preferably the same compound. The compound represented by formula (5a) and the compound represented by formula (5b) may be commercially available products.

[0177] The ratio of the compound represented by formula (4) to the total amount of the compound represented by formula (5a) and the compound represented by formula (5b) may be, for example, the former / latter (molar ratio) = about 1 / 2 to 1 / 10, and may be preferably 1 / 2.1 to 1 / 5, 1 / 2.2 to 1 / 4.5, or 1 / 2.3 to 1 / 4 in the following stepwise manner, and is more preferably 1 / 2.1 to 1 / 3.5, particularly preferably 1 / 2.1 to 1 / 2.3, in terms of enabling more efficient preparation.

[0178] The coupling reaction may be carried out in the presence of a catalyst. When synthesis is carried out by the Suzuki-Miyaura coupling reaction, the reaction may be carried out in the presence of a palladium catalyst, and examples of the palladium catalyst include conventional coupling catalysts such as palladium(0) catalysts and palladium(II) catalysts.

[0179] Examples of the palladium(0) catalyst include tetrakis(triphenylphosphine)palladium(0) [or Pd(PPh ３ ) ４ ], bis(tri-t-butylphosphine)palladium(0) [or Pd(P(t-Bu) ３ ) ２ ] and palladium(0)-phosphine complexes such as these.

[0180] Examples of palladium (II) catalysts include [1,2-bis(diphenylphosphino)ethane]palladium (II) dichloride [or PdCl ２ (dppe)], [1,3-bis(diphenylphosphino)propane]palladium(II) dichloride [or PdCl ２ (dppp)], [1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloride [or PdCl ２ (dppf)], bis(triphenylphosphine)palladium(II) dichloride [or PdCl ２ (PPh ３ ) ２ ], bis(tri-o-tolylphosphine)palladium(II) dichloride [or PdCl ２ (P(o-tolyl) ３ ) ２ In the case where a palladium(II) catalyst is used, the reaction is initiated by reduction to a zero-valent complex by a reducing compound in the reaction system, such as a phosphine, an amine, or an organometallic reagent.

[0181] The palladium catalyst may be, for example, tris(dibenzylideneacetone)dipalladium(0) chloroform complex [or Pd ２ (dba) ３ CHCl ３The catalyst precursor may be prepared in the reaction system by adding a catalyst precursor such as palladium(II) acetate, a phosphine such as triphenylphosphine, or a ligand such as a carbene. The ratio of the catalyst precursor to the ligand (molar ratio) may be, for example, about 1 / 4 to 1 / 10, and preferably 1 / 4 to 1 / 5.

[0182] These catalysts can be used alone or in combination of two or more. ３ ) ４ Palladium(0)-phosphine complexes such as these, catalyst precursors such as palladium(II) acetate, and palladium(II) acetate are particularly preferred from the viewpoint of excellent operability (stability in air). The proportion of the catalyst, in terms of metal, relative to 1 mole of the compound represented by formula (4) may be, for example, about 0.0001 to 0.1 moles, preferably 0.01 to 0.07 moles, and more preferably 0.04 to 0.06 moles. In terms of more efficient preparation, the proportion is particularly preferably 0.0001 to 0.001 moles, or 0.0003 to 0.0007 moles, as follows: when a catalyst precursor such as palladium(II) acetate is used, the proportion is particularly preferably 0.0003 to 0.002 moles, and most preferably 0.0005 to 0.0015 moles.

[0183] The Suzuki-Miyaura coupling reaction may be carried out in the presence of a base, such as a metal carbonate or hydrogen carbonate, a metal hydroxide, a metal fluoride, a metal phosphate, a metal organic acid salt, or a metal alkoxide.

[0184] Examples of metal carbonates or hydrogen carbonates include alkali metal carbonates or hydrogen carbonates such as sodium carbonate, potassium carbonate, cesium carbonate, and sodium hydrogen carbonate, and thallium (I) carbonate.

[0185] Examples of metal hydroxides include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and cesium hydroxide, alkaline earth metal hydroxides such as barium hydroxide, and thallium(I) hydroxide.

[0186] Examples of metal fluorides include alkali metal fluorides such as potassium fluoride and cesium fluoride.

[0187] Examples of metal phosphates include alkali metal phosphates such as tripotassium phosphate.

[0188] Examples of metal organic acid salts include alkali metal acetates such as potassium acetate.

[0189] Examples of metal alkoxides include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide.

[0190] These bases can be used alone or in combination of two or more. Preferred bases include metal carbonates such as sodium carbonate and potassium carbonate. The proportion of the base relative to 1 mole of the compound represented by formula (4) may be, for example, about 0.1 to 50 moles, preferably 0.2 to 10 moles, 0.5 to 9 moles, or 1 to 8 moles in the following stepwise manner, and more preferably 1.5 to 10 moles, 1.7 to 8 moles, or 2 to 7.5 moles in the following stepwise manner, in terms of enabling more efficient preparation.

[0191] The coupling reaction may be carried out in the presence or absence of a phase transfer catalyst. Examples of the phase transfer catalyst include tetraalkylammonium halides such as tetrabutylammonium bromide (TBAB) and trioctylmethylammonium chloride. These phase transfer catalysts may be used alone or in combination.

[0192] The coupling reaction may be carried out in the absence or presence of a solvent inert to the reaction. Examples of the solvent include water; alcohols such as methanol and ethanol; ethers such as cyclic ethers and chain ethers; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone (MIBK); esters such as ethyl acetate; nitriles such as acetonitrile and benzonitrile; amides such as N,N-dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxides such as dimethyl sulfoxide; and hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

[0193] Examples of cyclic ethers include dioxane and tetrahydrofuran. Examples of chain ethers include dialkyl ethers such as diethyl ether and diisopropyl ether, and glycol ethers. Examples of glycol ethers include (poly)alkylene glycol monoalkyl ethers such as methyl cellosolve and methyl carbitol, and (poly)alkylene glycol dialkyl ethers such as dimethoxyethane.

[0194] Examples of aliphatic hydrocarbons include hexane and dodecane. Examples of alicyclic hydrocarbons include cyclohexane. Examples of aromatic hydrocarbons include toluene and xylene.

[0195] These solvents may be used alone or in combination of two or more. Among these solvents, a mixed solvent of water and an aromatic hydrocarbon such as toluene or a ketone such as MIBK is preferred.

[0196] The coupling reaction may be carried out under an inert gas atmosphere, for example, under an atmosphere of nitrogen gas or a rare gas such as helium or argon. The reaction temperature is, for example, 50 to 200°C, preferably 60 to 100°C, more preferably 70 to 90°C, and particularly 75 to 83°C. The reaction time may be, for example, about 0.5 to 24 hours, preferably 10 to 20 hours, and is more preferably about 0.5 to 10 hours, or 0.5 to 8 hours, in terms of more efficient preparation.

[0197] After completion of the reaction, the reaction mixture may be separated and purified, if necessary, by a conventional separation and purification method, such as neutralization, washing, extraction, filtration, dehydration, concentration, decantation, drying, crystallization, reprecipitation, column chromatography, adsorption, or a combination thereof.

[0198] The fluorene compound represented by formula (1) may also be prepared by a method different from the above method, for example, according to the following reaction scheme (second reaction scheme).

[0199]

[0200] (In the formula, Y １ａ and Y １ｂ , R ２ａ and R ２ｂ , m2a and m2b, and Y ２ａ and Y ２ｂ is the same as in the formula (1) including preferred embodiments, and X １ａ and X ２ａ and X １ｂ and X ２ｂ are the same as those in the first reaction scheme, including preferred embodiments.

[0201] In the second reaction scheme, the compound represented by formula (3a) and the compound represented by formula (3b) are reacted to form a group Y ２ａ and Y ２ｂ and reacting the compound represented by formula (5a) with the compound represented by formula (5b) to introduce a group Y １ａ and Y １ｂis reversed from the first reaction scheme. Therefore, the compound represented by formula (6) in the second reaction scheme can be prepared by using the compound represented by formula (2) instead of the compound represented by formula (4) in the description of the section "(Preparation of compound represented by formula (1) in the first reaction scheme (reaction step (ii)))" (or by replacing formula (4) with formula (2)). Similarly, the compound represented by formula (1) in the second reaction scheme can be prepared by using the compound represented by formula (6) instead of the compound represented by formula (2) in the description of the section "(Preparation of compound represented by formula (4) in the first reaction scheme (reaction step (i)))" (or by replacing formula (2) with formula (6).

[0202] That is, the method for producing the fluorene compound (diol compound) represented by the formula (1) may include either (I) a step of coupling the compound represented by the formula (4) with the compound represented by the formula (5a) and the compound represented by the formula (5b); or (II) a step of reacting the compound represented by the formula (6) with the compound represented by the formula (3a) and the compound represented by the formula (3b), and the compounds represented by the formulas (4) and (6), which are reaction intermediates, may be prepared by the above-mentioned method or other conventional methods.

[0203] In the present disclosure, the fluorene compound is produced by the method described above, and therefore the fluorene compound can be prepared with high purity and in high yield.

[0204] The HPLC purity of the obtained fluorene compound represented by formula (1) can be, for example, 75% or more, preferably 80% or more, more preferably 85% or more, more preferably 90% or more, among them, 95% or more, particularly 97% or more.In addition, in this specification and claims, HPLC purity can be measured by the method described in the examples below.

[0205] The yield of the obtained fluorene compound represented by the formula (1) is, for example, 40% or more, preferably 50% or more, 55% or more, 60% or more, 70% or more, and more preferably 80% or more, in the following stepwise manner.

[0206] [(Meth)acrylate Compound Represented by Formula (7)] The (meth)acrylate compound [or (meth)acrylic resin] represented by the formula (7) is a (meth)acrylate compound corresponding to the fluorene compound (or diol compound) represented by the formula (1).

[0207] In the formula (7), Y １ａ , Y １ｂ (i.e., Z １ , R １ and m1), R ２ａ , R ２ｂ , m2a, m2b, A １ , R ３ , m3, A ２ , R ４ , m4, R ５ and m5, including preferred embodiments, are each the same as Y in the formula (1). １ａ , Y １ｂ , R ２ａ , R ２ｂ , m2a, m2b, A １ , R ３ , m3, A ２ , R ４ , m4, R ５ and m5.

[0208] In the formula (7), n1 can be selected from the range of integers of, for example, about 0 to 15, preferably in the following stepwise order: 0 to 10, 0 to 8, 0 to 6, 0 to 4, 1 to 3, 1 to 2, and particularly 1.

[0209] Representative examples of the (meth)acrylate compound represented by the formula (7) include compounds in which the hydroxyl group in the compounds exemplified as representative fluorene compounds (diol compounds) represented by the formula (1) is replaced with a (meth)acryloyloxy group, and specific examples thereof include 9,9-bis[(phenyl C) such as 9,9-bis[(3-phenylmethyl-4-(meth)acryloyloxy-5-phenyl)phenyl]-2,7-diphenylfluorene and 9,9-bis[(3-phenylmethyl-4-(meth)acryloyloxy-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene. １－４ alkyl-(meth)acryloyloxy-phenyl)phenyl]-di(C ６－１２ 9,9-bis[(phenyl C such as 9,9-bis[(3-phenylmethyl-4-(2-(meth)acryloyloxyethoxy)-5-phenyl)phenyl]-2,7-diphenylfluorene and 9,9-bis[(3-phenylmethyl-4-(2-(meth)acryloyloxyethoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene; １－４ Alkyl-(meth)acryloyloxy(poly)C ２－４ Alkoxy-phenyl)phenyl]-di(C ６－１２ aryl)fluorene and the like.

[0210] In the formula (7), R ６ may be either a hydrogen atom or a methyl group, but is preferably a hydrogen atom in terms of improving the reactivity (or curability) and refractive index.

[0211] The (meth)acrylate compound represented by formula (7) has high heat resistance. The 5% weight loss temperature of the (meth)acrylate compound may be, for example, about 350 to 500°C, and preferably the following stepwise temperatures: 355 to 480°C, 360 to 460°C, 365 to 450°C, 370 to 430°C, 380 to 420°C, 390 to 410°C, and 395 to 405°C. The glass transition temperature of the (meth)acrylate compound may be, for example, about 30 to 200°C, and preferably the following stepwise temperatures: 100 to 190°C, 120 to 180°C, and 150 to 170°C.

[0212] The (meth)acrylate compound represented by formula (7) has a specific chemical structure having an aromatic ring (benzene ring), and therefore has a high refractive index. The refractive index of the (meth)acrylate compound may be, for example, about 1.65 to 1.78 at a temperature of 25°C and a wavelength of 589 nm, and preferably ranges in the following stepwise order: 1.65 to 1.75, 1.655 to 1.72, 1.66 to 1.71, and 1.665 to 1.70.

[0213] In this specification and claims, the 5% weight loss temperature, glass transition temperature and refractive index of the (meth)acrylate compound represented by formula (7) can be measured by the method described in the examples below.

[0214] [Method for producing a (meth)acrylate compound represented by formula (7)] The (meth)acrylate compound represented by formula (7) can be prepared by reacting a fluorene compound represented by formula (1) with (meth)acrylic acid or an ester-forming derivative thereof (hereinafter referred to as "(meth)acrylic acid or a derivative thereof").

[0215] Unless otherwise specified in the present specification and claims, the term "ester-forming derivative" refers to an alkyl ester (particularly a lower alkyl ester), specifically, a C ester such as a methyl ester or an ethyl ester. １－４ It means alkyl esters, etc.; acid halides, such as acid chlorides; and acid anhydrides.

[0216] Examples of (meth)acrylic acid or a derivative thereof include (meth)acrylic acid or anhydride thereof; (meth)acrylic acid halides such as (meth)acrylic acid chloride and (meth)acrylic acid bromide; (meth)acrylic acid alkyl esters, specifically (meth)acrylic acid C such as methyl (meth)acrylate, ethyl (meth)acrylate, and t-butyl (meth)acrylate. １－４ Alkyl esters, etc. These (meth)acrylic acids or derivatives thereof are commercially available products, etc. Among the (meth)acrylic acids or derivatives thereof, (meth)acrylic acid is usually used frequently, and acrylic acid or derivatives thereof are preferred.

[0217] The proportion of (meth)acrylic acid or a derivative thereof is, for example, 1 to 10 mol, preferably 1.1 to 5 mol, more preferably 1.5 to 4 mol, even more preferably 2 to 3 mol, and more preferably 2.3 to 2.8 mol, relative to 1 mol of hydroxyl groups in the compound represented by formula (1).

[0218] When the (meth)acrylic acid or a derivative thereof is an acid halide, the reaction may be carried out in the presence of a base to trap the hydrogen halide produced by the reaction. The base can be broadly classified into, for example, inorganic bases and organic bases.

[0219] 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 hydrogen carbonates, specifically alkali metal or alkaline earth metal hydrogen carbonates such as sodium hydrogen carbonate.

[0220] 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.

[0221] The base may be used alone or in combination of two or more. Among these bases, amines, for example, trialkylamines such as triethylamine, are often used. The amount of the base used is not particularly limited, but is, for example, 1 to 2 mol, preferably 1.05 to 1.5 mol, and more preferably 1.1 to 1.2 mol per mol of the (meth)acrylic acid halide.

[0222] When the (meth)acrylic acid or its derivative is an acid (or its anhydride) or an acid alkyl ester, the reaction may be carried out using a conventional esterification catalyst. Examples of the catalyst include acid catalysts, base catalysts, and metal catalysts such as metal alkoxides, specifically titanium(IV) alkoxides such as titanium(IV) tetraisopropoxide. Among these catalysts, acid catalysts are preferably used.

[0223] The acid catalyst is not particularly limited and may include 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 alone or in combination. These acid catalysts may also be hydrates.

[0224] Examples of the inorganic acid include strong acids, specifically sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, etc.; and homo- or heteropoly acids, specifically tungstophosphoric acid, molybdophosphoric acid, tungstosilicic acid, molybdosilicic acid, etc.

[0225] Examples of the organic acid 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. Generally, arenesulfonic acids such as p-toluenesulfonic acid monohydrate are frequently used as the acid catalyst.

[0226] The proportion of the catalyst is not particularly limited, and is, for example, 0.001 to 1 mole, preferably 0.01 to 0.5 mole, per mole of the compound represented by the formula (1).

[0227] The reaction may be carried out in the presence of a polymerization inhibitor. Alternatively, the polymerization inhibitor may be added after completion of the reaction. Examples of polymerization inhibitors include benzoquinone; hydroquinones such as hydroquinone, hydroquinone monomethyl ether (MEHQ, p-methoxyphenol or methoquinone), t-butylhydroquinone, and p-benzoquinone; catechols such as p-t-butylcatechol; amines such as N,N-diethylhydroxylamine; 1,1-diphenyl-2-picrylhydrazyl; tri-p-nitrophenylmethyl; and phenothiazine. The polymerization inhibitor may be used alone or in combination of two or more. Among these polymerization inhibitors, hydroquinones such as p-methoxyphenol (or methoquinone) are often used.

[0228] The proportion of the polymerization inhibitor may be, for example, about 0.001 to 10 parts by mass relative to 100 parts by mass of (meth)acrylic acid or a derivative thereof, or may be, for example, about 0.0001 to 0.1 parts by mass relative to 100 parts by mass of the (meth)acrylate compound represented by formula (7) obtained by the reaction.

[0229] The reaction may be carried out in the presence of a solvent. Examples of the solvent 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. Among these solvents, aromatic hydrocarbons such as toluene are often used. The proportion of the solvent is not particularly limited, and may be, for example, about 10 to 1000 parts by mass, and preferably 50 to 150 parts by mass, relative to 100 parts by mass of the total amount of the fluorene compound represented by the formula (1) and (meth)acrylic acid or a derivative thereof.

[0230] The reaction temperature and reaction time can be appropriately selected depending on the types of raw materials used, and when the (meth)acrylic acid or a derivative thereof is a (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 or a derivative thereof is (meth)acrylic acid (or its anhydride) or a (meth)acrylic acid alkyl ester, 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 be carried out at reflux temperature. The reaction time is not particularly limited and may be, for example, about 1 to 24 hours.

[0231] The reaction can be carried out in air or in an inert atmosphere such as nitrogen gas or a rare gas with stirring, and may be carried out under normal pressure, elevated pressure, or reduced pressure. In addition, in order to effectively prevent unintended polymerization during the reaction, the reaction may be carried out while blowing air into the reaction solution.

[0232] After completion of the reaction, the produced (meth)acrylate compound represented by the formula (7) may be separated and purified by a conventional method, for example, a separation and purification means such as neutralization, washing, dehydration, filtration, adsorption, concentration, extraction, crystallization, recrystallization, reprecipitation, centrifugation, column chromatography, or a combination of these means.

[0233] [Epoxy Compound Represented by Formula (8)] The epoxy compound [or epoxy resin] represented by the formula (8) is an epoxy compound corresponding to the fluorene compound (or diol compound) represented by the formula (1).

[0234] In the formula (8), Y １ａ , Y １ｂ (i.e., Z １ , R １ and m1), R ２ａ , R ２ｂ , m2a, m2b, A １ , n1, R ３ , m3, A ２ , R ４ , m4, R ５ and m5, including preferred embodiments, are each the same as Y in the formula (1). １ａ , Y １ｂ , R ２ａ , R ２ｂ , m2a, m2b, A １ , n1, R ３ , m3, A ２ , R ４ , m4, R ５ and m5.

[0235] In the formula (8), n1 can be selected from the range of integers of, for example, about 0 to 15, and may be, for example, 1 or more, and is preferably 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 3, 0 to 2, 0 to 1, in the following stepwise order, and particularly 0.

[0236] In the formula (8), R ７ may be either a hydrogen atom or a methyl group, but is preferably a hydrogen atom in terms of improving the reactivity (or curability) and refractive index.

[0237] Representative examples of the epoxy compound represented by the formula (8) include compounds in which the hydroxyl group in the compounds exemplified as representative fluorene compounds (diol compounds) represented by the formula (1) is replaced with a glycidyloxy group or a 2-methylglycidyloxy group, and specific examples thereof include 9,9-bis[(phenyl C] such as 9,9-bis[(3-phenylmethyl-4-glycidyloxy-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene. １－４ alkyl-glycidyloxy-phenyl)phenyl]-di(C ６－１２ 9,9-bis[(phenyl C) such as 9,9-bis[(3-phenylmethyl-4-(2-methylglycidyloxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene １－４ alkyl-(2-methylglycidyloxy)-phenyl)phenyl]-di(C ６－１２ aryl)fluorene and the like.

[0238] The epoxy compound represented by formula (8) has high heat resistance. The 5% weight loss temperature of the epoxy compound may be, for example, about 300 to 410°C, and preferably the following stepwise temperatures: 310 to 405°C, 320 to 400°C, 330 to 395°C, 340 to 390°C, 350 to 385°C, 360 to 380°C, and 365 to 375°C. The melting point of the epoxy compound may be, for example, about 90 to 120°C, and preferably 95 to 115°C, and more preferably 100 to 110°C.

[0239] The epoxy compound represented by formula (8) has a specific chemical structure having an aromatic ring (benzene ring), and therefore has a high refractive index. The refractive index of the epoxy compound may be, for example, about 1.65 to 1.72 at a temperature of 25°C and a wavelength of 589 nm, and preferably ranges in the following stepwise order: 1.67 to 1.715, 1.68 to 1.71, 1.69 to 1.705, and 1.695 to 1.7.

[0240] In this specification and claims, the 5% weight loss temperature, melting point and refractive index of the epoxy compound represented by formula (8) can be measured by the method described in the examples below.

[0241] The epoxy equivalent of the epoxy compound represented by formula (8) may be selected from the range of, for example, 473 g / eq or more (e.g., about 480 to 1000 g / eq), preferably 500 to 600 g / eq, and more preferably 523 to 570 g / eq. In this specification and claims, the epoxy equivalent of the epoxy compound can be measured by the method described in the Examples below in accordance with JIS K 7236:2001.

[0242] The epoxy compound (or the curable composition described later) may be a mixture containing not only the epoxy compound (monomer) represented by formula (8) but also its multimer, for example, a dimer to decamer such as a dimer, trimer, tetramer, etc. The multimer may be contained alone or in combination of two or more kinds.

[0243] In this specification and claims, unless otherwise specified, the term "polymer" of an epoxy compound refers to an epoxy compound having, in its chemical structure, two or more structures (skeleton) derived from a raw material compound [the diol compound represented by formula (1)], and these two or more diol compound-derived structures are bonded (linked) via a linking group derived from an epihalohydrin component, such as a 2-hydroxypropane-1,3-diyl group, as described below. Such polymers may be unavoidably mixed in or as impurities during the production process of the compound (monomer) represented by formula (8) as described below, or, if necessary, a polymer prepared by a conventional method such as a one-stage method (the Toffee method or the direct method) or a two-stage method (the Advanced method, the melt method, or the indirect method) may be intentionally added to the monomer.

[0244] The proportion of the polymer relative to the total number of moles of the monomer and 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 %. The proportion may be, for example, 0.1 to 8 mol %, and preferably 0.2 to 3 mol %.

[0245] [Method for producing epoxy compound represented by formula (8)] The method for producing the epoxy compound represented by formula (8) is not particularly limited, and for example, the epoxy compound may be prepared by reacting the diol compound represented by formula (1) with an epihalohydrin component.

[0246] Examples of epihalohydrin components (epihalohydrins) include epihalohydrin and β-methylepihalohydrin. Examples of epihalohydrin include epichlorohydrin, epibromohydrin, and epiiodohydrin. Examples of β-methylepihalohydrin include β-methylepichlorohydrin, β-methylepibromohydrin, and β-methylepiiodohydrin. These epihalohydrin components can be used alone or in combination of two or more. Of these epihalohydrin components, epihalohydrins such as epichlorohydrin and β-methylepichlorohydrin are preferred, with epichlorohydrin being more preferred.

[0247] The proportion of the epihalohydrin component may be, for example, 2 moles or more per mole of the diol compound represented by formula (1), but is an excess amount relative to the diol compound, for example, 5 to 100 moles, preferably 10 to 60 moles, and more preferably 40 to 50 moles.

[0248] The reaction may be carried out in the presence or absence of a catalyst, as required. Examples of the catalyst include quaternary ammonium salts, specifically tetramethylammonium chloride, tetramethylammonium bromide, and other tetra-C １－２０ alkylammonium halides, benzyltrimethylammonium chloride, etc. １－４ alkylammonium halides, etc.; tri-C such as trimethylamine borane１－４ Examples of the catalyst include alkylamine borane, crown ether, phosphonium salt, pyridinium salt, etc. The catalyst may be used alone or in combination of two or more kinds.

[0249] When a catalyst is used, the proportion thereof is not particularly limited, but is, for example, 0.001 to 1 mol, preferably 0.01 to 0.2 mol, and more preferably 0.05 to 0.1 mol relative to 1 mol of the diol compound represented by formula (1).

[0250] Furthermore, the reaction may be carried out in the presence of a base to trap the hydrogen halide produced by the reaction. Examples of the base include inorganic bases such as metal hydroxides, metal carbonates, or hydrogen carbonates; 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 hydrogen carbonates include alkali metal or alkaline earth metal carbonates such as sodium carbonate and sodium hydrogen carbonate. 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. Among these bases, strong bases (strong alkalis) are preferred, and metal hydroxides such as sodium hydroxide are more preferred.

[0251] The ratio of the base is not particularly limited, but is, for example, 0.01 to 20 mol, preferably 0.05 to 10 mol, 1 to 5 mol, and 1.1 to 1.5 mol in the following stepwise manner, relative to 1 mol of the hydroxyl group of the diol compound represented by formula (1).

[0252] The reaction may be carried out in an inert solvent or without a solvent. Examples of the solvent that can be used include aprotic solvents, such as hydrocarbons, specifically aliphatic hydrocarbons such as hexane and heptane, and aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; esters such as ethyl acetate; ethers, specifically dialkyl ethers such as diethyl ether, and cyclic ethers such as tetrahydrofuran; 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. The solvents may be used alone or in combination. Among these solvents, ketones such as MEK and MIBK, amides, and sulfoxides are preferred from the viewpoint of reactivity, and amides such as DMF and sulfoxides such as dimethyl sulfoxide are more preferred.

[0253] The reaction may be carried out in air or in an inert atmosphere such as nitrogen gas or a rare gas, with stirring, or under normal pressure, elevated pressure, or reduced pressure.

[0254] The reaction temperature and reaction time may be appropriately selected depending on the types of raw materials, etc. The reaction temperature is, for example, 30 to 150°C, preferably 40 to 130°C, 50 to 100°C, and 60 to 80°C in a stepwise manner, and the reaction may be carried out under reflux (at the reflux temperature).

[0255] After completion of the reaction, the reaction mixture may be separated and purified, if necessary, by a conventional separation and purification method, such as neutralization, washing, extraction, filtration, dehydration, concentration, decantation, drying, crystallization, reprecipitation, column chromatography, adsorption, or a combination thereof.

[0256] [Epoxy(meth)acrylate compound represented by formula (9)] The epoxy(meth)acrylate compound represented by formula (9) [epoxy(meth)acrylate resin or vinyl ester resin] is an epoxy(meth)acrylate compound corresponding to the epoxy compound represented by formula (8) [or the fluorene compound (or diol compound) represented by formula (1)].

[0257] In the formula (9), Y １ａ , Y １ｂ (i.e., Z １ , R １ and m1), R ２ａ , R ２ｂ , m2a, m2b, A １ , n1, R ３ , m3, A ２ , R ４ , m4, R ５ and m5, including preferred embodiments, are Y in the formula (8) [or the formula (1)]. １ａ , Y １ｂ , R ２ａ , R ２ｂ , m2a, m2b, A １ , n1, R ３ , m3, A ２ , R ４ , m4, R ５ and m5, and R ７ is R in the formula (8), including preferred embodiments. ７ is the same as

[0258] In the formula (9), n1 can be selected from the range of integers of, for example, about 0 to 15, and may be, for example, 1 or more, and is preferably 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 3, 0 to 2, 0 to 1, in the following stepwise order, and particularly 0.

[0259] In the formula (9), R ８ may be either a hydrogen atom or a methyl group, but is preferably a hydrogen atom in terms of improving the reactivity (or curability) and refractive index.

[0260] Representative examples of the epoxy(meth)acrylate compound represented by the formula (9) include compounds in which the hydroxyl group in the compounds exemplified as representative fluorene compounds (diol compounds) represented by the formula (1) is replaced with a [3-(meth)acryloyloxy-2-hydroxy]propoxy group, and specific examples thereof include 9,9-bis[(phenyl C] such as 9,9-bis[(3-phenylmethyl-4-(3-acryloyloxy-2-hydroxypropoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene. １－４ alkyl-(3-(meth)acryloyloxy-2-hydroxypropoxy)-phenyl)phenyl]-di(C ６－１２ aryl)fluorene and the like.

[0261] The epoxy (meth)acrylate compound represented by formula (9) has high heat resistance. The 5% weight loss temperature of the epoxy (meth)acrylate compound may be, for example, about 300 to 420°C, and preferably the following stepwise temperatures: 330 to 415°C, 340 to 410°C, 350 to 405°C, 360 to 400°C, 365 to 395°C, 370 to 390°C, and 375 to 385°C. The glass transition temperature of the epoxy (meth)acrylate compound may be, for example, about 50 to 100°C, preferably 70 to 90°C, and more preferably 75 to 85°C.

[0262] The epoxy (meth)acrylate compound represented by formula (9) has a specific chemical structure having an aromatic ring (benzene ring), and therefore has a high refractive index. The refractive index of the epoxy (meth)acrylate compound may be, for example, about 1.64 to 1.69 at a temperature of 25°C and a wavelength of 589 nm, and preferably ranges in the following stepwise order: 1.65 to 1.695, 1.66 to 1.69, 1.67 to 1.685, and 1.675 to 1.68.

[0263] In this specification and claims, the 5% weight loss temperature, glass transition temperature, and refractive index of the epoxy (meth)acrylate compound represented by formula (9) can be measured by the method described in the examples below.

[0264] [Method for producing an epoxy (meth)acrylate compound represented by formula (9)] The epoxy (meth)acrylate compound represented by formula (9) can be prepared by reacting the epoxy compound represented by formula (8) with (meth)acrylic acid or a derivative thereof. Examples of (meth)acrylic acid or a derivative thereof include compounds similar to the (meth)acrylic acid or derivatives thereof exemplified in the section [Method for producing a (meth)acrylate compound represented by formula (7)] above, and salts of (meth)acrylic acid (e.g., alkali metal salts such as sodium). Of the (meth)acrylic acid or derivatives thereof, (meth)acrylic acid or a salt thereof is often used, and acrylic acid or a salt thereof is preferred.

[0265] The proportion of (meth)acrylic acid or a derivative thereof is, for example, 1 to 10 mol, preferably 1 to 2 mol, 1.05 to 1.5 mol, and 1.1 to 1.2 mol in the following stepwise manner, relative to 1 mol of the epoxy group (or glycidyl group) of the epoxy compound represented by formula (8).

[0266] The reaction may be carried out in the presence of a catalyst. The catalyst is preferably a base catalyst. The base catalyst may be an inorganic base or an organic base.

[0267] Examples of inorganic bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and alkaline earth metal hydroxides such as calcium hydroxide.

[0268] 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.

[0269] These catalysts can be used alone or in combination of two or more. Among these catalysts, quaternary ammonium salts are preferred, and tetra C such as tetramethylammonium bromide is preferred. １－２０ Alkylammonium halides are more preferred.

[0270] The proportion of the catalyst is, for example, 0.01 to 10 mol, preferably 0.1 to 5 mol, further preferably 0.3 to 4 mol, even more preferably 0.5 to 3 mol, and most preferably 0.7 to 2 mol, relative to 100 mol of the epoxy compound represented by the formula (8).

[0271] The reaction may be carried out in the presence of a polymerization inhibitor, if necessary. Examples of the polymerization inhibitor include those exemplified in the section "Method for producing a (meth)acrylate compound represented by formula (7)" above, and hydroquinones such as methoquinone are preferred.

[0272] The proportion of the polymerization inhibitor may be, for example, about 0.001 to 10 parts by mass, and preferably 0.005 to 1 part by mass, relative to 100 parts by mass of (meth)acrylic acid or a derivative thereof, and may be, for example, about 0.0001 to 0.1 part by mass relative to 100 parts by mass of the epoxy (meth)acrylate compound represented by formula (9) obtained by the reaction.

[0273] The reaction may be carried out in a solvent or without a solvent. Examples of the solvent 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). lactic acid esters such as methyl lactate, ethyl lactate, butyl lactate; lactones or cyclic esters such as γ-butyrolactone; ether esters such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), alkoxycarboxylic acid esters such as ethyl 3-ethoxypropionate; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone; and sulfoxides such as dimethyl sulfoxide.

[0274] These solvents can be used alone or in combination of two or more. Among these, ether esters are preferred, and alkylene glycol monoalkyl ether acetates such as PGMEA are particularly preferred.

[0275] The proportion of the solvent is, for example, 1 to 100 parts by mass, preferably 5 to 70 parts by mass, more preferably 10 to 50 parts by mass, and even more preferably 20 to 40 parts by mass, relative to 100 parts by mass of the epoxy compound represented by formula (8).

[0276] The reaction temperature is, for example, 50 to 150°C, preferably 70 to 140°C, further preferably 90 to 130°C, and even more preferably 100 to 120°C. The reaction time is not particularly limited and is, for example, 30 minutes to 100 hours, preferably 1 to 50 hours. The reaction is usually carried out in air or an inert gas atmosphere under normal pressure or pressure.

[0277] After completion of the reaction, the produced (meth)acrylate compound represented by the formula (7) may be separated and purified by a conventional method, for example, a separation and purification means such as neutralization, washing, dehydration, filtration, adsorption, concentration, extraction, crystallization, recrystallization, reprecipitation, centrifugation, column chromatography, or a combination of these means.

[0278] [Curable Composition and Cured Product Thereof] The present disclosure encompasses a curable composition containing at least one fluorene compound (polymerization component or curable resin) selected from the group consisting of a (meth)acrylate compound represented by formula (7) (also referred to as a first multifunctional (meth)acrylate), an epoxy compound represented by formula (8), and an epoxy (meth)acrylate compound represented by formula (9) (also referred to as a second multifunctional (meth)acrylate), and a cured product thereof. The curable composition may be a (meth)acrylate-based curable composition containing at least the (meth)acrylate compound represented by formula (7) and / or the epoxy (meth)acrylate compound represented by formula (9), or may be an epoxy-based curable composition containing at least the epoxy compound represented by formula (8).

[0279] In the case of a (meth)acrylate-based curable composition, it may contain at least a first polyfunctional (meth)acrylate. The (meth)acrylate-based curable composition may or may not contain other polymerization components, such as a third polyfunctional (meth)acrylate different from the formulas (7) and (9) above; a monofunctional polymerization component (or a reactive diluent) such as a monofunctional (meth)acrylate; etc.

[0280] The third polyfunctional (meth)acrylate is not particularly limited as long as it is a compound having a plurality (two or more) of (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, particularly preferably 2 to 3, and particularly preferably 2.

[0281] Examples of the third 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 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 third multifunctional (meth)acrylates may be used alone or in combination of two or more thereof. Commercially available products may be used as these third multifunctional (meth)acrylates.

[0282] 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.

[0283] Examples of the alicyclic epoxy (meth)acrylate include C 1,4-cyclohexanedimethanol diglycidyl ether di(meth)acrylate. ５－１０ Examples include di(meth)acrylates of epoxy compounds having an aliphatic ring.

[0284] Examples of the aromatic epoxy (meth)acrylate include di(meth)acrylates of diglycidyl ethers 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.

[0285] Examples of the alkylene glycol di(meth)acrylate include C alkylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, and the like. ２－１０ Alkylene glycol di(meth)acrylates are exemplified.

[0286] Examples of the polyalkylene glycol di(meth)acrylate include di- to hexa-C di(meth)acrylates such as diethylene glycol di(meth)acrylate. ２－１０ Alkylene glycol di(meth)acrylates are exemplified.

[0287] Examples of the di(meth)acrylate of the alicyclic diol include C di(meth)acrylate of 1,4-cyclohexanedimethanol. ５－１０Examples include di(meth)acrylates of diol compounds having an aliphatic ring.

[0288] Examples of the poly(meth)acrylate of a low molecular weight polyol compound having about 3 to 6 hydroxyl groups or an alkylene oxide (alkylene carbonate or haloalkanol) adduct thereof 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- to hexa(meth)acrylate.

[0289] The proportion of the first multifunctional (meth)acrylate represented by formula (7) relative to the total amount of the first and third multifunctional (meth)acrylates can be selected, for example, from 10% by mass or more, specifically from about 30 to 100% by mass, preferably in the following stepwise manner: 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, and more preferably 90% by mass or more. It is particularly preferable that the proportion is substantially 100% by mass, i.e., the multifunctional polymerization component is solely the first multifunctional (meth)acrylate. The proportion may be selected, for example, from about 60 to 99% by mass, specifically, 80 to 97% by mass. When the proportion of the first multifunctional (meth)acrylate is above the lower limit, the refractive index and heat resistance tend to be improved.

[0290] The proportion of the second multifunctional (meth)acrylate represented by formula (9) relative to the total amount of the second and third multifunctional (meth)acrylates can be selected, for example, from 10% by mass or more, specifically from about 30 to 100% by mass, preferably in the following stepwise manner: 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, and more preferably 90% by mass or more. It is particularly preferable that the proportion is substantially 100% by mass, i.e., the multifunctional polymerization component is solely the second multifunctional (meth)acrylate. The proportion may be selected, for example, from about 60 to 99% by mass, specifically, 80 to 97% by mass. When the proportion of the second multifunctional (meth)acrylate is above the lower limit, the refractive index and heat resistance tend to be improved.

[0291] The monofunctional polymerization component (or reactive diluent) may be a 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. Specific examples of the monofunctional vinyl monomer include monofunctional vinyl monomers and monofunctional (meth)acrylic monomers. Examples of the monofunctional vinyl monomer 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 the monofunctional (meth)acrylic monomer 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.

[0292] These monofunctional polymerization components can be used alone or in combination of two or more. Among these monofunctional polymerization components, monofunctional (meth)acrylic monomers, particularly monofunctional (meth)acrylates, are often used.

[0293] Examples of the monofunctional (meth)acrylate include aliphatic monofunctional (meth)acrylates, alicyclic monofunctional (meth)acrylates, aromatic monofunctional (meth)acrylates, and sulfur atom-containing monofunctional (meth)acrylates. These monofunctional (meth)acrylates can be used alone or in combination of two or more.

[0294] Examples of the aliphatic monofunctional (meth)acrylate include C acrylates such as methyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. １－２０ Examples include alkyl (meth)acrylates.

[0295] Examples of the alicyclic monofunctional (meth)acrylate include C cyclohexyl (meth)acrylate. ５－１０ Examples include bridged cyclic (meth)acrylates such as cycloalkyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate.

[0296] 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, C aryloxyalkyl (meth)acrylates such as 2-phenoxyethyl (meth)acrylate, 2-(2-naphthoxy)ethyl (meth)acrylate, and 2-(o-phenylphenoxy)ethyl (meth)acrylate. ６－１２ Aryloxy C ２－４ alkyl(meth)acrylates; mono(meth)acrylates of bisphenols or biphenols (or alkylene oxide adducts thereof), such as mono(meth)acrylate of an ethylene oxide adduct of bisphenol A; and (meth)acrylates having a fluorene skeleton, such as 9-(meth)acryloyloxymethylfluorene.

[0297] Examples of the monofunctional (meth)acrylate containing a sulfur atom include alkylthio(meth)acrylate, arylthio(meth)acrylate, aralkylthio(meth)acrylate, and arylthioalkyl(meth)acrylate. Examples of the alkylthio(meth)acrylate include C alkylthio(meth)acrylates such as methylthio(meth)acrylate. １－６ Examples of the arylthio(meth)acrylate include C thio(meth)acrylates such as phenylthio(meth)acrylate. ６－１０ Examples of the aralkylthio(meth)acrylate include C arylthio(meth)acrylate such as benzylthio(meth)acrylate. ６－１０ Aryl C １－６ Examples of the arylthioalkyl(meth)acrylate include C alkylthio(meth)acrylates such as phenylthioethyl(meth)acrylate. ６－１０ Arylthio C ２－４ Examples include alkyl (meth)acrylates.

[0298] When the curable composition is an epoxy-based curable composition containing at least an epoxy compound represented by the formula (8) (first epoxy compound), it may or may not contain another polymerization component (second epoxy compound) different from the formula (8).

[0299] Examples of the second epoxy compound (epoxy resin) different from the formula (8) 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, and condensed ring aromatic hydrocarbon-modified epoxy resins such as 1,6-bis(glycidyloxy)naphthalene; aromatic dicarboxylic acids (or hydrogenated products thereof); glycidyl ester-type epoxy resins such as tetraglycidyldiaminodiphenylmethane, tetraglycidylbisaminomethylcyclohexane, and triglycidylaminophenol; glycidylamine-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 resins.

[0300] The second epoxy compound may also contain a reactive diluent. The reactive diluent may be a monofunctional or polyfunctional epoxy compound having a low viscosity, for example, a viscosity at 25°C of about 200 mPa·s or less, preferably 100 mPa·s or less, and more preferably 30 mPa·s or less. Examples of monofunctional epoxy compounds include glycidyl ethers such as alkyl glycidyl ethers (e.g., 2-ethylhexyl glycidyl ether), alkenyl glycidyl ethers (e.g., allyl glycidyl ether), aryl glycidyl ethers (e.g., phenyl glycidyl ether and p-tert-butylphenyl glycidyl ether), and glycidyl ethers of alkylene oxide adducts corresponding to these compounds; and alkene oxides (e.g., octylene oxide, styrene oxide, and 4-vinylcyclohexene monoxide).

[0301] Examples of polyfunctional epoxy compounds include diglycidyl ether, polyol polyglycidyl ether, diglycidyl aniline, and cycloalkene oxide. Examples of the polyol polyglycidyl ether 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; cyclohexanedimethanol diglycidyl ether; trimethylolpropane diglycidyl ether, triglycidyl ether, and glycerin diglycidyl ether, triglycidyl ether, and cycloalkene oxide. Examples of the cycloalkene oxide include vinylcyclohexene dioxide and methylated vinylcyclohexene dioxide.

[0302] These reactive diluents may be used alone or in combination of two or more. The proportion of the reactive diluent is, for example, 1 to 1,000 parts by mass, preferably 5 to 500 parts by mass, and more preferably 10 to 200 parts by mass, relative to 100 parts by mass of the total amount of the epoxy resin components (compounds having an epoxy group) in the epoxy curing agent composition.

[0303] The second epoxy compound may be a monomer or a polymer such as a dimer or trimer. The second epoxy compound may be used alone or in combination of two or more. A preferred second epoxy compound is a bi- or bisphenol-type epoxy resin such as a bisphenol A-type epoxy resin.

[0304] The proportion of the epoxy compound represented by the formula (8) may be, for example, about 10 to 100% by mass, and is preferably 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, in the following stepwise manner, based on the total epoxy resin in the epoxy-based curable composition.

[0305] (Components Other Than Polymerizable Components) The curable composition may further contain, in addition to the polymerizable components (or monomer components), a radical polymerization initiator, a curing agent, a curing accelerator, a cationic polymerization initiator, a solvent, an additive, and the like.

[0306] The radical polymerization initiator may be a thermal polymerization initiator (thermal radical generator) or a photopolymerization initiator (photoradical generator), which may be contained in the (meth)acrylate-based curable composition.

[0307] 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 peresters) 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.

[0308] Examples of radical photopolymerization initiators include benzoins, specifically benzoin alkyl ethers such as benzoin and benzoin ethyl ether; acetophenones such as acetophenone and 2-hydroxy-2-methyl-1-phenylpropan-1-one; 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, etc. These photopolymerization initiators may be used alone or in combination of two or more.

[0309] The proportion of the 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, relative to 100 parts by mass of the total amount of the polymerization components.

[0310] The photopolymerization initiator may be combined with a photosensitizer. Typical examples of the photosensitizer include conventional photosensitizers such as tertiary amines, for example, trialkylamines; trialkanolamines such as triethanolamine; dialkylaminobenzoic acid alkyl esters, specifically, N,N-dimethylaminobenzoic acid ethyl esters such as p-(dimethylamino)benzoic acid ethyl esters, and N,N-dimethylaminobenzoic acid amyl esters such as p-(dimethylamino)benzoic acid amyl esters; bis(dialkylamino)benzophenones such as 4,4-bis(diethylamino)benzophenone; and dialkylaminobenzophenones such as 4-(dimethylamino)benzophenone. These photosensitizers may be used alone or in combination of two or more.

[0311] 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, relative to 100 parts by mass of the polymerization initiator.

[0312] Examples of the curing agent include an amine-based curing agent, a polyaminoamide-based curing agent, an acid anhydride-based curing agent, a phenolic resin-based curing agent, etc. These may be contained in the epoxy-based curable composition.

[0313] The amine curing agent may particularly be a primary amine, and examples thereof include chain aliphatic amines, specifically chain aliphatic polyamines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine; cyclic aliphatic amines, specifically monocyclic, crosslinked cyclic, or spirocyclic aliphatic polyamines such as menthenediamine, 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.

[0314] Examples of polyaminoamide-based curing agents include condensates of polyethylene polyamines such as ethylene diamine, diethylene triamine, and triethylene hexamine, dimer acid, and, if necessary, fatty acid.

[0315] Examples of acid anhydride 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, methylhimic anhydride and methylcyclohexene dicarboxylic anhydride; and aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride and benzophenone tetracarboxylic anhydride.

[0316] Examples of phenolic resin-based curing agents include novolak resins such as phenol novolak resins and cresol novolak resins, and resol-type phenolic resins.

[0317] These curing agents can be used alone or in combination of two or more. Among these curing agents, phenolic resin-based curing agents are preferred, and novolak resins such as phenolic novolak resins are more preferred.

[0318] The proportion of the curing agent is, for example, 0.1 to 500 parts by mass, preferably 1 to 300 parts by mass, and more preferably 10 to 150 parts by mass, relative to 100 parts by mass of the total amount of the epoxy resin component (compound having an epoxy group) in the curable composition. The proportion of the functional group (or active hydrogen) in the curing agent is, for example, 0.1 to 4 equivalents, preferably 0.3 to 2 equivalents and 0.5 to 1.5 equivalents in the following stepwise manner, relative to 1 equivalent of the epoxy group in the epoxy resin component.

[0319] Examples of the curing accelerator include amines such as tertiary amines, imidazoles, and derivatives thereof; alkali metal or alkaline earth metal alkoxides; phosphines, specifically triarylphosphines such as triphenylphosphine; amide compounds such as dimer acid polyamide; Lewis acid complex compounds such as boron trifluoride-ethylamine complex; sulfur compounds such as polysulfides and mercaptan compounds (thiol compounds); boron compounds such as phenyldichloroborane; and condensable organometallic compounds such as organotitanium compounds and organoaluminum compounds. With regard to 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 the imidazoles include mono- or dialkylimidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, and arylimidazoles such as 2-phenylimidazole. Examples of the derivatives include salts such as phenol salts, phenol novolac salts, carbonates, and formates. These curing accelerators may be used alone or in combination. Among these curing accelerators, phosphines are preferred, and triarylphosphines such as triphenylphosphine are more preferred. These curing accelerators may be included in the epoxy curable composition.

[0320] 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 0.1 to 5 parts by mass in the following stepwise manner, relative to 100 parts by mass of the total amount of the epoxy resin component (compound having an epoxy group) in the curable composition. 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, relative to 100 parts by mass of the total amount of the epoxy resin component and curing agent in the curable composition.

[0321] The cationic polymerization initiator may be a cationic photopolymerization initiator such as a photoacid generator. The cationic photopolymerization initiator may be contained in the epoxy curable composition. Examples of the cationic photopolymerization initiator include onium salts of Bronsted acids such as aromatic diazonium salts, aromatic sulfonium salts, and aromatic iodonium salts.

[0322] Examples of aromatic diazonium salts include benzenediazoniums such as benzenediazonium hexafluoroantimonate and benzenediazonium hexafluorophosphate.

[0323] Examples of aromatic sulfonium salts include triphenylsulfonium salts such as triphenylsulfonium hexafluorophosphate and triphenylsulfonium hexafluoroantimonate, and 4,4'-bis(diphenylsulfonio)diphenylsulfides such as 4,4'-bis(diphenylsulfonio)diphenylsulfide bishexafluorophosphate.

[0324] Examples of aromatic iodonium salts include diphenyliodoniums such as diphenyliodonium tetrakis(pentafluorophenyl)borate and diphenyliodonium hexafluorophosphate, and di(4-nonylphenyl)iodoniums such as di(4-nonylphenyl)iodonium hexafluorophosphate.

[0325] The cationic photopolymerization initiator may be used alone or in combination of two or more. The proportion of the cationic photopolymerization initiator may be about 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 the epoxy resin component (compound having an epoxy group) in the curing agent composition.

[0326] The curable composition may not contain a solvent, but since the (meth)acrylate compound represented by formula (7), the epoxy compound represented by formula (8), and the epoxy (meth)acrylate compound represented by formula (9) have unexpectedly high solubility, the curable composition may contain a solvent as needed to adjust handleability. The solvent is not particularly limited, and examples thereof 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, chain ethers such as diethyl ether, and cyclic ethers such as tetrahydrofuran and 1,4-dioxane; ketones, specifically, dialkyl ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and cyclohexanone. Examples of suitable solvents include cyclic ketones such as those listed above; esters, specifically, acetate esters such as methyl acetate, ethyl acetate, and butyl acetate; glycol ether acetates, specifically, (poly)alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and diethylene glycol monobutyl ether acetate; sulfoxides, specifically, dimethyl sulfoxide; amides, specifically, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; and nitriles, specifically, acetonitrile. These solvents can be used alone or as a mixed solvent of two or more of them.

[0327] The proportion of the solvent is not particularly limited, and the solvent may be contained so that the concentration of the solid content (components other than the solvent) is, for example, about 0.1 to 50 mass % relative to the entire curable composition.

[0328] 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 the stabilizers include heat stabilizers, antioxidants, ultraviolet absorbers, etc. These additives may be used alone or in combination of two or more.

[0329] The proportion of the additive is, for example, about 30% by mass or less, preferably 20% by mass or less, 10% by mass or less, and 5% by mass or less, stepwise, relative to the total amount of the curable composition. The proportion may be 0.001 to 15% by mass, specifically 0.01 to 3% by mass.

[0330] (Cured Product) The curable composition of the present disclosure can be easily cured 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 light or X-rays.

[0331] When heat treatment is carried out using thermal energy, the heating temperature is, for example, 50 to 200°C, preferably 60 to 150°C, and more preferably 70 to 120°C.

[0332] When light energy such as ultraviolet light is used for light irradiation, the amount of light irradiation energy can be appropriately selected depending on the application, and is, for example, 50 to 10,000 mJ / cm ２ , preferably 70 to 8000 mJ / cm ２ , more preferably 100 to 5000 mJ / cm ２ , more preferably 200 to 3000 mJ / cm ２ , most preferably 300 to 1000 mJ / cm ２ is.

[0333] The shape of the cured product is not particularly limited, and may be a cured product having a three-dimensional structure such as a lens shape or a tube shape; a cured product (or cured film) having a two-dimensional structure such as a film shape, a sheet shape or a plate shape; or a cured product having a one-dimensional structure such as a line shape, fiber shape or rod shape.

[0334] The method for producing the cured product is not particularly limited, and for example, the curable composition may be molded or poured (injected) into a predetermined mold depending on the shape of the cured product, followed by a curing treatment (heating and / or light irradiation). Furthermore, in the case of a cured product having a two-dimensional structure, the curable composition may be applied to a substrate or base, for example, a metal such as aluminum; an inorganic material or ceramic such as titanium oxide, glass, or quartz; an organic material or plastic such as a cyclic olefin resin or polycarbonate resin; or a porous body such as wood, to form a film-like coating (or thin film), followed by a curing treatment.

[0335] The cured product of the present disclosure exhibits a high refractive index because it is formed from the (meth)acrylate compound represented by formula (7), the epoxy compound represented by formula (8), and / or the epoxy (meth)acrylate compound represented by formula (9). 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, about 1.6 to 1.8, preferably in the following stepwise order: 1.63 to 1.77, 1.65 to 1.75, 1.655 to 1.74, 1.66 to 1.73, 1.665 to 1.71, 1.67 to 1.7, 1.675 to 1.695, 1.68 to 1.69, and more preferably 1.69 to 1.71 (particularly 1.695 to 1.705).

[0336] The cured product also has high heat resistance, and the glass transition temperature Tg of the cured product may be, for example, about 120 to 250°C, preferably 130 to 200°C, 140 to 190°C, 150 to 180°C, 155 to 170°C, or 160 to 165°C in the following stepwise manner, and more preferably 165 to 170°C.

[0337] The 5% weight loss temperature of the cured product may be, for example, about 300 to 450°C, and preferably the following stepwise temperatures: 330 to 440°C, 340 to 430°C, 350 to 420°C, 360 to 410°C, 370 to 400°C, 375 to 395°C, and 380 to 390°C.

[0338] The pencil hardness of the cured product (particularly the cured film) is, for example, HB or higher, preferably F or higher, and more preferably H or higher.

[0339] In this specification and claims, the refractive index, 5% weight loss temperature, glass transition temperature and pencil hardness of the cured product can be measured by the methods described in the examples below.

[0340] (Compositions containing each fluorene compound of the present disclosure) The fluorene compounds of the present disclosure, i.e., the fluorene compound (diol compound) represented by formula (1), the (meth)acrylate compound represented by formula (7), the epoxy compound represented by formula (8), and the epoxy (meth)acrylate compound represented by formula (9), despite having an aromatic ring (benzene ring) in their chemical structure, unexpectedly exhibit high solubility and excellent solvent solubility, and can easily or efficiently form a composition or mixture with a solvent. The 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. Furthermore, the composition easily dissolves the fluorene compound of the present disclosure, such as the fluorene compound represented by formula (1), even at high concentrations.

[0341] Examples of the solvent for forming a composition with the fluorene compound of the present disclosure, such as the fluorene compound represented by formula (1), include hydrocarbons, specifically aliphatic hydrocarbons such as hexane and heptane, and aromatic hydrocarbons such as benzene and toluene; alcohols such as methanol, ethanol, n-propanol, and benzyl alcohol; ethers, specifically dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran (THF) and 1,4-dioxane, and aromatic ethers such as anisole; 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). ketones, specifically, chain ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK), and cyclic ketones such as cyclohexanone; esters, 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, specifically, alkylene glycol monoalkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate (PGMEA), and alkoxycarboxylic acid esters such as ethyl 3-ethoxypropionate; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; and sulfoxides such as dimethyl sulfoxide.

[0342] These solvents can be used alone or in combination of two or more. Among these solvents, at least one selected from ketones, esters, ethers, ether esters, amides, and aromatic hydrocarbons is preferred. When the fluorene compound represented by formula (1) is included, ketones, esters, ethers, and aromatic hydrocarbons are preferred, with ketones such as acetone, MEK, and MIBK; and ethers such as tetrahydrofuran and 1,4-dioxane being particularly preferred, as the fluorene compound is readily soluble in these solvents. Furthermore, when the (meth)acrylate compound represented by formula (7) is included, ketones, ethers, ether esters, amides, and aromatic hydrocarbons are preferred, with ketones such as acetone and MEK, and amides such as DMF being more preferred. When the epoxy compound represented by formula (8) is included, ketones, ethers, ether esters, amides, and aromatic hydrocarbons are preferred, as they appear to exhibit higher solubility in any of these solvents. When the epoxy (meth)acrylate compound represented by formula (9) is contained, ketones, ethers, ether esters, amides, and aromatic hydrocarbons are preferred, and ketones such as acetone, MEK, and MIBK, ethers such as 1,4-dioxane, ether esters such as PGMEA, and amides such as DMF are more preferred.

[0343] When forming a composition (liquid composition or solution) containing a fluorene compound of the present disclosure, such as the fluorene compound represented by formula (1), and a solvent, the proportion of the fluorene compound [fluorene compound represented by formula (1), formula (7), formula (8), and / or formula (9)] is, for example, 1 to 70 mass%, preferably 2 to 60 mass%, more preferably 3 to 50 mass%, and particularly 5 to 45 mass%, based on the total amount of the fluorene compound and the solvent. Furthermore, the proportion of the fluorene compound is, for example, 1 to 70 mass%, preferably 2 to 60 mass%, more preferably 3 to 50 mass%, and particularly 5 to 45 mass%, based on the total amount of the fluorene compound and the solvent.

[0344] The composition may be a reaction solution (reaction mixture) further containing other reaction components and catalysts, for example, a reaction solution for solution polymerization of the fluorene compound represented by formula (1) as a monomer.

[0345] Thus, the fluorene compound or composition can achieve high levels of solubility, refractive index, heat resistance (or thermal decomposition resistance).Therefore, as mentioned above, the fluorene compound or composition can not only be effectively used as a reactive component such as a monomer (resin raw material), but also be easily or efficiently mixed into resin by melt-kneading or the like, and can also be effectively used as a resin modifier.

[0346] The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples. Details of evaluation methods etc. are shown below.

[0347] [Evaluation Method] (HPLC) Using an HPLC (high performance or high performance liquid chromatograph, also simply referred to as LC) apparatus "LC-2030" manufactured by Shimadzu Corporation and an "ODS-80TM" manufactured by Tosoh Corporation as a column, a sample was dissolved in acetonitrile and measured, and the HPLC purity [area %] was calculated.

[0348] ( １ H-NMR and １３ C-NMR) The sample was analyzed in a deuterated solvent (CDCl) containing tetramethylsilane as an internal standard. ３ ) and analyzed using a nuclear magnetic resonance apparatus ("AVANCE III HD" manufactured by BRUKER). １ H-NMR spectrum and １３ The C-NMR spectrum was measured. Note that the DNBBzOPPFG and DNBBzOPPFGA obtained in Examples 5 and 6 were obtained using DMSO-d ６ The measurement was carried out in the same manner except that the solution was dissolved in 100 ml of ...

[0349] (IR) Measurement was carried out by the ATR method (attenuated total reflection measurement method) using a Fourier transform infrared spectrophotometer ("FT / IR-4100" manufactured by JASCO Corporation).

[0350] (LC-MS) Using a Shimadzu Corporation "Nexera XR" as an HPLC (high performance or high performance liquid chromatograph) apparatus, an "LCMS-2020" as an MS unit, and a Phenomenex "Kinetex C-18" as a column, the sample was dissolved in a mixed solvent of acetonitrile and THF (acetonitrile / THF = 90 / 10 (mass ratio)) and measured.

[0351] (MALDI TOF-MS) Mass spectrometry (MS) was performed using the following measuring device and conditions. Device used: Shimadzu Corporation's "AXIMA Assurance" ＴＭ Ionization method: MALDI (matrix-assisted laser desorption) Detected ions: positive ions Matrix: α-cyano-4-hydroxycinnamic acid (CHCA)

[0352] (Refractive index nD) The refractive index was measured using a refractometer at a temperature of 25°C and a wavelength of 589 nm (D line). The refractive index before curing (refractive index of the (meth)acrylate compound) was measured using an "RX-7000i" refractometer manufactured by Atago Co., Ltd., and the refractive index of the cured product was measured using a "DR-M2 / 1410" refractometer manufactured by Atago Co., Ltd. Furthermore, the refractive index before curing was calculated by dissolving the sample in cyclohexanone to prepare solutions with concentrations of 10% by mass and 15% by mass, measuring the refractive index of the resulting solution and a solution with a concentration of 0% by mass (cyclohexanone only), and extrapolating the concentration to 100% by mass on a calibration curve (approximate straight line).

[0353] (5% Weight Loss Temperature Td5) Using a thermogravimetry-differential thermal analyzer (TG-DTA) (TG-DTA8122 manufactured by Rigaku Corporation), the temperature at which the mass of the sample decreased by 5% by mass was measured under conditions of a nitrogen atmosphere and a heating rate of 10°C / min.

[0354] (Melting Point) Measurement was performed using a differential scanning calorimeter (DSC) ("Discovery DSC25" manufactured by TA Instruments) under conditions of a nitrogen atmosphere, a measurement temperature of 30 to 280°C, and a temperature rise rate of 10°C / min. The peak top temperature of the endothermic peak was read from the obtained DSC chart.

[0355] (Glass Transition Temperature Tg) The glass transition temperature of the sample was measured using a differential scanning calorimeter (DSC6220 manufactured by SII Nanotechnology Inc.) at a measurement temperature of 30 to 350° C. and a temperature rise time of 10° C. / min.

[0356] (Pencil Hardness) In accordance with the pencil hardness method (JIS K-5600-5-4 (1999)), a pencil hardness tester ("HEIDON-14" manufactured by Shinto Scientific Co., Ltd.) was used to measure the hardness of a 10 μm-thick cured film formed on a polyethylene terephthalate plate under a load of 750 g.

[0357] (Solubility) Each of the solvents described below was added to 100 mg of a sample to a concentration of 10 mass%, 20 mass%, 30 mass%, or 50 mass%, and the sample was stirred for 1 hour at room temperature (25° C.), and the solubility of the sample in each solvent was confirmed. If the sample did not dissolve at room temperature (25° C.), the sample was gradually heated to 50° C. and stirred for 1 hour after reaching 50° C., or the stirring time at room temperature (25° C.) was extended to 2 hours, and the solubility was confirmed according to the following evaluation criteria.

[0358] ◎: Dissolved within 1 hour at 25°C. ○: Not dissolved within 1 hour at 25°C, but dissolved within 1 hour after heating to 50°C or dissolved within 2 hours at 25°C. ×: Not dissolved even after heating to 50°C for more than 1 hour or dissolved even after heating to 25°C for more than 2 hours.

[0359] (Epoxy Equivalent) Titration was carried out with a perchloric acid solution (acetic acid) using an automatic titrator (GT-100 manufactured by Mitsubishi Chemical Corporation) in accordance with JIS K 7236:2001.

[0360] Example 1 Synthesis of 9,9-bis[(3-benzyl-4-hydroxy-5-phenyl)phenyl]-2,7-dibromofluorene (hereinafter also referred to as DBrBBzOPPF)

[0361]

[0362] A separable flask was charged with 270.44 g (0.8 mol) of 2,7-dibromo-9-fluorenone, 458.55 g (1.76 mol, 2.2 eq) of 2-benzyl-6-phenylphenol (or 3-benzyl-2-hydroxy-biphenyl), 737.72 g of toluene, 92.84 g (0.48 mol) of p-toluenesulfonic acid monohydrate, and 9.04 g (0.04 mol) of dodecanethiol, and the mixture was stirred under reflux conditions (110°C to 120°C). The point at which the peak of 2,7-dibromo-9-fluorenone disappeared by LC (liquid chromatography) was defined as the end point. After cooling to 80°C, 566 g of N,N-dimethylformamide (DMF) and 102 g of toluene were added and dissolved uniformly. 300 g of ion-exchanged water was added to the resulting solution, which was then washed with water, and the aqueous layer was removed. After repeating this water washing procedure four times, the organic layer was concentrated under reduced pressure and crystallized from methanol to obtain 9,9-bis[(3-benzyl-4-hydroxy-5-phenyl)phenyl]-2,7-dibromofluorene (DBrBBzOPPF) with a purity of 99.9% and a yield of 50%. １ The results of H-NMR are shown below.

[0363] １ H-NMR (CDCl ３ , 300MHz): δ (ppm) 3.94 (s, 4H), 5.21 (s, 2H), 6.84 (d, 2H), 6.96 (d, 2H), 7.16-7.18 (m, 6H), 7.21-7.27 (m, 4 H), 7.28-7.30 (m, 4H), 7.31-7.37 (m, 2H), 7.39-7.41 (m, 4H), 7.45 (dd, 4H), 7.52 (d, 2H)

[0364] [Synthesis of 9,9-bis[(3-benzyl-4-hydroxy-5-phenyl)phenyl]-2,7-diphenylfluorene (hereinafter also referred to as DPBBzOPPF)]

[0365]

[0366] ​A flask equipped with a stirrer, a condenser, and a thermometer was charged with 27.6 g (0.03 mol) of DBrBBzOPPF synthesized in the section "Synthesis of 9,9-bis[(3-benzyl-4-hydroxy-5-phenyl)phenyl]-2,7-dibromofluorene (hereinafter, also referred to as DBrBBzOPPF)" in Example 1, 9.03 g (0.073 mol) of phenylboronic acid, 92.3 g of toluene, 7.8 g of sodium carbonate, and 33.6 g of ion-exchanged water, and dissolved. Then, 16.4 mg of palladium acetate and 37.3 mg of triphenylphosphine were added and stirred. The mixture was heated to reflux and stirred for 7 hours to react. After confirming the disappearance of the raw materials by HPLC, the aqueous layer was removed, and the mixture was washed twice with 22 g of ion-exchanged water. 4 g of activated carbon was added to the organic layer, stirred for 1 hour, and filtered. The resulting solution was concentrated under reduced pressure and crystallized from methanol to give 17.0 g of white crystals of DPBBzOPPF (yield 62%, HPLC purity 99.2%). The refractive index (nD) of the resulting DPBBzOPPF was 1.679, the melting point was 200°C, and the 5% weight loss temperature was 408.3°C. １ The results of H-NMR are shown below.

[0367] １ H-NMR (CDCl ３ , 300MHz): δ (ppm) 3.94 (s, 4H), 5.18 (s, 2H), 6.98 (d, 2H), 7.09-7.12 (m, 6H), 7.14-7.22 (m, 6H), 7.27- 7.28 (m, 2H), 7.29-7.44 (m, 14H), 7.52-7.56 (m, 4H), 7.58-7.60 (dd, 4H), 7.81 (d, 2H)

[0368] Example 2 Synthesis of 9,9-bis[(3-benzyl-4-hydroxy-5-phenyl)phenyl]-2,7-dibromofluorene (hereinafter also referred to as DBrBBzOPPF) DBrBBzOPPF was synthesized by the method described in Example 1.

[0369] [Synthesis of 9,9-bis[(3-benzyl-4-hydroxy-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene (hereinafter also referred to as DNBBzOPPF)]

[0370] ​

[0371] A flask equipped with a stirrer, condenser, and thermometer was charged with 29.31 g (0.035 mol) of DBrBBzOPPF synthesized by the method described in Example 1, 18.95 g (0.110 mol) of 2-naphthylboronic acid, 125.6 g of methyl isobutyl ketone (MIBK), 27.1 g of sodium carbonate, and 52.4 g of ion-exchanged water. After dissolution, 7.5 mg of palladium acetate and 23.6 mg of triphenylphosphine were added and stirred. The mixture was heated to reflux and stirred for 2 hours to allow the reaction to proceed. After confirming the disappearance of the raw materials by HPLC, the aqueous layer was removed, and the mixture was washed twice with 45 g of ion-exchanged water. 12 g of activated carbon was added to the organic layer, stirred for 1 hour, and the resulting solution was filtered. The resulting solution was concentrated under reduced pressure and crystallized from methanol to obtain 19 g of pale yellow crystals of DNBBzOPPF (yield 58%, HPLC purity 99.8%). The refractive index nD of the obtained DNBBzOPPF was 1.717, the melting point was 203°C, and the 5% weight loss temperature was 410.2°C. １ The results of H-NMR are shown below.

[0372] １ H-NMR (CDCl ３ , 300MHz): δ (ppm) 3.95 (s, 4H), 5.19 (s, 2H) 7.06-7.09 (m, 8H), 7.18 (dd, 6H), 7.30-7.38 (m, 10H) , 7.50 (q, 4H), 7.68 (d, 1H), 7.70-7.74 (m, 5H), 7.84-7.91 (m, 8H), 7.99 (d, 2H)

[0373] Comparative Example 1 9,9-bis(4-hydroxy-3,5-diphenylphenyl)fluorene (hereinafter also referred to as BDPPF) represented by the following formula was prepared by a method similar to Reference Example 1 described in JP 2017-155131 A, and its refractive index, melting point, and 5% weight loss temperature were measured. The refractive index nD of BDPPF was 1.687, the melting point was 320°C, and the 5% weight loss temperature was 400°C.

[0374]

[0375] ​Next, the fluorene compounds (final products) obtained in Examples 1 and 2 and Comparative Example 1 were dissolved in each solvent to give 10 mass %, 20 mass %, and 30 mass % solutions, and the solubility evaluation results are shown in Table 1.

[0376]

[0377] Example 1 (DPBBzOPPF) and Example 2 (DNBBzOPPF) exhibited high refractive indices. In particular, Example 2 (DNBBzOPPF) exhibited a higher refractive index than Example 1 (DPBBzOPPF) because it contained more benzene ring skeletons. The 5% weight loss temperatures of Example 1 (DPBBzOPPF) and Example 2 (DNBBzOPPF) were higher than that of Comparative Example 1 (BDPPF), and both Examples 1 and 2 exhibited excellent heat resistance.

[0378] On the other hand, since Example 1 (DPBBzOPPF) and Example 2 (DNBBzOPPF) contain many benzene ring skeletons, it was expected that their solubility would be significantly reduced. However, as is clear from the results in Table 1, while the solvents in which Comparative Example 1 (BDPPF) could be dissolved were largely limited, Example 1 (DPBBzOPPF) and Example 2 (DNBBzOPPF), which have more benzene ring skeletons than Comparative Example 1 (BDPPF), unexpectedly exhibited high solubility and were soluble in a variety of solvents. In particular, Example 1 (DPBBzOPPF) was soluble in a wide range of solvents and was soluble in various solvents even at high concentrations. Furthermore, Example 2 (DNBBzOPPF) exhibited a very high refractive index and, despite containing more benzene ring skeletons than Example 1 (DPBBzOPPF), was unexpectedly soluble in a wide range of solvents even at high concentrations.

[0379] That is, the compounds of Example 1 (DPBBzOPPF), Example 2 (DNBBzOPPF), and Comparative Example 1 (BDPPF) have many benzene ring (aromatic ring) skeletons, and all three compounds exhibit high heat resistance and high refractive index. It is expected that the inclusion of many aromatic ring skeletons will reduce solubility. However, it was a surprising result that Example 1 (DPBBzOPPF) and Example 2 (DNBBzOPPF) exhibited high solubility in various solvents, and Example 1 (DPBBzOPPF) and Example 2 (DNBBzOPPF) were able to satisfy high levels of refractive index, heat resistance, and solubility.

[0380] Example 3 Synthesis of 9,9-bis[(3-benzyl-4-(2-acroyloxyethoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene (hereinafter also referred to as DNBBzOPPEFA)

[0381] A separable flask was charged with 33.83 g (0.1 mol) of 2,7-dibromo-9-fluorenone, 57.51 g (0.22 mol, 2.2 eq) of 2-benzyl-6-phenylphenol, 87.2 g of toluene, 11.8 g (0.48 mol) of p-toluenesulfonic acid monohydrate, and 1.2 g (0.04 mol) of dodecanethiol. The mixture was stirred under reflux conditions (110-120°C), and the point at which the peak of 2,7-dibromo-9-fluorenone disappeared by LC (liquid chromatography) was used as the end point. After cooling to 80°C, 68 g of N,N-dimethylformamide (DMF) was added to dissolve the mixture uniformly. 68 g of ion-exchanged water was added to the resulting solution, which was then washed with water, and the aqueous layer was removed. This water washing procedure was repeated twice. The organic layer was subjected to azeotropic dehydration to obtain 171.73 g of a solution containing 9,9-bis[(3-benzyl-4-hydroxy-5-phenyl)phenyl]-2,7-dibromofluorene (DBrBBzOPPF).

[0382] To the resulting solution, 20.14 g (0.22 mol, 2.2 eq), 10.06 g (0.7 mol), and 59 g of DMF were added, and the mixture was stirred under reflux conditions (110-120°C) under a nitrogen atmosphere. The end point was the point at which the monosubstituted product (a compound in which only one molecule of ethylene carbonate reacts with DBrBBzOPPF) was 3% or less as determined by liquid chromatography (LC), and the mixture was cooled to 80°C. 71.1 g of a 24% by mass aqueous solution of NaOH was added, and the mixture was stirred at 80°C for 2 hours. After stirring, 67 g of DMF, 80 g of toluene, and 102 g of ion-exchanged water were added and dissolved, and the aqueous layer was removed. This procedure of adding 50 g of ion-exchanged water and removing the aqueous layer was repeated five times. The organic layer was concentrated, and methanol was added to obtain 124.7 g of crude crystals. The crude crystals were dissolved in 166 g of MIBK, and then ion exchange resin (+) K1221 and ion exchange resin (-) K1261 were added. The mixture was stirred at 85°C for 2 hours, and then poured onto activated carbon placed on celite and filtered. The solution was concentrated under reduced pressure, and 64.7 g (yield 69.7%) of 9,9-bis[(3-benzyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-2,7-dibromofluorene (DBrBBzOPPEF) was obtained by crystallization from methanol.

[0383] 28.09 g (0.03 mol) of DBrBBzOPPEF, 11.42 g (0.066 mol, 2.2 eq) of 2-naphthylboronic acid, 49.83 g of MIBK, 7.0 g (0.066 mol) of sodium carbonate, 30.4 g of ion-exchanged water, 7.0 mg (0.03 mmol, 0.001 eq) of palladium acetate, and 13.2 mg (0.05 mmol, 0.002 eq) of triphenylphosphine were added, degassed under reduced pressure, and purged with nitrogen. The mixture was then stirred under reflux conditions (90-100°C). The end point was the disappearance of the peak for the monosubstituted product (a compound in which only one molecule of 2-naphthylboronic acid reacts with DBrBBzOPPEF) in LC. The mixture was then cooled to 80°C and the lower layer was removed. 18 g of ion-exchanged water was added for washing, and the aqueous layer was removed. This procedure was repeated three times. 3.1 g of activated carbon was added to the organic layer, and the mixture was stirred at 70°C for 1 hour and then filtered. 18 g of ion-exchanged water was added to the resulting solution, and the aqueous layer was removed. This procedure was repeated twice. The solution was concentrated under reduced pressure, and 24.5 g (yield 79.8%) of 9,9-bis[(3-benzyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene (DNBBzOPPEF) was obtained by methanol crystallization.

[0384] 100.02 g (0.1 mol) of DNBBzOPPEF, 17.39 g (0.51 mol, 2.46 eq), 0.214 g (2.3 mmol, 0.02 eq), 98.21 g of toluene, and 2.8 g (0.014 mol) of p-toluenesulfonic acid monohydrate were added and stirred under reflux conditions (110-120 ° C) while discharging the water produced outside the system. The end point was determined by LC when the mono-substituted product (a compound in which only one molecule of acrylic acid has reacted with DNBBzOPPEF) reached 20% or less, and toluene was added. The mixture was washed once with 35 g of 20% by mass brine, once with 20% by mass brine and 10% by mass aqueous NaOH solution, twice with 35 g of 20% by mass brine, and twice with 35 g of ion-exchanged water. 25 g of activated carbon was added to the solution, followed by stirring at room temperature for 1 hour. The solution was filtered through Celite, and 0.012 g of methoquinone was added to the resultant solution, which was then concentrated under reduced pressure to obtain 90.1 g (yield 81.0%, HPLC purity 82.8%) of 9,9-bis[(3-benzyl-4-(2-acroyloxyethoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene (DNBBzOPPEFA) represented by the following formula.

[0385]

[0386] The obtained DNBBzOPPEFA １ H-NMR and １３ The results of C-NMR are shown below: １ The H-NMR spectrum is shown in FIG. １３ The C-NMR spectrum is shown in FIG.

[0387] １ H-NMR (CDCl ３ , 300MHz): δ (ppm) 3.44 (t, 4H), 4.03 (t, 8H), 5.73 (d, 2H), 6.02 (dd, 2H), 6.31 (d, 2H), 6.95-7.05 (m, 6H), 7 .10-7.19 (m, 8H), 7.20-7.34 (m, 6H), 7.40-7.53 (m, 8H), 7.65-7.74 (m, 6H), 7.83-7.91 (m, 8H), 7.97 (d, 2H)

[0388] １３ C-NMR (CDCl ３ ​​, 75MHz): δ (ppm) 36.2, 63.6, 65.0, 70.2, 120.8, 125.0, 125.7, 125.8, 125.9, 126.0, 126.4, 127.3, 127.7, 128.2, 128.3, 128.4, 128.5, 128.7, 129.0, 130.5, 131.1, 132.7, 133.7, 134.5, 134.6, 138.6, 138.7, 139.1, 140.8, 140.9, 141.5, 152.4, 153.0, 166.0

[0389] The refractive index nD of the obtained DNBBzOPPEFA was 1.668, the glass transition temperature Tg was 163°C, and the 5% weight loss temperature was 399.3°C.

[0390] (Preparation of Curable Composition) To 100 parts by mass (3.00 g) of DNBBzOPPEFA, 3 parts by mass of photopolymerization initiator A ("Irgacure 184" manufactured by BASF Japan Ltd.) and 2 parts by mass of photopolymerization initiator B ("Darocur TPO" manufactured by BASF Japan Ltd.) were added, and the mixture was diluted with 101 parts by mass (3.02 g) of N,N-dimethylformamide (DMF), mixed, heated on a hot plate at 80°C for 3 minutes, and then irradiated with UV (500 mJ / cm) using a high-pressure mercury lamp. ２ ) to obtain a cured film.

[0391] The resulting cured product of DNBBzOPPEFA had a refractive index of 1.685, a Tg of 167°C, a 5% weight loss temperature of 385.8°C and a pencil hardness of H.

[0392] Example 4 Synthesis of 9,9-bis[(3-benzyl-4-(2-acroyloxyethoxy)-5-phenyl)phenyl]-2,7-diphenylfluorene (hereinafter also referred to as DPBBzOPPEFA)

[0393] 41.9 g (0.045 mol) of DBrBBzOPPEF obtained in Example 3, 12.3 g (0.99 mol, 2.2 eq), MIBK 74.8 g, 10.7 g (0.99 mol) of sodium carbonate, 30.4 g of ion-exchanged water, 7.4 mg (0.032 mmol, 0.0007 eq) of palladium acetate, and 15.9 mg (0.063 mmol, 0.0007 eq) of triphenylphosphine were added, degassed under reduced pressure, and purged with nitrogen. The mixture was then stirred under reflux conditions (90-100°C). The end point was the disappearance of the peak for the monosubstituted product (a compound in which only one molecule of phenylboronic acid reacts with DBrBBzOPPF) in LC. The mixture was then cooled to 80°C and the lower layer was removed. 28 g of ion-exchanged water was added for washing, and the aqueous layer was removed. This procedure was repeated three times. 3.1 g of activated carbon was added to the organic layer, and the mixture was stirred at 70° C. for 1 hour to obtain 49.1 g of a solution containing 9,9-bis[(3-benzyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-2,7-diphenylfluorene (DPBBzOPPEF).

[0394] 49.1 g (0.045 mol) of DPBBzOPPEF solution, 10.3 g (0.14 mol, 3.15 eq), 0.101 g (0.79 mmol, 0.0175 eq), 61.6 g of toluene, and 1.45 g (0.008 mol) of p-toluenesulfonic acid monohydrate were added and stirred under reflux conditions (110-120 ° C) while discharging the water produced outside the system. The end point was determined by LC when the mono-substituted product (a compound in which only one molecule of acrylic acid reacts with DPBBzOPPEF) reached 20% or less, and toluene was added. The mixture was washed once with 16.3 g of 20% by weight saline, once with 20% by weight saline and 10% by weight aqueous NaOH solution, twice with 16.3 g of 20% by weight saline, and twice with 16 g of ion-exchanged water. To the solution, 8.9 g of activated carbon was added, followed by stirring at room temperature for 1 hour. The solution was filtered through Celite, to which 5.9 mg of methoquinone was added, and the mixture was concentrated under reduced pressure to obtain 18.0 g (yield 39%, HPLC purity 76.7%) of 9,9-bis[(3-benzyl-4-(2-acroyloxyethoxy)-5-phenyl)phenyl]-2,7-diphenylfluorene (DPBBzOPPEFA) represented by the following formula.

[0395]

[0396] The obtained DPBBzOPPEFA １ H-NMR and １３ The results of C-NMR are shown below.

[0397] １ H-NMR (CDCl ３ , 300MHz): δ (ppm) 3.34 (t, 4H), 3.89 (s, 4H), 3.95 (t, 4H), 5.64 (d, 2H), 5.94 (dd, 2H), 6.22 (d, 2H), 6.96-7.04 (m, 12H), 7.07-7.08 (m, 2H), 7.11-7.25 (m, 8H), 7.31-7.35 (m, 8H), 7.42-7.44 (m, 4H), 7.49-7.51 (m, 4H), 7.70 (d, 2H)

[0398] １３ C-NMR (CDCl ３ , 75MHz): δ (ppm) 36.2, 63.4, 64.9, 70.2, 120.7, 124.8, 126.0, 127.3, 127.3, 128.3, 128.4, 128.7, 128.8, 128.9, 129.2, 130.6, 131.1, 134.4, 134.5, 138.6, 139.0, 140.8, 141.0, 141.3, 141.5, 152.3, 153.0, 166.0

[0399] The resulting DPBBzOPPEFA had a refractive index nD of 1.6276, a glass transition temperature Tg of 160°C, and a 5% weight loss temperature of 395.8°C.

[0400] (Preparation of Curable Composition) To 100 parts by mass (5.00 g) of DPBBzOPPEFA, 3 parts by mass of photopolymerization initiator A ("Irgacure 184" manufactured by BASF Japan Ltd.) and 2 parts by mass of photopolymerization initiator B ("Darocur TPO" manufactured by BASF Japan Ltd.) were added, and the mixture was diluted with 100 parts by mass (5.00 g) of methyl ethyl ketone (MEK), mixed, heated on a hot plate at 100°C for 3 minutes, and then irradiated with UV (500 mJ / cm) using a high-pressure mercury lamp. ２ ) to obtain a cured film.

[0401] ​​The resulting cured product of DPBBzOPPEFA had a refractive index of 1.655, a Tg of 166°C, a 5% weight loss temperature of 369.4°C, and a pencil hardness of HB.

[0402] Comparative Example 2 2,7-dinaphthylfluorene-9,9-dipropyl diacrylate [or 9,9-bis(3-acryloyloxypropyl)-2,7-di(2-naphthyl)fluorene] (DNFPA) represented by the following formula was obtained by the method described in Example 1 of WO2021 / 131942.

[0403]

[0404] The refractive index nD of the obtained DNFPA (the method described in Example 1 of WO2021 / 131942) was 1.682.

[0405] (Preparation of curable composition) A cured film was obtained by the method described in Example 1 of WO2021 / 131942. The obtained cured product of DNFPA had a refractive index of 1.701, a Tg of 23°C, a 5% weight loss temperature of 382°C, and a pencil hardness of HB.

[0406] The (meth)acrylate compounds obtained in Examples 3 and 4 and Comparative Example 2 were dissolved in each solvent to a concentration of 50% by mass, and the evaluation results of the solubility are shown in Table 2.

[0407]

[0408] In Table 2, "x*" corresponds to x in the evaluation criteria, but means that the solution dissolved at 25°C within 1 hour at a concentration of about 10% by mass.

[0409] The (meth)acrylate compounds of Example 3 (DNBBzOPPEFA) and Example 4 (DPBBzOPPEFA) had excellent solvent solubility despite containing many benzene rings. Furthermore, the (meth)acrylate compounds of Examples 3 and 4 exhibited high solvent solubility even at a high concentration of 50 mass% in various solvents.

[0410] The refractive index, thermal properties, and mechanical properties of the (meth)acrylate compounds obtained in Examples 3 and 4 and Comparative Example 2 before and after curing are evaluated, and the results are shown in Table 3.

[0411]

[0412] The (meth)acrylate compounds of Example 3 (DNBBzOPPEFA) and Example 4 (DPBBzOPPEFA) had a high refractive index and excellent heat resistance.

[0413] Furthermore, when the cured products of the (meth)acrylate compound of Example 3 and the (meth)acrylate compound of Comparative Example 2 (DNFPA) were compared, the cured products of Example 3 had a high refractive index, excellent optical properties, a high glass transition temperature and a high 5% weight loss temperature, excellent thermal properties, and a high pencil hardness. In contrast, the cured products of the (meth)acrylate compound of Comparative Example 2 had a low glass transition temperature, low heat resistance, and low pencil hardness.

[0414] That is, in the examples, even if the chemical structure contains many benzene rings, it was possible to achieve both a high refractive index and high solubility in a solvent.

[0415] Example 5 Synthesis of 9,9-bis[(3-benzyl-4-glycidyloxy-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene (hereinafter also referred to as DNBBzOPPFG) 28.1 g (0.03 mol) of DNBBzOPPF, 130.1 g (1.42 mol) of epichlorohydrin, and 15.3 g of dimethyl sulfoxide (DMSO) were added, and the temperature was raised to 50° C. 2.71 g of sodium hydroxide was added, and the mixture was stirred at 70° C. The point at which the DNBBzOPPF peak disappeared in LC (liquid chromatography) was defined as the end point, and residual epichlorohydrin and DMSO were removed by concentration under reduced pressure at 85° C. 100 g of methyl isobutyl ketone (MIBK) was added and dissolved uniformly, followed by the addition of 0.8 g of a 30% by mass aqueous solution of sodium hydroxide. The mixture was stirred at 75°C for 1 hour, and the insoluble matter was filtered off using Celite. 50 g of MIBK was added to the resulting solution, and 80 g of ion-exchanged water was added for washing, after which the aqueous layer was removed. This washing procedure was repeated five times. The solution was concentrated under reduced pressure, and reprecipitation with methanol yielded 29.8 g (yield 95%) of 9,9-bis[(3-benzyl-4-glycidyloxy-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene (DNBBzOPPFG) represented by the following formula:

[0416]

[0417] The obtained DNBBzOPPFG １ H-NMR and １３ The results of C-NMR are shown below: １ The H-NMR spectrum is shown in FIG. １３ The C-NMR spectrum is shown in FIG.

[0418] １ H-NMR (DMSO-d ６ , 300MHz): δ (ppm) 2.26 (dd, 2H), 2.57 (t, 2H), 2.90 (sext, 2H), 3.16 (dd, 2H), 3.41 (dd, 2H), 3.99 (s, 4H), 6.99 (t d, 8H), 7.18 (dd, 4H), 7.24-7.40 (m, 12H), 7.49-7.58 (m, 4H), 7.82-7.88 (m, 4H), 7.95-8.06 (m, 10H), 8.25 (s, 2H)

[0419] １３ C-NMR (DMSO-d ６ , 75MHz): δ (ppm) 35.4, 43.7, 49.6, 64.5, 73.6, 121.4, 124.2, 125.1, 125.3, 125.8, 126.2, 126.5, 126.9, 127.4, 127.5, 127.8, 128.1, 128. 2,128.4,128.5,128.6,128.7,130.5,132.3,133.3,133.7,135.0,137.2,137.2,137.2,137.9,138.5,139.7,140.7,141.2,151.8,152.8

[0420] The obtained LC-MS spectrum of DNBBzOPPFG showed m / z=1088 (=1046 (DNBBzOPPFG) + 41 [acetonitrile] + 1 [e ＋ ]) was confirmed. In addition, in the IR spectrum of DNBBzOPPFG shown in FIG. 6, the peak due to O—H (3518 cm ) observed in DNBBzOPPF shown in FIG. －１ and 3,477 cm －１ ) disappeared, and the peak due to the ether bond (1254 cm －１ and 1217 cm －１ ​​) and a peak presumed to be derived from an epoxy ring (1011 cm －１ These results also supported the success of the synthesis of DNBBzOPPFG.

[0421] The refractive index nD of the obtained DNBBzOPPFG was 1.6988, the melting point was 105.04°C, the 5% weight loss temperature was 370.02°C, and the epoxy equivalent was 547.41 g / eq.

[0422] Example 6 Synthesis of 9,9-bis[(3-benzyl-4-(3-acryloyloxy-2-hydroxypropoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene (hereinafter also referred to as DNBBzOPPFGA) 19.89 g of DNBBzOPPFG, 3.02 g (2.2 eq.) of acrylic acid, 6.03 g of propylene glycol monomethyl ether acetate (PGMEA), 33.8 mg of methoquinone, and 43.1 mg of tetramethylammonium bromide were added and stirred at 110° C. for 30 hours. 15.85 g of 9,9-bis[(3-benzyl-4-(3-acryloyloxy-2-hydroxypropoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene (DNBBzOPPFGA) represented by the following formula was added to obtain a 50.0 mass % solution of PGMEA in PGMEA. PGMEA was removed from the obtained solution to obtain DNBBzOPPFGA.

[0423]

[0424] The obtained DNBBzOPPFGA １ H-NMR and １３ The results of C-NMR are shown below: １ The H-NMR spectrum is shown in FIG. １３ The C-NMR spectrum is shown in FIG.

[0425] １ H-NMR (DMSO-d ６ ​, 300MHz): δ (ppm) 3.30 (d, 4H), 3.69 (sext, 2H), 3.85-3.98 (m, 4H), 4.02 (s, 4H), 5.15 (OH, 2H), 5.86 (dd, 2H), 6.02 (dd, 2H), 6.22 (dd, 2H), 6.98 (dd, 8H), 7.18 (dd, 4H), 7.28-7.38 (m, 12H), 7.51-7.59 (m, 4H), 7.84-8.06 (m, 14H), 8.25 (s, 2H)

[0426] １３ C-NMR (DMSO-d ６ , 75MHz): δ (ppm) 30.4, 32.1, 34.4, 35.0, 38.7, 39.0, 39.2, 39.5, 39.8, 40.1, 40.4, 55 .8, 64.4, 65.3, 66.9, 73.5, 121.4, 124.2, 125.1, 125.3, 125.7, 126.2, 126.5, 126.9, 127.4, 127.6, 127.8, 128.1, 128.1, 128.2, 128.4, 128.5, 128.6, 130.4, 131.5, 132.3, 133.4, 133.8, 134.8, 137.2, 138.0, 138.5, 139.7, 140.8, 141.0, 151.8, 152.8, 165.2

[0427] The obtained LC-MS spectrum of DNBBzOPPFGA showed m / z=1191 (=1190(DNBBzOPPFGA)+1[e ＋ ]), and in the MALDI TOF-MS spectrum, a peak at m / z = 1190 corresponding to DNBBzOPPFGA was confirmed. In addition, in the IR spectrum of DNBBzOPPFGA shown in FIG. 9, a peak derived from O-H (3440 cm) was observed, which was not observed in DNBBzOPPFG shown in FIG. －１ ), a peak due to C═O (1724 cm －１ ) and a peak due to C═C (1633 cm －１ These results also supported the success of the synthesis of DNBBzOPPFGA.

[0428] ​The refractive index nD of the obtained DNBBzOPPFGA was 1.6776, the glass transition temperature Tg was 80.46°C, and the 5% weight loss temperature was 377.45°C.

[0429] (Preparation of Curable Composition) 3 parts by mass of photopolymerization initiator A ("Irgacure 184" manufactured by BASF Japan Ltd.) and 2 parts by mass of photopolymerization initiator B ("Darocur TPO" manufactured by BASF Japan Ltd.) were added to 100 parts by mass (2.00 g) of DNBBzOPPFGA, and the mixture was diluted with 101 parts by mass (2.01 g) of PGMEA, mixed, heated on a hot plate at 80°C for 3 minutes, and then irradiated with UV (500 mJ / cm) using a high-pressure mercury lamp. ２ ) to obtain a cured film.

[0430] The resulting cured product of DNBBzOPPFGA had a refractive index of 1.701, a Tg of 158.22°C, a 5% weight loss temperature of 355.24°C, and a pencil hardness of H.

[0431] The epoxy compounds (epoxy resins) and epoxy (meth)acrylate compounds obtained in Examples 5 and 6 were dissolved in various solvents to give 50% by mass, and the evaluation results of the solubility are shown in Table 4.

[0432]

[0433] Examples 5 and 6, which were epoxy compounds (epoxy resins) or epoxy (meth)acrylate compounds, not only exhibited a high refractive index and excellent heat resistance, but also, as is clear from the results in Table 4, exhibited excellent solvent solubility even at a high concentration of 50 mass % in various solvents.

[0434] As described above, all of the fluorene compounds of the present disclosure [diol compound represented by formula (1), (meth)acrylate compound represented by formula (7), epoxy compound (epoxy resin) represented by formula (8), and epoxy (meth)acrylate compound represented by formula (9)] contain many benzene ring (aromatic ring) skeletons in their chemical structures, yet are able to achieve both a high refractive index and high solubility in a solvent.

[0435] The fluorene compound represented by formula (1) of the present disclosure exhibits a high refractive index and excellent heat resistance, and therefore can be effectively used as a resin raw material, for example, a monomer component of thermoplastic resins such as polyester resins such as polyarylate resins, polycarbonate resins, polyether resins, polyether ketone resins, polyether ether ketone resins such as polyether ketone resins, and raw materials for curable resins such as (meth)acrylic resins, vinyl ester resins (or epoxy (meth)acrylate resins), vinyl ether resins, and epoxy resins. In particular, the fluorene compound represented by formula (1) has a high 5% mass loss temperature, exhibits high heat resistance, and also has excellent solubility, and therefore may be used as a monomer for melt polymerization or solution polymerization.

[0436] In addition, the fluorene compound represented by formula (1) can be effectively used as an additive (or resin additive) such as a refractive index improver, a heat resistance improver, or a curing agent [for example, a curing agent for an epoxy resin such as an epoxy compound represented by formula (8)]. The fluorene compound represented by formula (1) also has excellent solubility (compatibility), so a homogeneous composition may be easily or efficiently prepared by melt-kneading or the like.

[0437] A resin made from the fluorene compound represented by formula (1) of the present disclosure or a composition containing fluorene as an additive can be suitably used for optical components (optical materials or transparent materials), membranes for fuel cells, etc. Examples of the optical components include optical lenses such as reflow lenses, pickup lenses, and microlenses, optical films such as polarizing films, anti-reflection films, films for touch panels, films for flexible substrates, and films for displays, OCRs or OCAs (optical adhesives or pressure-sensitive adhesives), optical fibers, optical waveguides, and holograms.

Claims

1. The following formula (1) [In the formula, Y １ａ and Y １ｂ are independently represented by the following formula (Y1): (In the formula, Z １ represents an arene ring, R １ represents a substituent, and m1 represents an integer of 0 or 1 or more; ２ａ and R ２ｂ each independently represents a substituent; m2a and m2b each independently represents an integer of 0 to 3; Y ２ａ and Y ２ｂ are independently represented by the following formula (Y2): (In the formula, A １ represents an alkylene group, n1 represents 0 or an integer of 1 or more, R ３ represents a substituent, m3 represents an integer of 0 to 5, ２ represents an alkylene group; R ４ represents a substituent, m4 represents an integer of 0 to 5, R ５ represents a substituent, and m5 represents an integer of 0 to 2), 2. In the formula (1), Z １ C ６－１２ m1 represents an integer of 0 to 2; m2a and m2b each independently represents an integer of 0 to 2; m3, m4, and m5 each independently represent an integer of 0 to 2; R １ ~R ５ each independently represents a hydrocarbon group; １ C ２－６ represents an alkylene group, n1 represents 0 or an integer of 1 to 6, ２ C １－４ The fluorene compound of claim 1, which represents an alkylene group.

3. In the formula (1), Y １ａ and Y １ｂ Z in formula (Y1) represents １ 3. The fluorene compound according to claim 1 or 2, wherein represents a benzene ring or a naphthalene ring.

4. The fluorene compound according to claim 1 or 2, which is crystalline and has a melting point of 195 to 210°C.

5. The fluorene compound according to claim 1 or 2, which is at least one member selected from the group consisting of monomers for melt polymerization or solution polymerization and resin additives for modifying resins.

6. A method for producing the fluorene compound according to claim 1 or 2, comprising the following reaction steps (i) and (ii): (i) a step of reacting a compound represented by the following formula (2) with a compound represented by the following formula (3a) and a compound represented by the following formula (3b), and (ii) a step of coupling reacting a compound represented by the following formula (4) with a compound represented by the following formula (5a) and a compound represented by the following formula (5b). [In the formula, X １ａ and X ２ａ And X １ｂ and X ２ｂ each independently represents a pair of reactive groups capable of forming a carbon-carbon bond by a coupling reaction; Y １ａ and Y １ｂ , R ２ａ and R ２ｂ , m2a and m2b, and Y ２ａ and Y ２ｂ is the same as formula (1) above.

7. A resin made from the fluorene compound according to claim 1 or 2.

8. An optical member comprising the resin according to claim 7.

9. The following formula (7) [In the formula, Y １ａ and Y １ｂ are independently represented by the following formula (Y1): (In the formula, Z １ represents an arene ring, R １ represents a substituent, and m1 represents an integer of 0 or 1 or more; ２ａ and R ２ｂ each independently represents a substituent; m2a and m2b each independently represents an integer of 0 to 3; Y ３ａ and Y ３ｂ are independently represented by the following formula (Y3): (In the formula, A １ represents an alkylene group, n1 represents 0 or an integer of 1 or more, R ３ represents a substituent, m3 represents an integer of 0 to 5, ２ represents an alkylene group; R ４ represents a substituent, m4 represents an integer of 0 to 5, R ５ represents a substituent, m5 represents an integer of 0 to 2, R ６ represents a hydrogen atom or a methyl group), and 10. In the formula (7), Z １ C ６－１２ m1 represents an integer of 0 to 2; m2a and m2b each independently represents an integer of 0 to 2; m3, m4, and m5 each independently represent an integer of 0 to 2; R １ ~R ５ each independently represents a hydrocarbon group; １ C ２－６ represents an alkylene group, n1 represents 0 or an integer of 1 to 6, ２ C １－４ The (meth)acrylate compound according to claim 9, which represents an alkylene group.

11. A method for producing the (meth)acrylate compound according to claim 9 or 10, comprising a step of reacting a fluorene compound represented by formula (1) according to claim 1 with (meth)acrylic acid or an ester-forming derivative thereof.

12. The following formula (8) [In the formula, Y １ａ and Y １ｂ are independently represented by the following formula (Y1): (In the formula, Z １ represents an arene ring, R １ represents a substituent, and m1 represents an integer of 0 or 1 or more; ２ａ and R ２ｂ each independently represents a substituent; m2a and m2b each independently represents an integer of 0 to 3; Y ４ａ and Y ４ｂ are independently represented by the following formula (Y4): (In the formula, A １ represents an alkylene group, n1 represents 0 or an integer of 1 or more, R ３ represents a substituent, m3 represents an integer of 0 to 5, ２ represents an alkylene group; R ４ represents a substituent, m4 represents an integer of 0 to 5, R ５ represents a substituent, m5 represents an integer of 0 to 2, R ７ represents a hydrogen atom or a methyl group), and 13. In the formula (8), Z １ C ６－１２ m1 represents an integer of 0 to 2; m2a and m2b each independently represents an integer of 0 to 2; m3, m4, and m5 each independently represent an integer of 0 to 2; R １ ~R ５ each independently represents a hydrocarbon group; １ C ２－６ represents an alkylene group, n1 represents 0 or an integer of 1 to 6, ２ C １－４ Epoxy compound according to claim 12, which exhibits an alkylene group.

14. A method for producing the epoxy compound according to claim 12 or 13, comprising a step of reacting the fluorene compound represented by formula (1) according to claim 1 with an epihalohydrin component.

15. The following formula (9) [In the formula, Y １ａ and Y １ｂ are independently represented by the following formula (Y1): (In the formula, Z １ represents an arene ring, R １ represents a substituent, and m1 represents an integer of 0 or 1 or more; ２ａ and R ２ｂ each independently represents a substituent; m2a and m2b each independently represents an integer of 0 to 3; Y ５ａ and Y ５ｂ are independently represented by the following formula (Y5): (In the formula, A １ represents an alkylene group, n1 represents 0 or an integer of 1 or more, R ３ represents a substituent, m3 represents an integer of 0 to 5, ２ represents an alkylene group; R ４ represents a substituent, m4 represents an integer of 0 to 5, R ５ represents a substituent, m5 represents an integer of 0 to 2, R ７ represents a hydrogen atom or a methyl group; R ８ represents a hydrogen atom or a methyl group), and 16. In the formula (9), Z １ C ６－１２ m1 represents an integer of 0 to 2; m2a and m2b each independently represents an integer of 0 to 2; m3, m4, and m5 each independently represent an integer of 0 to 2; R １ ~R ５ each independently represents a hydrocarbon group; １ C ２－６ represents an alkylene group, n1 represents 0 or an integer of 1 to 6, ２ C １－４ 16. The epoxy (meth)acrylate compound of claim 15, which exhibits an alkylene group.

17. A method for producing the epoxy (meth)acrylate compound according to claim 15 or 16, comprising a step of reacting the epoxy compound represented by formula (8) according to claim 12 with (meth)acrylic acid or an ester-forming derivative thereof.

18. A curable composition comprising at least one selected from the group consisting of a (meth)acrylate compound represented by formula (7) according to claim 9, an epoxy compound represented by formula (8) according to claim 12, and an epoxy (meth)acrylate compound represented by formula (9) according to claim 15.

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

20. An optical component comprising the cured product according to claim 19.

21. A composition comprising at least one selected from the group consisting of a fluorene compound represented by formula (1) according to claim 1, a (meth)acrylate compound represented by formula (7) according to claim 9, an epoxy compound represented by formula (8) according to claim 12, and an epoxy (meth)acrylate compound represented by formula (9) according to claim 15, and a solvent.

22. The composition according to claim 21, wherein the solvent is at least one member selected from the group consisting of ketones, esters, ethers, ether esters, amides and aromatic hydrocarbons.

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