Fluorene compound as well as preparation method and application thereof

Abstract

Provided is a fluorene compound having both a high refractive index and high solubility. This fluorene compound is represented by formula (1). [In formula (1), Y1a and Y1b are groups represented by formula (Y1), R2a and R2b are substituents, m2a and m2b are integers of 0-3, and Y2a and Y2b are groups represented by formula (Y2). (In formula (Y1), Z1 is an aromatic hydrocarbon ring, R1 is a substituent group, and m1 is an integer of 0 or more than 1, and in formula (Y2), R3, R4 and R5 are substituent groups, m3 is an integer of 0-5, m4 is an integer of 0-5, m5 is an integer of 0-2, A1 and A2 are alkylene groups, and n1 is an integer of 0 or more than 1. ]

Description

Technical Field

[0001] This disclosure relates to compounds having a fluorene skeleton, methods of manufacturing the same, and uses thereof. Background Technology

[0002] Compounds with a fluorene framework possess excellent optical properties due to their chemical structure and are used as resin materials (optical materials) for forming optical components.

[0003] Japanese Patent Application Publication No. 2020-75866 (Patent Document 1) discloses a compound crystal represented by the following formula (A), whose maximum melting endothermic temperature, as measured by differential scanning calorimetry, is 201~205°C, and describes that the crystal has a high bulk density.

[0004] [Chemistry 1]

[0005]

[0006] Furthermore, Japanese Patent Application Publication No. 2018-90560 (Patent Document 2) discloses bisphenols represented by the following general formula (B):

[0007] [Chemistry 2]

[0008]

[0009] (In the formula, R1~R4 are the same or different, representing alkyl, aryl or halogen atoms; n1 and n2 are the same or different, representing integers from 1 to 4; k1~k4 are the same or different, representing 0 or integers from 1 to 4. When at least one of k1~k4 is 2 or more, the corresponding R1~R4 can be the same or different.)

[0010] Patent Document 2 also describes that the resin made from the bisphenols has excellent refractive index and heat resistance, as well as excellent flowability and solvent solubility when melted.

[0011] Existing technical documents

[0012] Patent documents

[0013] Patent Document 1: Japanese Patent Application Publication No. 2020-75866

[0014] Patent Document 2: Japanese Patent Application Publication No. 2018-90560 Summary of the Invention

[0015] The problem that the invention aims to solve

[0016] The compound represented by formula (A) of Patent Document 1 includes the bisphenols represented by formula (B) of Patent Document 2, which describes the characteristics of a resin made from the aforementioned bisphenols.

[0017] However, in Patent Documents 1 and 2, there is no disclosure or indication of compounds with aryl groups (especially multiple aryl groups such as two aryl groups) bonded at positions 1 to 8 of the fluorene ring and their optical properties.

[0018] It should be noted that, generally speaking, when a chemical structure contains a benzene ring (aromatic ring), it tends to exhibit increased heat resistance (boiling point, 5% weight reduction temperature, etc.) and refractive index, but decreased solubility. Therefore, the applications of fluorene compounds containing benzene rings are greatly limited.

[0019] Therefore, the purpose of this disclosure is to provide a fluorene compound that can achieve both high refractive index and high solubility even when its chemical structure contains a large number of benzene rings, as well as a method for its manufacture and its uses.

[0020] Methods for solving problems

[0021] The inventors have discovered that fluorene compounds with specific chemical structures can simultaneously satisfy high refractive index and high solubility, thus completing the present invention (this disclosure).

[0022] That is, this disclosure may include the following schemes.

[0023] Option [1]:

[0024] Fluorene compounds (diol compounds) represented by the following formula (1).

[0025] [Chemistry 3]

[0026]

[0027] [In the formula, Y] 1a and Y 1b Independently represent the monovalent group represented by the following formula (Y1),

[0028] [Chemistry 4]

[0029]

[0030] (where Z) 1 R represents an aromatic ring. 1 (This represents a substituent, and m1 represents an integer greater than or equal to 0 or 1.)

[0031] R 2a and R 2b The substituents are represented independently, and m2a and m2b independently represent integers from 0 to 3.

[0032] Y 2a and Y 2b Independently represent the monovalent group represented by the following formula (Y2),

[0033] [Chemistry 5]

[0034]

[0035] (where A) 1 Indicates an alkylene group, n1 represents an integer of 0 or higher.

[0036] R 3 This represents a substituent, and m3 represents an integer from 0 to 5.

[0037] A 2 Indicates alkylene,

[0038] R 4 This represents a substituent, and m4 represents an integer from 0 to 5.

[0039] R 5 This represents a substituent, and m5 represents an integer from 0 to 2.

[0040] Option [2]:

[0041] The fluorene compound described in scheme [1], wherein, in formula (1) [and formulas (Y1) and (Y2)], Z 1 Indicate C 6-12 In an aromatic ring, m1 represents an integer from 0 to 2, m2a and m2b independently represent integers from 0 to 2, and m3, m4, and m5 independently represent integers from 0 to 2. R 1 ~R 5 (that is, R) 1 R 2a R 2b R 3 R 4 and R 5 A represents a hydrocarbon group independently. 1 Indicate C 2-6 Alkylene, n1 represents 0 or an integer from 1 to 6, A 2 Indicate C 1-4 Alkylene.

[0042] Option [3]:

[0043] The fluorene compound described in scheme [1] or [2], wherein, in formula (1), Y represents 1a and Y 1b Z in equation (Y1) 1 It indicates a benzene ring or a naphthalene ring.

[0044] Option [4]:

[0045] The fluorene compound described in any one of schemes [1] to [3] is a crystal and has a melting point of 195 to 210 °C.

[0046] Option [5]:

[0047] The fluorene compound described in schemes [1] to [4] is selected from at least one of monomers used for melt polymerization or solution polymerization and resin additives used for modifying resins.

[0048] Option [6]:

[0049] The method for manufacturing the fluorene compound according to any one of schemes [1] to [5] includes the reaction steps described in (i) and (ii) below:

[0050] (i) A process for reacting the compound represented by formula (2) with the compound represented by formula (3a) and the compound represented by formula (3b),

[0051] (ii) A step of coupling the compound represented by formula (4) with the compound represented by formula (5a) and the compound represented by formula (5b),

[0052] [Chemistry 6]

[0053]

[0054] [In the formula, X] 1a and X 2a and X 1b and X 2b Y represents independently a pair of reactive groups capable of forming a carbon-carbon bond through a coupling reaction. 1a and Y 1b R 2a and R 2b m2a and m2b, and Y 2a and Y 2b Same as equation (1) above.

[0055] Option [7]:

[0056] A resin made from a fluorene compound represented by any one of the above schemes [1] to [5].

[0057] Option [8]:

[0058] An optical component comprising the resin described in the above scheme [7].

[0059] Option [9]:

[0060] (Meth)acrylate compounds [(meth)acrylate resins] represented by the following formula (7).

[0061] [Chemistry 7]

[0062]

[0063] [In the formula, Y] 1a and Y 1b Independently represent the monovalent group represented by the following formula (Y1),

[0064] [Chemistry 8]

[0065]

[0066] (where Z) 1 R represents an aromatic ring. 1 (This represents a substituent, and m1 represents an integer greater than or equal to 0 or 1.)

[0067] R 2a and R 2b The substituents are represented independently, and m2a and m2b independently represent integers from 0 to 3.

[0068] Y 3a and Y 3b Independently represent the monovalent group represented by the following formula (Y3),

[0069] [Chemistry 9]

[0070]

[0071] (where A) 1 Indicates an alkylene group, n1 represents an integer of 0 or higher.

[0072] R 3 This represents a substituent, and m3 represents an integer from 0 to 5.

[0073] A 2 Indicates alkylene,

[0074] R 4 This represents a substituent, and m4 represents an integer from 0 to 5.

[0075] R 5 This represents a substituent, and m5 represents an integer from 0 to 2.

[0076] R 6 This represents a hydrogen atom or a methyl group.

[0077] Option

[10] :

[0078] The (meth)acrylate compound of scheme [9], wherein, in formula (7) [and formulas (Y1) and (Y3)], Z 1 Indicate C 6-12 In an aromatic ring, m1 represents an integer from 0 to 2, m2a and m2b independently represent integers from 0 to 2, and m3, m4, and m5 independently represent integers from 0 to 2. R 1 ~R 5(that is, R) 1 R 2a R 2b R 3 R 4 and R 5 A represents a hydrocarbon group independently. 1 Indicate C 2-6 Alkylene, n1 represents 0 or an integer from 1 to 6, A 2 Indicate C 1-4 Alkylene.

[0079] Option

[11] :

[0080] The method for manufacturing the (meth)acrylate compound described in scheme [9] or

[10] includes a step of reacting the fluorene compound represented by formula (1) in any one of schemes [1] to [5] with (meth)acrylate or its ester-forming derivative.

[0081] Option

[12] :

[0082] Epoxy compounds (epoxy resins) represented by the following formula (8).

[0083] [Chemistry 10]

[0084]

[0085] [In the formula, Y] 1a and Y 1b Independently represent the monovalent group represented by the following formula (Y1),

[0086] [Chemistry 11]

[0087]

[0088] (where Z) 1 R represents an aromatic ring. 1 (This represents a substituent, and m1 represents an integer greater than or equal to 0 or 1.)

[0089] R 2a and R 2b The substituents are represented independently, and m2a and m2b independently represent integers from 0 to 3.

[0090] Y 4a and Y 4b Independently represent the monovalent group represented by the following formula (Y4),

[0091] [Chemistry 12]

[0092]

[0093] (where A) 1Indicates an alkylene group, n1 represents an integer of 0 or higher.

[0094] R 3 This represents a substituent, and m3 represents an integer from 0 to 5.

[0095] A 2 Indicates alkylene,

[0096] R 4 This represents a substituent, and m4 represents an integer from 0 to 5.

[0097] R 5 This represents a substituent, and m5 represents an integer from 0 to 2.

[0098] R 7 This represents a hydrogen atom or a methyl group.

[0099] Option

[13] :

[0100] The epoxy compound described in scheme

[12] , wherein, in formula (8) [and formulas (Y1) and (Y4)], Z 1 Indicate C 6-12 In an aromatic ring, m1 represents an integer from 0 to 2, m2a and m2b independently represent integers from 0 to 2, and m3, m4, and m5 independently represent integers from 0 to 2. R 1 ~R 5 (that is, R) 1 R 2a R 2b R 3 R 4 and R 5 A represents a hydrocarbon group independently. 1 Indicate C 2-6 Alkylene, n1 represents 0 or an integer from 1 to 6, A 2 Indicate C 1-4 Alkylene.

[0101] Option

[14] :

[0102] The method for manufacturing the epoxy compound described in scheme

[12] or

[13] includes a step of reacting the fluorene compound represented by formula (1) in any one of schemes [1] to [5] with the epihaloalcohol component.

[0103] Option

[15] :

[0104] The epoxy (meth)acrylate compound represented by the following formula (9) [vinyl ester resin (or epoxy (meth)acrylate resin)].

[0105] [Chemistry 13]

[0106]

[0107] [In the formula, Y] 1a and Y 1b Independently represent the monovalent group represented by the following formula (Y1),

[0108] [Chemistry 14]

[0109]

[0110] (where Z) 1 R represents an aromatic ring. 1 (This represents a substituent, and m1 represents an integer greater than or equal to 0 or 1.)

[0111] R 2a and R 2b The substituents are represented independently, and m2a and m2b independently represent integers from 0 to 3.

[0112] Y 5a and Y 5b Independently represent the monovalent group represented by the following formula (Y5),

[0113] [Chemistry 15]

[0114]

[0115] (where A) 1 Indicates an alkylene group, n1 represents an integer of 0 or higher.

[0116] R 3 This represents a substituent, and m3 represents an integer from 0 to 5.

[0117] A 2 Indicates alkylene,

[0118] R 4 This represents a substituent, and m4 represents an integer from 0 to 5.

[0119] R 5 This represents a substituent, and m5 represents an integer from 0 to 2.

[0120] R 7 Indicates a hydrogen atom or a methyl group.

[0121] R 8 This represents a hydrogen atom or a methyl group.

[0122] Option

[16] :

[0123] The epoxy (meth)acrylate compound of scheme

[15] , wherein, in formula (9) [and formulas (Y1) and (Y5)], Z 1 Indicate C 6-12In an aromatic ring, m1 represents an integer from 0 to 2, m2a and m2b independently represent integers from 0 to 2, and m3, m4, and m5 independently represent integers from 0 to 2. R 1 ~R 5 (that is, R) 1 R 2a R 2b R 3 R 4 and R 5 A represents a hydrocarbon group independently. 1 Indicate C 2-6 Alkylene, n1 represents 0 or an integer from 1 to 6, A 2 Indicate C 1-4 Alkylene.

[0124] Option

[17] :

[0125] The method for manufacturing the epoxy (meth)acrylate compound described in scheme

[15] or

[16] includes a step of reacting the epoxy compound represented by formula (8) described in scheme

[12] or

[13] with (meth)acrylate or its ester-forming derivatives.

[0126] Solution

[18] :

[0127] A curable composition comprising at least one of the following: a (meth)acrylate compound represented by formula (7) as described in scheme [9] or

[10] , an epoxy compound represented by formula (8) as described in scheme

[12] or

[13] , and an epoxy (meth)acrylate compound represented by formula (9) as described in scheme

[15] or

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

[0128] Option

[19] :

[0129] A cured product formed by curing the curing composition described in scheme

[18] .

[0130] Option

[20] :

[0131] An optical component comprising the cured material described in the above scheme

[19] .

[0132] Solution

[21] :

[0133] A composition (liquid composition or solution, or liquid mixture) comprising a solvent and at least one selected from the following: a fluorene compound (diol compound) represented by formula (1) of any one of the above schemes [1] to [5], a (meth)acrylate compound [(meth)acrylate resin] represented by formula (7) of schemes [9] or

[10] , an epoxy compound (epoxy resin) represented by formula (8) of schemes

[12] or

[13] , and an epoxy (meth)acrylate compound [vinyl ester resin (or epoxy (meth)acrylate resin)] represented by formula (9) of schemes

[15] or

[16] .

[0134] Option

[22] :

[0135] The composition of Scheme

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

[0136] It should be noted that this disclosure can achieve (solve) the following secondary objectives (issues).

[0137] Other objects of this disclosure are to provide fluorene compounds with high heat resistance (or heat decomposition resistance), methods for manufacturing the same, and compositions (or mixtures) containing said compounds.

[0138] In this specification and claims, C1, C6, C are sometimes used. 10 The number of carbon atoms in a substituent is indicated by "C1 alkyl". For example, alkyl groups with 1 carbon atom are represented by "C1 alkyl", and aryl groups with 6 to 10 carbon atoms are represented by "C1 alkyl". 6-10 "Aromatic" indicates.

[0139] In this specification and claims, "independently" means that the two constituent elements are each independent constituent elements, for example, in group Y 1a and Y 1b In this case, it means group Y 1a With group Y 1b They do not need to be the same group; they can also be different groups.

[0140] Furthermore, in this specification and claims, when using "X~Y" to represent a numerical range, the values ​​X and Y at both ends may be included.

[0141] Invention Effects

[0142] According to this disclosure, it is possible to provide fluorene compounds that have both high refractive index and high solubility, methods for manufacturing the same, and compositions (liquid compositions) containing said compounds. Attached Figure Description

[0143] [ Figure 1 ] Figure 1 The 9,9-bis[(3-benzyl-4-(2-acryloyloxyethoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene obtained in Example 3 1 H-NMR spectrum.

[0144] [ Figure 2 ] Figure 2 The 9,9-bis[(3-benzyl-4-(2-acryloyloxyethoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene obtained in Example 3 13 C-NMR spectrum.

[0145] [ Figure 3 ] Figure 3 The 9,9-bis[(3-benzyl-4-glycidoxy-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene obtained in Example 5 1 H-NMR spectrum.

[0146] [ Figure 4 ] Figure 4 The 9,9-bis[(3-benzyl-4-glycidoxy-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene obtained in Example 5 13 C-NMR spectrum.

[0147] [ Figure 5 ] Figure 5 The IR spectrum of 9,9-bis[(3-benzyl-4-hydroxy-5-phenyl)phenyl]-2,7-bis(2-naphthyl)fluorene obtained in Example 2.

[0148] [ Figure 6 ] Figure 6 The IR spectrum of 9,9-bis[(3-benzyl-4-glycidoxy-5-phenyl)phenyl]-2,7-bis(2-naphthyl)fluorene obtained in Example 5.

[0149] [ Figure 7 ] Figure 7 The 9,9-bis[(3-benzyl-4-(3-acryloyloxy-2-hydroxypropoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene obtained in Example 6 1 H-NMR spectrum.

[0150] [ Figure 8 ] Figure 8 The 9,9-bis[(3-benzyl-4-(3-acryloyloxy-2-hydroxypropoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene obtained in Example 6 13 C-NMR spectrum.

[0151] [ Figure 9 ] Figure 9 The 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.

[0152] Implementation

[0153] [Fluorene compounds (or diol compounds) represented by formula (1)]

[0154] In the above formula (1), Y represents a monovalent group. 1a and Y 1b The above equation (Y1) is derived from Z 1 The aromatic rings referred to are, for example, monocyclic aromatic rings such as benzene rings and polycyclic aromatic rings. Examples of polycyclic aromatic rings include fused polycyclic aromatic rings and cyclic polycyclic aromatic rings.

[0155] Examples of fused polycyclic aromatic rings include fused bicyclic aromatic rings, fused tricyclic aromatic rings, and fused bicyclic to tetracyclic aromatic rings. Examples of fused bicyclic aromatic rings include naphthalene rings and indene rings. 10-16 Aromatic rings, etc. Examples of fused tricyclic aromatic rings include anthracene rings, phenanthrene rings, and other fused tricyclic C4 rings. 14-20 Aromatic rings, etc. Preferred fused polycyclic aromatic rings are fused polycyclic C-rings such as naphthalene rings. 10-14 Aromatic rings.

[0156] Examples of cyclic aromatic rings include: biphenyl rings, phenylnaphthalene rings, and binaphthalene rings (biphenyl rings); triphenyl rings and other triphenyl rings. Preferred cyclic aromatic rings are biphenyl rings and other C-rings. 12-18 Biaromatic ring.

[0157] It should be noted that in this specification and claims, "cyclic aromatic ring" refers to a compound in which two or more ring systems (aromatic ring systems) are directly connected by single or double bonds, and the number of bonds in the connecting rings is only one less than the number of ring systems. For example, as mentioned above, phenylnaphthalene rings, binaphthalene rings, etc., even if they have a fused polycyclic aromatic ring skeleton, are classified as cyclic aromatic rings, and are clearly distinguished from "fused polycyclic aromatic rings" such as naphthalene rings (acyclic aromatic rings).

[0158] As a preferred ring Z 1 Examples include: C 6-14 Aromatic rings, more preferably benzene rings, naphthalene rings, biphenyl rings, etc. 6-12 Aromatic rings (e.g., naphthalene rings, biphenyl rings, etc.) 10-12 Aromatic rings, etc.), and more preferably benzene rings, naphthalene rings, etc. 6-10Aromatic rings, especially benzene and naphthalene rings. Please explain, if Z 1 If it is a benzene ring, it not only easily and effectively improves solubility (compatibility), but also exhibits high refractive index and heat resistance, thus it is preferred; if Z 1 It is a polycyclic aromatic ring, such as naphthalene ring, biphenyl ring, etc. 10-12 Polycyclic aromatic rings, especially fused polycyclic aromatic rings such as naphthalene rings, not only easily and effectively improve refractive index and heat resistance, but also sometimes exhibit high solubility (compatibility), and are therefore preferred.

[0159] In addition, the monovalent group Y 1a and Y 1b The ring Z in 1 It can replace any position 1 to 4 and 5 to 8 of the fluorene skeleton, for example, position 2, position 3 and / or position 7. The preferred replacement positions (or bonding positions) are the positions 1, 8, 2, 7, 3, 6, 4 and 5 of the above formula (1) that are symmetrical on the paper, and positions 2 and 7 are particularly preferred.

[0160] To clarify, the fluorene framework is located in the Z-ring. 1 The bonding positions on the ring Z 1 In the case of a naphthalene ring, it can be any position of the 1st or 2nd position of the naphthalene ring, preferably the 2nd position of the naphthalene ring.

[0161] As a result of R 1 The substituents represented (non-reactive or non-polymerizable substituents) can be, for example, halogen atoms, hydrocarbon groups (or groups [-R]). h ]), group [-OR h (where R is the formula) h (representing hydrocarbon group), group [-SR] h (where R is the formula) h It can represent hydrocarbon groups, acyl groups, nitro groups, cyano groups, mono- or disubstituted amino groups, etc.

[0162] In this specification and claims, R h It is an independent hydrocarbon group with two or more R groups. h The types can be the same or different from each other.

[0163] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0164] The R h The hydrocarbon group represented can be saturated or unsaturated, aliphatic (including alicyclic) or aromatic, and can be chain-like (straight-chain or branched), cyclic, or a combination of chain and cyclic structures. It should be specified that the hydrocarbon group (or R) constitutes a hydrocarbon group. hThere is no particular limitation on the number of carbon atoms in the hydrocarbon group (R), for example, it can be less than about 20, preferably in the following ranges: 1~16, 1~12, 1~10, 1~8, 1~6. As a representative hydrocarbon group (or R... h Examples of such compounds include alkyl, cycloalkyl, aryl, and aralkyl groups.

[0165] Examples of alkyl groups (straight-chain or branched alkyl groups) include: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc. 1-10 Alkyl group, preferably C 1-6 Alkyl, more preferably C 1-4 alkyl.

[0166] Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, etc. 5-10 Cycloalkyl.

[0167] Examples of aryl groups include: phenyl, alkylphenyl, biphenyl, naphthyl, etc. 6-12 Aryl. Examples of alkylphenyl groups include: methylphenyl (or tolyl), dimethylphenyl (or xylyl), etc., with one to three carbon atoms. 1-4 Alkyl-phenyl.

[0168] Examples of aralkyl groups include benzyl, phenethyl, etc. 6-10 Aryl-C 1-4 alkyl.

[0169] As the above-mentioned group [-OR h Examples include: alkoxy, cycloalkoxy, aryloxy, arylalkoxy, etc. Specifically, examples include those related to the aforementioned hydrocarbon groups R... h Examples of corresponding groups include alkoxy groups (straight-chain or branched alkoxy groups), such as methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, tert-butoxy, etc. 1-10 Alkyl groups. Examples of cycloalkoxy groups include cyclohexyloxy, etc. (C) 5-10 Cycloalkoxy. Examples of aryloxy groups include phenoxy groups, etc. 6-10 Aryloxy group. Examples of aryl alkoxy groups include: benzyloxy group, etc. 6-10 Aryl-C 1-4 Alkyl group.

[0170] As the above-mentioned group [-SR h Examples include: alkylthio, cycloalkylthio, arylthio, arylalkylthio, etc. Specifically, examples include those related to the aforementioned hydrocarbon groups R... h Examples of corresponding groups include: methylthio, ethylthio, propylthio, n-butylthio, tert-butylthio, etc. 1-10 Alkylthio group. Examples of cycloalkylthio groups include cyclohexylthio group, etc.5-10 Cycloalkylthio group. Examples of aryl thio groups include: thiophenoxy (phenylthio), etc. 6-10 Arylthio group. Examples of aryl thio groups include benzyl thio group, etc. 6-10 Aryl-C 1-4 Alkylthio group.

[0171] Examples of acyl groups include acetyl groups, etc. 1-6 Alkyl-carbonyl, etc.

[0172] Examples of mono- or disubstituted amino groups include dialkylamino and bis(alkylcarbonyl)amino. Examples of dialkylamino groups include dimethylamino and other dicarbonylamino compounds. 1-4 Alkylamino. Examples of bis(alkylcarbonyl)amino groups include diacetylamino and other bis(C)amino groups. 1-4 Alkyl-carbonyl)amino.

[0173] R, as a representative group 1 Examples include: hydrocarbon groups, alkoxy groups, acyl groups, nitro groups, cyano groups, and substituted amino groups. When m1 is 1 or more, R is the preferred group. 1 Examples include: straight-chain or branched alkyl groups, and straight-chain or branched alkoxy groups; specifically, examples include: methyl groups, etc. 1-6 Alkyl, methoxy, and other C 1-4 Alkoxy, wherein alkyl is preferred, and methyl and other C-aryl groups are particularly preferred. 1-4 alkyl.

[0174] The substitution number m1 is an integer greater than or equal to 0 or 1, which can be determined according to ring Z. 1 The type of substitution m1 can be selected from integers around 0 to 7, preferably in the following order: integers from 0 to 6, integers from 0 to 5, integers from 0 to 4, integers from 0 to 3, integers from 0 to 2, more preferably 0 or 1, especially 0.

[0175] It should be noted that when the substitution number m1 is 2 or more, in ring Z... 1 Two or more substituent groups R 1 The types can be the same or different from each other. Additionally, the group R... 1 There are no particular restrictions on the replacement position; it can be determined according to the Z-ring. 1 Type selection.

[0176] As a representative monovalent group represented by the above formula (Y1), Y 1a and Y 1b Examples of naphthyl groups include phenyl, 1-naphthyl, 2-naphthyl, biphenyl, etc., preferably phenyl or naphthyl, more preferably phenyl or 2-naphthyl, and particularly preferably 2-naphthyl or naphthyl.

[0177] To explain, group Y1a and Y 1b The types can be different from each other, but it is preferable to be the same.

[0178] By R 2a Or R 2b The substituents indicated (non-reactive or non-polymerizable substituents) are simply groups Y. 1a Y 1b Any group other than alkyl groups is acceptable. Representative examples include: alkyl groups (excluding aryl groups), fluorine atoms, chlorine atoms, bromine atoms, halogen atoms, cyano groups, etc. Examples of alkyl groups (straight-chain or branched alkyl groups) include: methyl, ethyl, tert-butyl, etc. 1-6 Alkyl groups, etc. When the substitution numbers m2a and m2b are 1 or more, R is preferred. 2a R 2b It is methyl and other C 1-4 alkyl.

[0179] As R 2a and R 2b The substitution numbers m2a and m2b are each, for example, integers from 0 to 3, preferably integers from 0 to 2, more preferably 0 or 1, and especially 0. m2a and m2b may be different from each other, but are preferably the same. It should be noted that when m2a and m2b are each 1 or more, R... 2a and R 2b The types of [benzene compounds] can be different, but are preferably the same. Furthermore, when m2a and m2b are 2 or more, two or more R [representations] on the same benzene ring are substituted in the two benzene rings forming the fluorene skeleton. 2a 2 or more R 2b The types can be the same or different from each other. It should be noted that R... 2a and R 2b There are no particular restrictions on the substitution position, as long as the substitution occurs in group Y. 1a Y 1b Simply replace the position other than the given position.

[0180] In the above formula (1), Y represents a monovalent group (or a hydroxyl-containing group) bonded to the 9,9 position of the fluorene skeleton. 2a and Y 2b The above formula (Y2) is composed of A 1 Examples of alkylene compounds include straight-chain or branched alkylene compounds, such as ethylene, propylene (1,2-propanediyl), trimethylene, 1,2-butanediyl, tetramethylene, etc. 2-6 Alkylenes, etc., are preferably C when the repetition number n1 is 1 or more. 2-4 Alkylene, more preferably ethylene, propylene, etc. 2-3 Alkylene, particularly ethylene.

[0181] oxyalkylene (-A) 1 The number of repetitions (additional moles) n1 of O- can be any integer greater than or equal to 0 or 1. For example, it can be selected from an integer range of approximately 0 to 15, preferably in the following ranges: 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, 0 to 1, and especially 0. Furthermore, considering the potential to improve polymerization reactivity, the number of repetitions n1 can be greater than 1, for example, it can be selected from an integer range of approximately 1 to 15, preferably in the following ranges: 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, 1 to 2, and particularly preferably 1. It should be noted that in this specification and claims, "number of repetitions (additional moles)" can be an average value (arithmetic mean, summative average) or an average addition of moles, and the preferred range is the same as the aforementioned preferred range (the range of integers). If the number of repetitions n1 is below the upper limit, it is easier to improve the refractive index and heat resistance.

[0182] When n1 is 2 or more, there are 2 or more oxoalkylene groups (-A) 1 The types of O- can be different from each other, but it is preferred that they are the same.

[0183] Group [-O-(A 1 O) n1 The substitution position of -H] on the benzene ring can replace any position from 2 to 6 of the phenyl group bonded to the 9-position of the fluorene ring. For example, substitution at the 2, 4, or 6-position of the phenyl group is preferred, and substitution at the 4-position is particularly preferred.

[0184] Y represents a monovalent group (or a hydroxyl-containing group) bonded to the 9,9 position of the fluorene skeleton. 2a and Y 2b The above equation (Y2) is derived from R 3 Examples of substituents (non-reactive or non-polymerizable substituents) represented by R in formula (Y1) above include: 1 Identical groups, etc. When the number of substitutions m3 is 1 or more, the preferred substituent R is... 3 Examples of such groups include: halogen atoms; alkyl, cycloalkyl, aryl, aralkyl, and other hydrocarbon groups; alkoxy groups; acyl groups; nitro groups; cyano groups; substituted amino groups, etc. More preferably, examples include: alkyl groups (straight-chain or branched-chain alkyl groups), cycloalkyl groups, alkoxy groups (straight-chain or branched-chain alkoxy groups), and even more preferably, examples include: methyl groups, etc. 1-6 Alkyl, cyclohexyl, and other C 5-8 Cycloalkyl, methoxy, and other C 1-4 Alkoxy. Among these, alkyl groups are preferred, and particularly methyl groups are preferred. 1-4 alkyl.

[0185] Group R 3The substitution number m3 is an integer from 0 to 5, preferably an integer from 0 to 4, an integer from 0 to 3, an integer from 0 to 2, more preferably 0 or 1, and particularly preferably 0. It should be noted that when m3 is 2 or more, two or more groups R... 3 The types can be the same or different from each other. Additionally, the group R... 3 There are no particular restrictions on the substitution position, when it is with group R 3 In the bonded benzene ring, most of the substitutions are in group A. 2 The adjacent or opposite position.

[0186] As alkylene A 2 It can be used as an alkylene A 1 The alkylene compounds exemplified are specifically: straight-chain or branched alkylene compounds, such as methylene, ethylene, propylene (1,2-propyl), trimethylene, 1,2-butadiene, tetramethylene, etc. 1-6 Alkylene, preferably C 1-4 Alkylene, more preferably methylene, ethylene, etc. 1-3 Alkylene, particularly methylene.

[0187] Group [-A] 2 -Ph-(R 3 ) m3 There are no particular restrictions on the substitution position of the group [-O-(A)] (where Ph represents the benzene ring (phenyl or phenylene)). 1 O) n1 -H] and the group [-Ph-(R 4 ) m4 (where Ph is the same as above) can be substituted at positions other than the bonding position, mostly in the group [-O-(A 1 O) n1 The adjacent position of -H] (with the group [-O-(A)) 1 O) n1 The carbon atom adjacent to the bonding position of [-H].

[0188] Y represents a monovalent group (or a hydroxyl-containing group) bonded to the 9,9 position of the fluorene skeleton. 2a and Y 2b The above equation (Y2) is derived from R 4 Examples of substituents (non-reactive or non-polymerizable substituents) represented by R in formula (Y1) above include: 1 Identical groups, etc. When the number of substitutions m4 is 1 or more, the preferred substituent R is... 4Examples of such groups include: halogen atoms; alkyl, cycloalkyl, aryl, aralkyl, and other hydrocarbon groups; alkoxy groups; acyl groups; nitro groups; cyano groups; substituted amino groups, etc. More preferably, examples include: alkyl groups (straight-chain or branched-chain alkyl groups), cycloalkyl groups, alkoxy groups (straight-chain or branched-chain alkoxy groups), and even more preferably, examples include: methyl groups, etc. 1-6 Alkyl, cyclohexyl, and other C 5-8 Cycloalkyl, methoxy, and other C 1-4 Alkoxy. Among these, alkyl groups are preferred, and particularly methyl groups are preferred. 1-4 alkyl.

[0189] Group R 4 The substitution number m4 is an integer from 0 to 5, preferably an integer from 0 to 4, an integer from 0 to 3, an integer from 0 to 2, more preferably 0 or 1, and particularly preferably 0. It should be noted that when m4 is 2 or more, two or more groups R... 4 The types can be the same or different from each other. Additionally, the group R... 4 There are no particular restrictions on the replacement position; any appropriate choice can be made.

[0190] With group R 4 There are no particular restrictions on the substitution position of the bonded benzene ring, as long as the substitution occurs in the [-O-(A] group. 1 O) n1 -H] and the group [-A] 2 -Ph-(R 3 ) m3 (where Ph is the same as above) can be substituted at positions other than the bonding position, mostly in the group [-O-(A 1 O) n1 The adjacent position of -H] (with the group [-O-(A)) 1 O) n1 The carbon atom adjacent to the bonding position of [-H].

[0191] Y represents a monovalent group (or a hydroxyl-containing group) bonded to the 9,9 position of the fluorene skeleton. 2a and Y 2b The above equation (Y2) is derived from R 5 Examples of substituents (non-reactive or non-polymerizable substituents) represented by R in formula (Y1) above include: 1 The same group, etc. When the number of substitutions m5 is 1 or more, the preferred substituent R is... 5 Examples of such groups include: halogen atoms; alkyl, cycloalkyl, aryl, aralkyl, and other hydrocarbon groups; alkoxy groups; acyl groups; nitro groups; cyano groups; substituted amino groups, etc. More preferably, examples include: alkyl groups (straight-chain or branched-chain alkyl groups), cycloalkyl groups, alkoxy groups (straight-chain or branched-chain alkoxy groups), and even more preferably, examples include: methyl groups, etc. 1-6 Alkyl, cyclohexyl, and other C 5-8Cycloalkyl, methoxy, and other C 1-4 Alkoxy. Among these, alkyl groups are preferred, and particularly methyl groups are preferred. 1-4 alkyl.

[0192] Group R 5 The substitution number m5 is an integer from 0 to 2, preferably 0 or 1, and more preferably 0. It should be noted that when m5 is 2, the two groups R... 5 The types can be the same or different from each other.

[0193] Group R 5 There are no particular restrictions on the substitution position, as long as the substitution occurs in the [-O-(A] group. 1 O) n1 -H], group [-A] 2 -Ph-(R 3 ) m3 ] (where Ph is the same as above) and the group [-Ph-(R 4 ) m4 (where Ph is the same as above) can be any position other than the bonding position.

[0194] For example, preferably, a group R is substituted at the 3 or 5 position of the benzene ring bonded to the 9 position of the fluorene ring. 4 A bonded benzene ring; a benzene ring bonded to the 9-position of the fluorene ring has a substituent group [-A] at the 5- or 3-position. 2 -Ph-(R 3 ) m3 (where Ph is the same as above); a group [-O-(A) is substituted at the 4-position of the benzene ring bonded to the 9-position of the fluorene ring. 1 O) n1 -H].

[0195] The monovalent group (or hydroxyl-containing group) represented by the above formula (Y2) Y 2a and Y 2b Representative groups include: (phenylalkyl-hydroxy-phenyl)phenyl with n1 of 0 and substituents; and (phenylalkyl-hydroxy(poly)alkoxy-phenyl)phenyl with n1 of 1 or more and substituents. It should be noted that in this specification and claims, "(poly)alkoxy" is used to encompass both alkoxy and polyalkoxy groups.

[0196] Examples of the above-mentioned (phenylalkyl-hydroxy-phenyl)phenyl (or phenylalkyl-hydroxy-biphenyl or (hydroxy-phenylalkyl-phenyl)phenyl) include: (3-phenylmethyl-4-hydroxy-5-phenyl)phenyl (or 5-phenylmethyl-6-hydroxy-3-biphenyl or 5-benzyl-6-hydroxy-3-biphenyl), (3-phenylethyl-4-hydroxy-5-phenyl)phenyl, etc. (phenyl C) 1-6Alkyl-hydroxy-phenyl)phenyl, preferably: (phenyl C 1-4 Alkyl-hydroxy-phenyl)phenyl, etc.

[0197] Examples of the above-mentioned (phenylalkyl-hydroxy(poly)alkoxy-phenyl)phenyl include: (3-phenylmethyl-4-hydroxy(poly)alkoxy-5-phenyl)phenyl [or 5-phenylmethyl-6-(2-hydroxyethoxy)-3-biphenyl or 5-benzyl-6-(2-hydroxyethoxy)-3-biphenyl], (3-phenylethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl, (3-phenylmethyl-4-(2-hydroxypropoxy)-5-phenyl)phenyl, etc. (phenyl C 1-6 Alkyl-hydroxy (mono-to-deca-C) 2-4 Alkoxy-phenyl)phenyl, preferably: (phenyl C 1-4 Alkyl-hydroxy (mono-to-deca-C) 2-4 Alkoxy-phenyl)phenyl, etc.

[0198] These monovalent groups (or hydroxyl-containing groups) Y 2a and Y 2b In this embodiment, n1 is preferably an integer from 0 to 6 (preferably 0 or 1, especially 0), and may be a (phenylalkyl-hydroxy-phenyl)phenyl or (phenylalkyl-hydroxy(poly)alkoxy-phenyl)phenyl with substituents, particularly preferably (3-phenylmethyl-4-hydroxy-5-phenyl)phenyl (or (3-benzyl-4-hydroxy-5-phenyl)phenyl) or (3-phenylmethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl, more preferably (3-phenylmethyl-4-hydroxy-5-phenyl)phenyl.

[0199] The (phenylalkyl-hydroxy-phenyl)phenyl and (phenylalkyl-hydroxy(poly)alkoxy-phenyl)phenyl may have substituents (including those in preferred embodiments) and as a group R 3 , group R 4 and group R 5 The substituents shown are the same.

[0200] Y 2a and Y 2b The types can be the same or different from each other. When Y 2a and Y 2b When the types are different from each other, Y 2a and Y 2b m3, m4, and m5, as well as group A 1 , group R 3 , group R 4 , group R 5 Group A 2 The types and their substitution positions can be the same, only the repetition number n1 can be different. Y is preferred.2a and Y 2b They are of the same type.

[0201] As a representative fluorene compound represented by the above formula (1), Y can be cited as an example. 1a and Y 1b The ring Z in 1 The same compounds, etc. Examples of such fluorene compounds include: Y 1a and Y 1b The ring Z in 1 Compounds containing benzene rings, naphthalene rings, or biphenyl rings, preferably benzene rings or naphthalene rings. It should be noted that in such fluorene compounds, m1, m2a, m2b, m3, m4, and m5 can be 0, A... 1 It can be ethylene, propylene, etc. C 2-3 Alkylene, n1 can be 0 or more, A 2 It can be methylene, ethylene, etc. C 1-3 Alkylene. Among such fluorene compounds, Z is preferred. 1 Compounds that are benzene rings or naphthalene rings, more preferably: Z 1 It is a benzene ring or a naphthalene ring, and m1, m2a, m2b, m3, m4 and m5 are 0, A 1 It is ethylene or propylene, n1 is 0 or 1, A 2 Compounds that are methylene or ethylene.

[0202] As mentioned above, Z 1 Compounds that are benzene rings and whose m1, m2a, m2b, m3, m4, and m5 are 0, such as 9,9-bis[(phenylalkyl-hydroxy-phenyl)phenyl]-diphenylfluorene (corresponding to compounds with n1=0) and 9,9-bis[(phenylalkyl-hydroxy(poly)alkoxy-biphenyl]-diphenylfluorene (corresponding to compounds with n1≥1), etc.

[0203] Examples of 9,9-bis[(phenylalkyl-hydroxy-phenyl)phenyl]-diphenylfluorene include: 9,9-bis[(3-phenylmethyl-4-hydroxy-5-phenyl)phenyl]-2,7-diphenylfluorene [or 9,9-bis(5-phenylmethyl-6-hydroxy-3-biphenyl)-2,7-diphenylfluorene or 9,9-bis(5-benzyl-6-hydroxy-3-biphenyl)-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, 9,9-bis[(5-phenylethyl-6-hydroxy-3-biphenyl)-3,6-diphenylfluorene, etc. 9,9-bis[(phenylC] 1-4 Alkyl-hydroxy-phenyl)phenyl]-diphenylfluorene, etc.

[0204] Examples of 9,9-bis[(phenylalkyl-hydroxy(poly)alkoxy-phenyl)phenyl]-diphenylfluorene include: 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, 9,9-bis[(3-phenylethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-3,6-diphenylfluorene, etc. 1-4 Alkyl-hydroxy (mono-to-deca-C) 2-4 Alkoxy-phenyl)phenyl]-diphenylfluorene, etc.

[0205] As mentioned above, Z 1 Compounds that are naphthalene rings and have m1, m2a, m2b, m3, m4 and m5 as 0, such as 9,9-bis[(phenylalkyl-hydroxy-phenyl)phenyl]-dinaphthylfluorene and 9,9-bis[(phenylalkyl-hydroxy(poly)alkoxy-phenyl)phenyl]-dinaphthylfluorene.

[0206] Examples of 9,9-bis[(phenylalkyl-hydroxy-phenyl)phenyl]-dinaphthylfluorene include: 9,9-bis[(3-phenylmethyl-4-hydroxy-5-phenyl)phenyl]-2,7-bis(2-naphthyl)fluorene [or 9,9-bis(5-phenylmethyl-6-hydroxy-3-biphenyl)-2,7-bis(2-naphthyl)fluorene or 9,9-bis(5-benzyl-6-hydroxy-3-biphenyl)-2,7-bis(2-naphthyl)fluorene], 9,9-bis[(3-phenylethyl-4-hydroxy-5-phenyl)phenyl]-2, 7-Di(2-naphthyl)fluorene, 9,9-bis[(3-phenylmethyl-4-hydroxy-5-phenyl)phenyl]-2,7-bis(1-naphthyl)fluorene, 9,9-bis[(3-phenylethyl-4-hydroxy-5-phenyl)-2,7-bis(1-naphthyl)fluorene, 9,9-bis[(3-phenylmethyl-4-hydroxy-5-phenyl)phenyl]-3,6-bis(2-naphthyl)fluorene, 9,9-bis[(3-phenylethyl-4-hydroxy-5-phenyl)phenyl]-3,6-bis(2-naphthyl)fluorene, etc. 9,9-bis[(phenylC 1-4 Alkyl-hydroxy-phenyl)phenyl]-dinaphthylfluorene, etc.

[0207] Examples of 9,9-bis[phenylalkyl-hydroxy(poly)alkoxy-phenyl]-dinaphthylfluorene include, for example: 9,9-bis[(3-phenylmethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-2,7-bis(2-naphthyl)fluorene {or 9,9-bis[5-phenylmethyl-6-(2-hydroxyethoxy)-3-biphenyl]-2,7-bis(2-naphthyl)fluorene or 9,9-bis[5-benzyl-6-(2-hydroxyethoxy)-3-biphenyl]-2,7-bis(2-naphthyl)fluorene}, 9,9-bis[(3-phenylethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-2, 7-Di(2-naphthyl)fluorene, 9,9-bis[(3-phenylmethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-2,7-bis(1-naphthyl)fluorene, 9,9-bis[(3-phenylethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-2,7-bis(1-naphthyl)fluorene, 9,9-bis[(3-phenylmethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-3,6-bis(2-naphthyl)fluorene, 9,9-bis[(3-phenylethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-3,6-bis(2-naphthyl)fluorene, etc. 9,9-bis[(phenylC 1-4 Alkyl-hydroxy (mono-to-deca-C) 2-4 Alkoxy-phenyl)phenyl]-dinaphthylfluorene, etc.

[0208] Among the above-mentioned 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; 9,9-bis[(3-phenylmethyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene, more preferably 9,9-bis[(3-phenylmethyl-4-hydroxy-5-phenyl)phenyl]-2,7-diphenylfluorene; 9,9-bis[(3-phenylmethyl-4-hydroxy-5-phenyl)phenyl]-2,7-di(2-naphthyl)phenylfluorene.

[0209] The fluorene compound represented by the above formula (1) can be crystalline, amorphous, or non-crystalline.

[0210] When the above-mentioned fluorene compound is in the form of crystals, its melting point is about 195~210°C, preferably 196~209°C, and more preferably 197~208°C. Therefore, the above-mentioned fluorene compound can be effectively used as a monomer for melt polymerization.

[0211] In addition, the above-mentioned fluorene compounds have high heat resistance. The 5% weight reduction temperature of the above-mentioned fluorene compounds can be, for example, about 350~500°C, preferably in the following ranges: 355~480°C, 360~460°C, 365~450°C, 370~440°C, 380~430°C, 390~420°C, and 400~415°C.

[0212] The fluorene compound represented by formula (1) above has a high refractive index due to its specific chemical structure having an aromatic ring (benzene ring). The refractive index of the above fluorene compound at a temperature of 25°C and a wavelength of 589 nm can be, for example, about 1.65 to 1.78, preferably in the following ranges: 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.

[0213] It should be noted that, in this specification and claims, the melting point, 5% weight reduction temperature and refractive index of the fluorene compound represented by formula (1) above can be determined by the methods described in the examples below.

[0214] [The method for manufacturing fluorene compounds (diol compounds) represented by formula (1)]

[0215] (Reaction process)

[0216] The fluorene compound represented by formula (1) above can be prepared according to the following reaction equation (reaction equation 1), that is, the manufacturing method including the reaction steps described in (i) and (ii) below.

[0217] (i) A process for reacting the compound represented by formula (2) with the compound represented by formula (3a) and the compound represented by formula (3b),

[0218] (ii) A process for coupling the compound represented by formula (4) with the compound represented by formula (5a) and the compound represented by formula (5b).

[0219] [Chemistry 16]

[0220]

[0221] (where X) 1a and X 2a and X 1b and X 2b Y represents a pair of reactive groups that can form a carbon-carbon bond through a coupling reaction. 1a and Y 1b R 2a and R 2b m2a and m2b, and Y2a and Y 2b (Including preferred embodiments) Same as the above formula (1).

[0222] (Preparation of the compound represented by equation (4) in the first reaction equation (reaction step (i)))

[0223] As reaction step (i), the compound represented by formula (4) above can be prepared by reacting the compound represented by formula (2) above with the compound represented by formula (3a) above and the compound represented by formula (3b) above, for example, by the methods described in Japanese Patent Application Publication No. 2011-68624, Japanese Patent Application Publication No. 2020-75904, etc.

[0224] In the above equation (2), X is... 1a and X 1b Examples 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 equation (reaction step (ii)))” described later.

[0225] Examples of compounds represented by formula (2) above include dihalo-9-fluorenones such as 2,7-dibromo-9-fluorenone. One compound represented by formula (2) above may be used alone or in combination of two or more, but it is preferred to use it alone. The compound represented by formula (2) above is preferably 2,7-dihalo-9-fluorenones such as 2,7-dibromo-9-fluorenone.

[0226] The compounds represented by formula (3a) and formula (3b) above are compounds that can have the same monovalent group (hydroxyl group) as the above-mentioned Y. 2a and Y 2b The preferred embodiments of the corresponding substituent phenylalkyl-hydroxybiphenyls (compounds corresponding to n1=0) or phenylalkyl-hydroxy(poly)alkoxybiphenyls (compounds corresponding to n1≥1) are also the same as those of Y described above. 2a and Y 2b correspond.

[0227] Specific examples of phenylalkyl-hydroxy-biphenyl compounds include: 3-phenylmethyl-2-hydroxy-biphenyl (3-benzyl-2-hydroxy-biphenyl), 3-phenylethyl-2-hydroxy-biphenyl, etc. 1-4 Alkyl-hydroxy-biphenyl, etc.

[0228] Specific examples of phenylalkyl-hydroxy(poly)alkoxy-biphenyl compounds include: 3-phenylmethyl-2-(2-hydroxyethoxy)-biphenyl, 3-phenylethyl-2-(2-hydroxyethoxy)-biphenyl, 3-phenylmethyl-2-(2-hydroxypropoxy)-biphenyl, etc. 1-4 Alkyl-hydroxy (mono-to-deca-C) 2-4 Alkoxy-biphenyl, etc.

[0229] Phenylalkyl-hydroxy-biphenyl and phenylalkyl-hydroxy(poly)alkoxy-biphenyl derivatives may have substituents (including those in preferred embodiments) and R as a group. 3 , group R 4 and group R 5 The exemplified substituents are the same, group R 3 , group R 4 and group R 5 The substitution numbers m3, m4, and m5 (including the preferred embodiments) are also the same.

[0230] The compounds represented by formula (3a) and formula (3b) above can be used alone or in combination of two or more, but are preferably used alone. It should be noted that the compounds represented by formula (3a) and formula (3b) above are preferably the same compound. Among the compounds represented by formula (3a) and formula (3b) above, phenylmethyl-hydroxy-biphenyl compounds such as 3-phenylmethyl-2-hydroxy-biphenyl are preferred.

[0231] The total stoichiometric ratio of the compound represented by formula (2) above to the compound represented by formula (3a) above and the compound represented by formula (3b) above can be, for example, the former / the latter (molar ratio) = about 1 / 2 to 1 / 10, especially about 1 / 2 to 1 / 1.25, preferably in the following ranges: 1 / 2.1 to 1 / 7, 1 / 2.2 to 1 / 5, 1 / 2.5 to 1 / 4, 1 / 2.7 to 1 / 3.3.

[0232] To clarify, in the above formula (1), Y represents 2a and Y 2b The oxoalkylene group (-A) in formula (Y2) 1 When the number of repetitions n1 of O-) is 1 or more, Y, as the 9,9-position bonding group of the fluorene skeleton of the compound represented by the above formula (2), 2a and Y 2b Instead of directly reacting the 9,9 positions of the fluorene skeleton with the compounds represented by formula (3a) and (3b) above, the method can be to react the 9,9 positions of the fluorene skeleton with the compounds in formulas (3a) and (3b) where n1 is 0, to obtain an unaddition epoxide precursor, and then add the precursor to A... 1The method for producing alkylene oxides (alkylene carbonates or haloalkanols) corresponding to straight-chain or branched alkylene groups. In this method, the total stoichiometric ratio of the compound represented by formula (2) above to the compound in formulas (3a) and (3b) where n1 is 0 (including the preferred embodiment) is the same as the total stoichiometric ratio of the compound represented by formula (2) above to the compound represented by formula (3a) and the compound represented by formula (3b) above.

[0233] The addition reaction of alkylene oxides (alkylene carbonates or haloalkanols) can be carried out by conventional methods, such as those described in International Publication No. 2013 / 022065. Specifically, this can be exemplified by reacting ethylene oxide or similar substances with A in the presence of an alkaline catalyst such as potassium carbonate or potassium hydroxide. 1 Corresponding methods for the reaction of epoxides, etc.

[0234] The reaction of the compound represented by formula (2) with the compounds represented by formula (3a) and (3b) can be carried out in the presence of an acid catalyst. Examples of acid catalysts include inorganic acids, organic acids, and solid acids. These acid catalysts can be in the form of hydrates, etc. Examples of inorganic acids include sulfuric acid, hydrochloric acid, and phosphoric acid. Inorganic acids can be in the form of aqueous solutions, such as hydrochloric acid, etc.

[0235] To clarify, when sulfuric acid is used as an acid catalyst, the aforementioned sulfuric acid includes, for example, dilute sulfuric acid with a concentration of about 30 to 90% by mass, concentrated sulfuric acid with a concentration of more than 90% by mass, fuming sulfuric acid, etc. As long as it can be converted into sulfuric acid in the reaction system, sulfur trioxide can be used as a sulfuric acid precursor.

[0236] Examples of organic acids include sulfonic acids, and examples of sulfonic acids include methanesulfonic acid, trifluoromethanesulfonic acid, and other (halogenated) alkyl sulfonic acids, p-toluenesulfonic acid, and other aromatic sulfonic acids.

[0237] The aforementioned solid acids can be broadly classified into inorganic solid acids and organic solid acids. Inorganic solid acids include, for example, metal compounds such as metal oxides, complex metal oxides, metal sulfides, metal sulfates, and metal-containing polyacids; non-metal sulfates such as (NH4)2SO4; clay minerals such as acidic clay and montmorillonite; zeolites with acidic OH groups, such as Y-type, X-type, A-type, ZSM5, mordenite, VIPI5, AlPO4-5, and AlPO4-11; and kaolin.

[0238] Examples of the aforementioned metal oxides include: SiO2, Al2O3, TiO2, Fe2O3, ZrO2, SnO2, V2O5, etc. Examples of the aforementioned composite metal oxides include: SiO2-Al2O3, SiO2-TiO2, TiO2-ZrO2, SiO2-ZrO2, etc. Examples of the aforementioned metal sulfides include: ZnS, etc. Examples of the aforementioned metal sulfates include: CaSO4, Fe2(SO4)3, CuSO4, NiSO4, Al2(SO4)3, MnSO4, BaSO4, CoSO4, ZnSO4, etc. Examples of the aforementioned metal-containing polyacids include: polyacids containing elements such as P, Mo, V, W, Si, etc., specifically: phosphates, such as AlPO4; phosphates of Ti, dodecyltungsten(VI) phosphate n-hydrate, and other tungsten phosphates, etc.

[0239] Examples of organic solid acids include cation exchange resins such as strongly acidic cation exchange resins and weakly acidic cation exchange resins. Solid acids can be porous or non-porous, depending on their type.

[0240] These acid catalysts can be used alone or in combination of two or more. From the viewpoint of improving purity and yield, the preferred acid catalyst is an organic acid, more preferably a sulfonic acid, and particularly preferably an aromatic sulfonic acid such as p-toluenesulfonic acid.

[0241] The proportion of acid catalyst relative to 1 mole of the compound represented by formula (2) above is, for example, 0.01 to 10 moles. From the viewpoint of enabling 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. If the proportion of acid catalyst is above the lower limit, the reaction tends to proceed efficiently.

[0242] Alternatively, the reaction can proceed in the presence of thiols. Examples of thiols include mercaptocarboxylic acids, aminoalkane thiols, thiocarboxylic acids, alkyl thiols, aralkyl thiols, and their salts.

[0243] Examples of thiol carboxylic acids include: 3-mercaptopropionic acid (or β-mercaptopropionic acid) and other 3-mercaptoalkanoic acids, 2-mercaptoalkanoic acids, mercaptosuccinic acid, mercaptobenzoic acid, etc. Examples of 2-mercaptoalkanoic acids include: mercaptoacetic acid (mercaptoacetic acid or mercaptoethane acid), thiolactic acid (or α-mercaptopropionic acid), 2-mercaptobutyric acid (or 2-mercapto-n-butyric acid), 2-mercaptoisobutyric acid (or 2-mercapto-isobutyric acid), etc. 2-6 Alkyl acids, etc.

[0244] Examples of aminoalkane thiols include: 2-aminoethanethiol (or cysteine), 2-aminopropanethiol, 3-aminopropanethiol, 2-aminobutanethiol, 3-aminobutanethiol, 4-aminobutanethiol, 6-aminohexanethiol, 8-aminooctanethiol, 11-aminoundecanethiol, 16-aminohexadecanethiol, etc. 2-20 Alkanes, thiols, etc.

[0245] Examples of thiocarboxylic acids include thioacetic acid and thiooxalic acid.

[0246] Examples of alkyl thiols include: methanethiol, ethanethiol, propanethiol, isopropanethiol, n-butanethiol, dodecylthiol (1-dodecanethiol), etc. 1-16 Alkyl thiols, etc.

[0247] Examples of aralkyl thiols include benzyl thiols.

[0248] For example, representative salts of these salts include: inorganic acid salts such as hydrochlorides and sulfates; organic acid salts such as acetates; alkali metal salts such as sodium and potassium salts; alkaline earth metal salts such as calcium and magnesium salts; tetraalkylammonium salts such as ammonium salts and tetramethylammonium salts; or their complex salts. Alkali metal salts such as sodium salts are preferred. Specific compounds include, for example, sodium methanethiol and sodium ethanethiol.

[0249] These thiols can be used alone or in combination of two or more. Among these thiols, the following are preferred: 3-mercaptopropionic acid, mercaptoacetic acid, thiolactic acid and other mercaptoalkanoic acids, aminoalkane thiols such as cysteine, alkyl thiols such as dodecyl thiols.

[0250] The proportion of thiols, relative to 100 parts by mass of the compound represented by formula (2) above, can be selected from, for example, in the range of about 0.01 to 50 parts by mass, preferably in the following ranges: 0.05 to 20 parts by mass, 0.1 to 10 parts by mass, and 0.15 to 6 parts by mass. Furthermore, the proportion of thiols, relative to 1 mole of the compound represented by formula (2) above, can be selected from, for example, in the range of about 0.001 to 0.5 moles, preferably in the following ranges: 0.003 to 0.4 moles, 0.005 to 0.3 moles, and 0.0075 to 0.2 moles. To clarify, the proportion of thiols, relative to 100 parts by mass of the acid catalyst above, can be selected from, for example, in the range of about 0.001 to 50 parts by mass, preferably in the following ranges: 0.01 to 30 parts by mass, 0.05 to 15 parts by mass, and 0.1 to 10 parts by mass. If the proportion of thiols is above the lower limit, the reaction proceeds efficiently; if it is below the upper limit, thiols can be effectively prevented from remaining as impurities such as sulfur components.

[0251] The reaction can be carried out in a solvent. Examples of solvents include: ethers, specifically chain ethers such as diethyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; tetrahydrofuran (THF); and 1,4-di(ethylene glycol dimethyl ether). Alkane and other cyclic ethers; 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, and cyclic esters (lactones) such as γ-butyrolactone, γ-valerolactone, and γ-caprolactone; carbonates, specifically chain carbonates such as dimethyl carbonate and diethyl carbonate, and cyclic carbonates such as ethylene carbonate and propylene carbonate; amides, specifically chain amides such as N,N-dimethylformamide (DMF), N,N-diethylformamide, and N,N-dimethylacetamide (DMAc), and cyclic amides such as N-methyl-2-pyrrolidone (NMP); ureas, specifically chain ureas such as tetramethylurea and tetraethylurea, and 1,3-dimethyl-2- Imidazolinones (DMI or N,N'-dimethylethyl urea), N,N'-dimethyl-N,N'-trimethylene urea (or N,N'-propylidene urea), and other cyclic ureas; nitriles, specifically cyanide hydrocarbons such as acetonitrile, propionitrile, and benzyl nitrile; nitrated hydrocarbons such as nitromethane, nitrobenzene, nitrobenzene, and nitrosylpropane; phosphoramides such as hexamethylphosphoramide; sulfones, specifically chain sulfones such as ethylmethyl sulfone and cyclic sulfones such as sulfolane; sulfoxides such as dimethyl sulfoxide (DMSO); hydrocarbons, specifically aliphatic hydrocarbons such as hexane, heptane, octane, and decane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; halogenated hydrocarbons, specifically halogenated alkanes such as dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane, and halogenated benzenes such as chlorobenzene and dichlorobenzene.

[0252] These solvents can be used alone or in combination of two or more. Preferably, these solvents contain at least one selected from ethers, carbonates, sulfones and hydrocarbons; more preferably, they contain at least one selected from carbonates such as ethylene carbonate and aromatic hydrocarbons such as toluene; and particularly preferably, they contain at least an aromatic hydrocarbon such as toluene.

[0253] The proportion of solvent (total proportion), relative to 100 parts by mass of the compound represented by formula (2) above, can be selected from, for example, in the range of about 50 to 10,000 parts by mass, preferably in the following ranges: 75 to 2,000 parts by mass, 100 to 1,500 parts by mass, and 150 to 1,000 parts by mass. If the proportion of solvent is below the upper limit, the concentration of the raw material can be adjusted to an appropriate range, which can improve reactivity; if the proportion of solvent is above the lower limit, the viscosity of the raw material can be adjusted to an appropriate range, which can easily improve reactivity.

[0254] The reaction temperature can be selected from about 0 to 200°C, and can be below 150°C. However, from the viewpoint of improving yield and purity, it can be below 130°C, preferably below 125°C, more preferably below 120°C, for example 100 to 120°C, further preferably 105 to 120°C, and most preferably 110 to 120°C. The reaction time can be selected from about 30 minutes to 48 hours, preferably 1 to 24 hours, more preferably 3 to 18 hours, and further preferably 6 to 12 hours.

[0255] The reaction can be carried out under normal or increased pressure, or under reduced pressure.

[0256] The reaction can be carried out with stirring, in air, or in an inert atmosphere such as nitrogen or rare gases. Alternatively, the reaction can occur simultaneously with dehydration.

[0257] It should be noted that the reaction mixture (reaction solution or reaction mixture) after the reaction is completed can be separated (or purified) by conventional methods, such as filtration, concentration, extraction, neutralization, washing, drying, crystallization, column chromatography, or a combination of these methods.

[0258] (Preparation of the compound represented by equation (1) in the first reaction equation (reaction step (ii)))

[0259] The fluorene compound (diol compound) represented by formula (1) above can be prepared by coupling (or cross-coupling) the compound represented by formula (4) above with the compound represented by formula (5a) above and the compound represented by formula (5b) above.

[0260] Examples of coupling reactions include conventional coupling reactions such as the Suzuki-Miyaura coupling reaction, the Yuda-Kosugi-Stille coupling reaction, the Negishi coupling reaction, and the Hiyama coupling reaction, which use palladium catalysts (or palladium(O) catalysts), and the Kumada-Tamao-Corriu coupling reaction, which use nickel catalysts (or nickel(O) catalysts). Among these coupling reactions, the Suzuki-Miyaura coupling reaction is preferred.

[0261] In the above equation (4) (or equation (2)), X 1a and X 1b Each independently represents a reactive group capable of forming a carbon-carbon bond (or a direct bond) through a coupling reaction; in formulas (5a) and (5b) above, X 2a This indicates that it can react with the above-mentioned reactive group X. 1a Together, they form reactive groups that form carbon-carbon bonds through a coupling reaction, X 2b This indicates that it can react with the above-mentioned reactive group X. 1b Reactive groups that form carbon-carbon bonds together through a coupling reaction. Reactive group X1a and X 1b and X 2a and X 2b The appropriate type of coupling reaction can be selected based on the type of coupling reaction described above. When synthesizing via the Suzuki-Miyaura coupling reaction, the reactive group on one side, such as group X... 1a and X 1b Examples of halogen atoms include halogen atoms or fluoroalkyl sulfonyloxy groups. Examples of halogen atoms include iodine atoms, bromine atoms, and chlorine atoms. Examples of fluoroalkyl sulfonyloxy groups include trifluoromethanesulfonyloxy groups (or groups [-OTf]), etc. 1-4 Alkylsulfonyloxy groups, etc. One of these reactive groups may be used alone or in combination of two or more. Among these reactive groups, halogen atoms are preferred, iodine atoms and bromine atoms are more preferred, and bromine atoms are even more preferred.

[0262] In the Suzuki-Miyaura coupling reaction, X is a reactive group that can react with one of the above-mentioned groups. 1a and X 1b The reactive group X of the other coupling party 2a and X 2b Examples of such reactive groups include: borate groups (dihydroxyboryl or the group [-B(OH)2]), borate ester groups, etc. Examples of borate ester groups include: dimethoxyboryl, diisopropoxyboryl, dibutoxyboryl, etc., alkoxyboryl groups; pinacolboryl (or the group [-Bpin]), 1,3,2-dioxaborinane-2-yl, 5,5-dimethyl-1,3,2-dioxaborinane-2-yl, etc. These reactive groups can be used individually or in combination of two or more. Among the reactive groups, the group [-B(OH)2] is preferred.

[0263] To clarify, group X 1a and X 1b With group X 2a and X 2b Any pair of reactive groups that can couple together can be any reactive group, group X. 1a and X 1b It can be a borate group or other reactive group from the other party mentioned above, group X 2a and X 2b It can be a reactive group such as a halogen atom, but group X is preferred. 1a and X 1b It is a reactive group of one of the above, such as a halogen atom, group X 2a and X 2b It is a reactive group such as borate group or the other one mentioned above.

[0264] Examples of compounds represented by formula (4) above include compounds corresponding to the preferred form of fluorene compounds represented by formula (1) above, such as 9,9-bis(5-phenylmethyl-6-hydroxy-3-biphenyl)-2,7-dibromofluorene, etc. 1-4 alkyl-hydroxy-biphenyl)-dihalofluorene; 9,9-bis[5-phenylmethyl-6-(2-hydroxyethoxy)-3-biphenyl]-2,7-dibromofluorene, etc. 9,9-bis[phenylC 1-4 Alkyl-hydroxy (poly)C 2-4 Alkoxy-biphenyl]-dihalofluorene, etc.

[0265] Examples of compounds represented by formula (5a) and formula (5b) above include compounds corresponding to the preferred embodiment of the fluorene compound represented by formula (1) above, such as phenylboronic acid, 1-naphthylboronic acid, 2-naphthylboronic acid, etc. 6-10 Arylboronic acid. The compound represented by formula (5a) above and the compound represented by formula (5b) above are preferably the same compound. The compound represented by formula (5a) above and the compound represented by formula (5b) above can be commercially available products, etc.

[0266] The total stoichiometric ratio of the compound represented by formula (4) above to the compound represented by formula (5a) and the compound represented by formula (5b) above can be, for example, the former / the latter (molar ratio) = about 1 / 2 to 1 / 10, preferably in the following ranges: 1 / 2.1 to 1 / 5, 1 / 2.2 to 1 / 4.5, 1 / 2.3 to 1 / 4, and more preferably 1 / 2.1 to 1 / 3.5 from the viewpoint of more efficient preparation, particularly preferably 1 / 2.1 to 1 / 2.3.

[0267] The coupling reaction can be carried out in the presence of a catalyst. In the synthesis via the Suzuki-Miyaura coupling reaction, the reaction can be carried out in the presence of a palladium catalyst. Examples of palladium catalysts include conventional coupling catalysts such as palladium(0) catalysts and palladium(II) catalysts.

[0268] Examples of palladium(0) catalysts include tetra(triphenylphosphine)palladium(0) [or Pd(PPh3)4], bis(tri-tert-butylphosphine)palladium(0) [or Pd(P(t-Bu)3)2], and other palladium(0)-phosphine complexes.

[0269] Examples of palladium(II) catalysts include: [1,2-bis(diphenylphosphino)ethane]palladium(II) dichloride [or PdCl2(dppe)], [1,3-bis(diphenylphosphino)propane]palladium(II) dichloride [or PdCl2(dppp)], [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride [or PdCl2(dppf)], bis(triphenylphosphine)palladium(II) dichloride [or PdCl2(PPh3)2], bis(tri-o-tolylphosphine)palladium(II) dichloride [or PdCl2(P(o-tolyl)3)2], and other palladium(II)-phosphine complexes. It should be noted that when using a palladium(II) catalyst, the reaction is initiated by reducing a reducing compound in the reaction system, such as a phosphine, amine, or organometallic reagent, to a zero-valent complex.

[0270] To clarify, the aforementioned palladium catalyst can be prepared, for example, by adding catalyst precursors such as tris(dibenzylacetone)dipalladium(O)chloroform complex [or Pd2(dba)3·CHCl3], palladium(II) acetate, and ligands such as triphenylphosphine or carbene to the reaction system. The ratio of the catalyst precursor to the ligand can be, for example, the former / the latter (molar ratio) of approximately 1 / 4 to 1 / 10, preferably 1 / 4 to 1 / 5.

[0271] These catalysts can be used alone or in combination of two or more. Among these catalysts, from the viewpoint of excellent operability (stability in air), palladium(O)-phosphine complexes such as Pd(PPh3)4 and catalyst precursors such as palladium(II) acetate are preferred, and palladium(II) acetate is particularly preferred. The proportion of the catalyst, relative to 1 mole of the compound represented by the above formula (4), in metal conversion, can be, for example, about 0.0001 to 0.1 moles, preferably 0.01 to 0.07 moles, more preferably 0.04 to 0.06 moles. From the viewpoint of more efficient preparation, the following ranges are particularly preferred: 0.0001 to 0.001 moles, 0.0003 to 0.0007 moles, and when using the above-mentioned catalyst precursors such as palladium(II) acetate, 0.0003 to 0.002 moles are particularly preferred, and 0.0005 to 0.0015 moles are most preferred.

[0272] The Suzuki-Miyaura coupling reaction can proceed in the presence of a base. Examples of bases include: metal carbonates or bicarbonates, metal hydroxides, metal fluorides, metal phosphates, organometallic acid salts, and metal alkoxides.

[0273] Examples of metal carbonates or metal bicarbonates include: sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, thallium carbonate (I), etc.

[0274] 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 hydroxide (I).

[0275] Examples of metal fluorides include alkali metal fluorides such as potassium fluoride and cesium fluoride.

[0276] Examples of metal phosphates include alkali metal phosphates such as tripotassium phosphate.

[0277] Examples of organometallic acid salts include alkali metal acetates such as potassium acetate.

[0278] Examples of metal alkoxides include sodium methoxide, sodium ethoxide, potassium tert-butoxide, and other alkali metal alkoxides.

[0279] 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 ratio of the base relative to 1 mole of the compound represented by the above formula (4) can be, for example, about 0.1 to 50 moles, preferably in the following ranges: 0.2 to 10 moles, 0.5 to 9 moles, 1 to 8 moles, and from the viewpoint of more efficient preparation, further preferred ranges are: 1.5 to 10 moles, 1.7 to 8 moles, 2 to 7.5 moles.

[0280] The coupling reaction can be carried out in the presence or absence of a phase transfer catalyst. Examples of phase transfer catalysts include tetrabutylammonium bromide (TBAB), tetraalkylammonium halides such as trioctylmethylammonium chloride, etc. These phase transfer catalysts can be used alone or in combination of two or more.

[0281] Coupling reactions can occur in the presence or absence of solvents that are inactive to the reaction. Examples of solvents 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 benzyl nitrile; 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.

[0282] Examples of cyclic ethers include: 2 Alkane, tetrahydrofuran, etc. Examples of chain ethers include: dialkyl ethers such as diethyl ether and diisopropyl ether, and glycol ethers. Examples of the aforementioned glycol ethers include: (poly)alkylene glycol monoalkyl ethers such as methyl cellosolve and methyl carbitol, and (poly)alkylene glycol dialkyl ethers such as dimethoxyethane.

[0283] Examples of aliphatic hydrocarbons include hexane and dodecane. Examples of alicyclic hydrocarbons include cyclohexane. Examples of aromatic hydrocarbons include toluene and xylene.

[0284] These solvents can be used alone or in combination of two or more. Among these solvents, a mixture of water and aromatic hydrocarbons such as toluene or ketones such as MIBK is preferred.

[0285] The coupling reaction can be carried out in an inert gas atmosphere, such as nitrogen, helium, argon, or other rare gases. The reaction temperature is, for example, 50–200°C, preferably 60–100°C, more preferably 70–90°C, and particularly 75–83°C. The reaction time is, for example, about 0.5–24 hours, preferably 10–20 hours, and from the viewpoint of more efficient preparation, further preferably about 0.5–10 hours or 0.5–8 hours.

[0286] After the reaction is complete, the reaction mixture can be separated and purified as needed using conventional separation and purification methods, such as neutralization, washing, extraction, filtration, dehydration, concentration, decantation, drying, crystallization, reprecipitation, column chromatography, adsorption, or combinations of these methods.

[0287] In addition, the fluorene compound represented by the above formula (1) can also be prepared by a different method than the above method, for example according to the following reaction equation (reaction equation 2).

[0288] [Chemistry 17]

[0289]

[0290] (where Y) 1a and Y 1b R 2a and R 2b m2a and m2b, and Y 2a and Y 2b (Including preferred embodiments) Same as formula (1) above,

[0291] X 1a and X 2a and X 1b and X 2b (Including the preferred embodiment) is the same as the first reaction equation described above.

[0292] In the second reaction equation, the compound represented by formula (3a) and the compound represented by formula (3b) above are reacted to introduce the group Y. 2a and Y 2b The process of reacting the compound represented by formula (5a) and the compound represented by formula (5b) above to introduce the group Y.1a and Y 1b The order of the steps is interchanged with that of the first reaction equation above. Therefore, the preparation of the compound represented by formula (6) in the second reaction equation can be achieved by using the compound represented by formula (2) instead of the compound represented by formula (4) in the description of "(Preparation of the compound represented by formula (1) in the first reaction equation (reaction step (ii)))" above (or by replacing formula (4) with formula (2) above). In addition, the preparation of the compound represented by formula (1) in the second reaction equation can also be achieved by using the compound represented by formula (6) instead of the compound represented by formula (2) in the description of "(Preparation of the compound represented by formula (4) in the first reaction equation (reaction step (i)))" above (or by replacing formula (2) with formula (6) above.

[0293] That is, the method for manufacturing the fluorene compound (diol compound) represented by formula (1) above only needs to include any one of the following steps: (I) a step of coupling the compound represented by formula (4) above with the compound represented by formula (5a) above and the compound represented by formula (5b) above; or (II) a step of reacting the compound represented by formula (6) above with the compound represented by formula (3a) above and the compound represented by formula (3b) above, wherein the compound represented by formula (4) and (6) above, which is a reaction intermediate, can be prepared by the above method or other conventional methods.

[0294] In this disclosure, since the above-mentioned fluorene compounds are manufactured by the above-described method, the above-mentioned fluorene compounds can be prepared with high purity and high yield.

[0295] The HPLC purity of the fluorene compound represented by the above formula (1) can be, for example, 75% or more, preferably 80% or more, more preferably 85% or more, even more preferably 90% or more, especially 95% or more, and particularly 97% or more. It should be noted that, in this specification and claims, the HPLC purity can be determined by the methods described in the examples described later.

[0296] In addition, the yield of the fluorene compound represented by the above formula (1) is, for example, 40% or more, preferably in the following ranges: 50% or more, 55% or more, 60% or more, 70% or more, and more preferably 80% or more.

[0297] [The (meth)acrylate compound represented by formula (7)]

[0298] The (meth)acrylate compound [or (meth)acrylate resin] represented by formula (7) above is a (meth)acrylate compound corresponding to the fluorene compound (or diol compound) represented by formula (1) above.

[0299] In the above equation (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 Both m5 (including the preferred embodiment) and Y in the above formula (1) are the same. 1a Y 1b R 2a R 2b m2a, m2b, A 1 R 3 m3, A 2 R 4 m4, R 5 Same as m5.

[0300] In the above formula (7), n1 can be selected from an integer range of about 0 to 15, preferably the following ranges in order: 0 to 10, 0 to 8, 0 to 6, 0 to 4, 1 to 3, 1 to 2, and especially 1.

[0301] Representative (meth)acrylate compounds represented by the above formula (7) include, for example, compounds in which the hydroxyl group is replaced by (meth)acryloyloxy in the compounds exemplified as representative fluorene compounds (diol compounds) represented by the above formula (1). Specific examples include: 9,9-bis[(3-phenylmethyl-4-(meth)acryloyloxy-5-phenyl)phenyl]-2,7-diphenylfluorene, 9,9-bis[(3-phenylmethyl-4-(meth)acryloyloxy-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene, etc. 1-4 [alkyl-(meth)acryloyloxy-phenyl)phenyl]-di(C 6-12 Aryl)fluorene; 9,9-bis[(3-phenylmethyl-4-(2-(meth)acryloyloxyethoxy)-5-phenyl)phenyl]-2,7-diphenylfluorene, 9,9-bis[(3-phenylmethyl-4-(2-(meth)acryloyloxyethoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene, etc. 9,9-bis[(phenylC 1-4 Alkyl-(meth)acryloyloxy(poly)C 2-4 [alkoxy-phenyl)phenyl]-di(C 6-12 Aryl)fluorene, etc.

[0302] In the above equation (7), R 6It can be either a hydrogen atom or a methyl group, but from the viewpoint of improving reactivity (or curability) and refractive index, a hydrogen atom is preferred.

[0303] The (meth)acrylate compound represented by formula (7) above exhibits high heat resistance. The 5% weight reduction temperature of the above (meth)acrylate compound can be, for example, about 350-500°C, preferably in the following ranges: 355-480°C, 360-460°C, 365-450°C, 370-430°C, 380-420°C, 390-410°C, and 395-405°C. The glass transition temperature of the above (meth)acrylate compound can be, for example, about 30-200°C, preferably in the following ranges: 100-190°C, 120-180°C, and 150-170°C.

[0304] The (meth)acrylate compound represented by formula (7) above has a high refractive index due to its specific chemical structure having an aromatic ring (benzene ring). The refractive index of the above (meth)acrylate compound can be, for example, about 1.65 to 1.78 at a temperature of 25°C and a wavelength of 589 nm, preferably in the following ranges: 1.65 to 1.75, 1.655 to 1.72, 1.66 to 1.71, and 1.665 to 1.70.

[0305] It should be noted that, in this specification and claims, the 5% weight reduction temperature, glass transition temperature and refractive index of the (meth)acrylate compound represented by formula (7) above can be determined by the methods described in the examples below.

[0306] [Method for manufacturing (meth)acrylate compounds represented by formula (7)]

[0307] The (meth)acrylate compound represented by formula (7) above can be prepared by reacting the fluorene compound represented by formula (1) above with (meth)acrylic acid or its ester-forming derivatives (hereinafter referred to as "(meth)acrylic acid or its derivatives").

[0308] It should be noted that, unless otherwise stated in this specification and claims, "ester-forming derivative" refers to alkyl esters (especially lower alkyl esters), specifically methyl esters, ethyl esters, etc. 1-4 Alkyl esters, etc.; acyl halides such as acyl chlorides; acid anhydrides.

[0309] Examples of (meth)acrylic acid or its derivatives include: (meth)acrylic acid or its anhydrides; (meth)acryloyl chloride, (meth)acryloyl bromide, and other (meth)acryloyl halides; and alkyl esters of (meth)acrylic acid, specifically including: methyl (meth)acrylate, ethyl (meth)acrylate, tert-butyl (meth)acrylate, and other (meth)acrylic acid C. 1-4Alkyl esters, etc. These (meth)acrylic acids or their derivatives can be commercially available. Among the above-mentioned (meth)acrylic acids or their derivatives, (meth)acrylic acid is commonly used, and acrylic acid or its derivatives are preferred.

[0310] The proportion of (meth)acrylic acid or its derivatives relative to 1 mole of hydroxyl groups in the compound represented by formula (1) above is, for example, 1 to 10 moles, preferably 1.1 to 5 moles, more preferably 1.5 to 4 moles, further preferably 2 to 3 moles, and even more preferably 2.3 to 2.8 moles.

[0311] When (meth)acrylic acid or its derivatives are acyl halides, they can react in the presence of a base in order to capture the hydrogen halide generated in the reaction. Bases can be broadly classified into inorganic bases and organic bases, for example.

[0312] Examples of inorganic bases include: metal hydroxides, specifically hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide and calcium hydroxide; metal carbonates, specifically carbonates of alkali metals or alkaline earth metals such as sodium carbonate and calcium carbonate; and metal bicarbonates, specifically bicarbonates of alkali metals or alkaline earth metals such as sodium bicarbonate.

[0313] 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.

[0314] One type of alkali can be used alone or in combination of two or more. Among these alkalis, amines such as triethylamine and trialkylamines are commonly used. There is no particular limitation on the amount of alkali used; for example, it is 1 to 2 moles relative to 1 mole of (meth)acryloyl halide, preferably 1.05 to 1.5 moles, and more preferably 1.1 to 1.2 moles.

[0315] Furthermore, when (meth)acrylic acid or its derivatives are acids (or their anhydrides) or alkyl esters, the reaction can be carried out using conventional esterification catalysts. Examples of catalysts include: acid catalysts; base catalysts; and metal catalysts such as metal alkoxides, specifically titanium(IV) alkoxides such as tetraisopropoxytitanium(IV). Among these catalysts, acid catalysts are preferred.

[0316] There are no particular limitations on acid catalysts, and examples include: inorganic acids; organic acids; Lewis acids such as boron trifluoride diethyl ether complexes and tin tetrachloride; and solid acid catalysts such as cation exchange resins. These acid catalysts can be used alone or in combination of two or more. Additionally, these acid catalysts can also be hydrates.

[0317] Examples of such inorganic acids include: strong acids, such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid; and homogeneous or heteropoly acids, such as tungstic acid, molybdenum phosphate, tungstic silicic acid, and molybdenum silicic acid.

[0318] Examples of the aforementioned organic acids include sulfonic acids, specifically alkyl sulfonic acids such as methanesulfonic acid and ethanesulfonic acid, fluoroalkyl sulfonic acids such as trifluoromethanesulfonic acid, and aromatic sulfonic acids such as p-toluenesulfonic acid. Aromatic sulfonic acids, such as p-toluenesulfonic acid monohydrate, are commonly used as acid catalysts.

[0319] There is no particular limitation on the proportion of the catalyst, which is, for example, 0.001 to 1 mole relative to 1 mole of the compound represented by the above formula (1), preferably 0.01 to 0.5 moles.

[0320] The reaction can be carried out in the presence of a polymerization inhibitor. Alternatively, a polymerization inhibitor can be added after the reaction is complete. Examples of polymerization inhibitors include: benzoquinone; hydroquinone, hydroquinone monomethyl ether (MEHQ, p-methoxyphenol, or methoxyquinone), tert-butylhydroquinone, p-benzoquinone, and other hydroquinones; catechols such as p-tert-butylcatechol; amines such as N,N-diethylhydroxylamine; 1,1-diphenyl-2-picrylhydrazine; tri-p-nitrotoluene; phenothiazine, etc. One polymerization inhibitor can be used alone or in combination of two or more. Among these inhibitors, hydroquinones such as p-methoxyphenol (or methoxyquinone) are commonly used.

[0321] The proportion of the polymerization inhibitor relative to 100 parts by mass of (meth)acrylic acid or its derivative may be, for example, about 0.001 to 10 parts by mass; relative to 100 parts by mass of the (meth)acrylic acid compound represented by the above formula (7) obtained from the reaction may be, for example, about 0.0001 to 0.1 parts by mass.

[0322] The reaction can proceed in the presence of a solvent. Examples of solvents include: hydrocarbons, specifically aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons, specifically dichloromethane, chloroform, 1,2-dichloroethane, and chlorobenzene; and ethers, specifically dialkyl ethers such as diethyl ether, tetrahydrofuran (THF), and 1,4-dialkyl ether. Alkane and other cyclic ethers; ketones, specifically acetone, methyl ethyl ketone, etc.; sulfoxides, specifically dimethyl sulfoxide, etc.; amides, specifically N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.; acetonitrile and other nitriles, etc. These solvents can be used alone or in combination of two or more. Among these solvents, aromatic hydrocarbons such as toluene are commonly used. There is no particular limitation on the proportion of the solvent, but relative to 100 parts by mass of the total amount of fluorene compound and (meth)acrylic acid or its derivatives represented by formula (1) above, it can be, for example, about 10 to 1000 parts by mass, preferably 50 to 150 parts by mass.

[0323] The reaction temperature and reaction time can be appropriately selected according to the type of raw materials used. When (meth)acrylic acid or its derivative is (meth)acryloyl 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 (meth)acrylic acid or its derivative is (meth)acrylic acid (or its anhydride) or (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. It should be noted that the reaction can also be carried out at reflux temperature. The reaction time is not particularly limited, for example, it can be about 1 to 24 hours.

[0324] The reaction can be carried out in air or in an inert atmosphere such as nitrogen or rare gases, with stirring, and can be conducted under normal pressure, pressure, or reduced pressure. Furthermore, to effectively prevent accidental polymerization during the reaction, air can be blown into the reaction solution while the reaction proceeds.

[0325] After the reaction is complete, the (meth)acrylate compound represented by the above formula (7) can be separated and purified by conventional methods, such as neutralization, washing, dehydration, filtration, adsorption, concentration, extraction, crystallization, recrystallization, reprecipitation, centrifugation, column chromatography, or a combination of these methods.

[0326] [Epoxy compound represented by formula (8)]

[0327] The epoxy compound [or epoxy resin] represented by formula (8) above is the epoxy compound corresponding to the fluorene compound (or diol compound) represented by formula (1) above.

[0328] In the above equation (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 Both m5 (including the preferred embodiment) and Y in the above formula (1) are the same. 1a Y 1b R 2a R 2b m2a, m2b, A 1 n1, R 3 m3, A 2 R 4 m4, R 5 Same as m5.

[0329] In the above formula (8), n1 can be selected from an integer range of about 0 to 15, for example, it can be 1 or more, preferably the following ranges in order: 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 3, 0 to 2, 0 to 1, especially 0.

[0330] In the above equation (8), R 7 It can be either a hydrogen atom or a methyl group, but from the viewpoint of improving reactivity (or curability) and refractive index, a hydrogen atom is preferred.

[0331] Representative epoxy compounds represented by the above formula (8) include, for example, compounds in which the hydroxyl group is replaced by glycidoxy or 2-methylglycidoxy in the compounds exemplified as representative fluorene compounds (diol compounds) represented by the above formula (1). Specific examples include: 9,9-bis[(3-phenylmethyl-4-glycidoxy-5-phenyl)phenyl]-2,7-bis(2-naphthyl)fluorene, etc. 1-4 [alkyl-glycidoxy-phenyl]phenyl]-di(C 6-12 Aryl)fluorene, 9,9-bis[(3-phenylmethyl-4-(2-methylglycidoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene, etc. 9,9-bis[(phenylC 1-4 [alkyl-(2-methylglycidoxy)-phenyl)phenyl]-di(C 6-12 Aryl)fluorene, etc.

[0332] The epoxy compound represented by formula (8) above has high heat resistance. The 5% weight reduction temperature of the above epoxy compound can be, for example, about 300~410°C, preferably in the following ranges: 310~405°C, 320~400°C, 330~395°C, 340~390°C, 350~385°C, 360~380°C, and 365~375°C. The melting point of the above epoxy compound can be, for example, about 90~120°C, preferably 95~115°C, and more preferably 100~110°C.

[0333] The epoxy compound represented by formula (8) above has a high refractive index due to its specific chemical structure having an aromatic ring (benzene ring). The refractive index of the above epoxy compound at a temperature of 25°C and a wavelength of 589 nm can be, for example, about 1.65 to 1.72, preferably in the following ranges: 1.67 to 1.715, 1.68 to 1.71, 1.69 to 1.705, and 1.695 to 1.7.

[0334] It should be noted that, in this specification and claims, the 5% weight reduction temperature, melting point and refractive index of the epoxy compound represented by formula (8) above can be determined by the methods described in the examples below.

[0335] Furthermore, the epoxy equivalent of the epoxy compound represented by formula (8) above can be selected, for example, from the range of 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. It should be noted that, in this specification and claims, the epoxy equivalent of the above-mentioned epoxy compound can be determined according to JIS K 7236:2001 by the method described in the examples below.

[0336] It should be noted that the epoxy compound (or the curable composition described below) can be not only the epoxy compound (monomer) represented by the above formula (8), but also a mixture of dimers, trimers, tetramers, etc., containing polymers, such as dimers, trimers, tetramers, etc. Polymers may contain one type alone or two or more types in combination.

[0337] In this specification and claims, unless otherwise stated, the term "polymer" of the aforementioned epoxy compound means an epoxy compound having two or more structural (skeleton) components derived from the starting material compound [the diol compound represented by formula (1) above] in its chemical structure, wherein the two or more structural components derived from the diol compound are bonded (linked) by linking groups derived from epihaloalcohol components, such as 2-hydroxypropane-1,3-diyl, as described later. Such a polymer may be inevitably introduced or introduced as an impurity during the manufacture of the compound (monomer) represented by formula (8) above, as described later, or may be intentionally added to the monomer as needed by conventional methods such as one-step (Taffy method or direct method) or two-step (Advanced method, melt method or indirect method).

[0338] The proportion of the polymer, relative to the total moles of the monomer and the polymer, can be, for example, about 0 to 50 mol%, specifically about 0 to 20 mol%, preferably 0 to 10 mol%, more preferably 0 to 5 mol%. The proportion can be, for example, 0.1 to 8 mol%, preferably 0.2 to 3 mol%.

[0339] [The method for manufacturing epoxy compounds represented by formula (8)]

[0340] There are no particular limitations on the method of manufacturing the epoxy compound represented by the above formula (8). For example, it can be prepared by reacting the diol compound represented by the above formula (1) with the epihalo alcohol component.

[0341] Examples of epihaloalcohol components (ephaloalcohols) include epihaloalcohols and β-methylephaloalcohols. Examples of epihaloalcohols include epichlorohydrin, epibromohydrin, and epiiodohydrin. Examples of β-methylephaloalcohols include β-methylephalohydrin, β-methylephalobromohydrin, and β-methylephalodohydrin. These epihaloalcohol components can be used alone or in combination of two or more. Among these epihaloalcohol components, epihaloalcohols such as epichlorohydrin and β-methylephalohydrin are preferred, and epichlorohydrin is more preferred.

[0342] The proportion of the haloalcohol component is, for example, 2 moles or more relative to 1 mole of the diol compound represented by the above formula (1), but is in excess relative to the above diol compound, for example, 5 to 100 moles, preferably 10 to 60 moles, and more preferably 40 to 50 moles.

[0343] It should be noted that, depending on the needs, the reaction can be carried out in the presence of a catalyst or in the absence of a catalyst. Examples of catalysts include quaternary ammonium salts, specifically tetramethylammonium chloride, tetramethylammonium bromide, etc. 1-20 Alkyl ammonium halides, benzyltrimethylammonium chloride, etc. (benzyl triC) 1-4 Alkyl ammonium halides, etc.; trimethylamine borane, etc. (three Cs) 1-4 Alkylamine borane, crown ether, Salt, pyridine Salts, etc. Catalysts can be used alone or in combination of two or more.

[0344] When using a catalyst, there is no particular limitation on its proportion. It is, for example, 0.001 to 1 mole relative to 1 mole of the diol compound represented by the above formula (1), preferably 0.01 to 0.2 moles, and more preferably 0.05 to 0.1 moles.

[0345] Furthermore, to capture the hydrogen halides generated in the reaction, the reaction can be carried out in the presence of a base. Examples of bases include inorganic bases such as metal hydroxides, metal carbonates, or bicarbonates; and organic bases such as amines. Examples of metal hydroxides include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides such as calcium hydroxide. Examples of metal carbonates or bicarbonates include alkali metal carbonates or alkaline earth metal carbonates such as sodium carbonate and sodium bicarbonate. Examples of amines include trialkylamines such as triethylamine, aromatic tertiary amines such as benzyldimethylamine, and heterocyclic tertiary amines such as pyridine. One base can be used alone or in combination of two or more. Among these bases, strong bases are preferred, and metal hydroxides such as sodium hydroxide are more preferred.

[0346] There is no particular limitation on the proportion of base. For example, it is 0.01 to 20 moles of hydroxyl group relative to 1 mole of the diol compound represented by formula (1) above, preferably in the following ranges: 0.05 to 10 moles, 1 to 5 moles, and 1.1 to 1.5 moles.

[0347] The reaction can be carried out in an inert solvent or without a solvent. Suitable solvents include aprotic solvents such as: hydrocarbons, specifically aliphatic hydrocarbons like hexane and heptane, and aromatic hydrocarbons like benzene and toluene; halogenated hydrocarbons like dichloromethane, chloroform, and carbon tetrachloride; esters such as ethyl acetate; ethers, specifically dialkyl ethers like diethyl ether and cyclic ethers like 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. One solvent can be used alone or in combination of two or more. From a reactivity point of view, ketones such as MEK and MIBK, amides, and sulfoxides are preferred, and amides such as DMF and sulfoxides such as dimethyl sulfoxide are even more preferred.

[0348] The reaction can be carried out in air or inert atmospheres such as nitrogen or rare gases, and can be conducted with stirring. Furthermore, the reaction can be carried out under normal pressure, under pressure, or under reduced pressure.

[0349] The reaction temperature and reaction time can be appropriately selected according to the type of raw materials, etc. The reaction temperature can be, for example, 30~150℃, preferably in the following ranges: 40~130℃, 50~100℃, 60~80℃, or it can be carried out while refluxing (at reflux temperature).

[0350] After the reaction is complete, the reaction mixture can be separated and purified as needed using conventional separation and purification methods, such as neutralization, washing, extraction, filtration, dehydration, concentration, decantation, drying, crystallization, reprecipitation, column chromatography, adsorption, or combinations of these methods.

[0351] [The epoxy (meth)acrylate compound represented by formula (9)]

[0352] The epoxy (meth)acrylate compound represented by formula (9) above [epoxy (meth)acrylate resin or vinyl ester resin] is the epoxy (meth)acrylate compound corresponding to the epoxy compound represented by formula (8) above [or the fluorene compound (or diol compound) represented by formula (1) above].

[0353] In the above equation (9), Y 1a Y 1b (i.e., Z) 1 R 1 and m1), R 2a R 2bm2a, m2b, A 1 n1, R 3 m3, A 2 R 4 m4, R 5 Both m5 (including the preferred embodiment) and Y in the above formula (8) [or the above formula (1)] 1a Y 1b R 2a R 2b m2a, m2b, A 1 n1, R 3 m3, A 2 R 4 m4, R 5 Similar to m5, R 7 (Including preferred embodiments) and R in the above formula (8) 7 same.

[0354] In the above formula (9), n1 can be selected from an integer range of about 0 to 15, for example, it can be 1 or more, preferably the following ranges in order: 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 3, 0 to 2, 0 to 1, especially 0.

[0355] In the above equation (9), R 8 It can be either a hydrogen atom or a methyl group, but from the viewpoint of improving reactivity (or curability) and refractive index, a hydrogen atom is preferred.

[0356] Representative epoxy (meth)acrylate compounds represented by the above formula (9) include, for example, compounds in which the hydroxyl group is replaced with [3-(meth)acryloyloxy-2-hydroxy]propoxy in the compounds exemplified as representative fluorene compounds (diol compounds) represented by the above formula (1). Specific examples include 9,9-bis[(3-phenylmethyl-4-(3-acryloyloxy-2-hydroxypropoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene, etc. 1-4 [alkyl-(3-(meth)acryloyloxy-2-hydroxypropoxy)-phenyl)phenyl]-di(C 6-12 Aryl)fluorene, etc.

[0357] The epoxy (meth)acrylate compound represented by formula (9) above exhibits high heat resistance. The 5% weight reduction temperature of the above epoxy (meth)acrylate compound can be, for example, about 300-420°C, preferably in the following ranges: 330-415°C, 340-410°C, 350-405°C, 360-400°C, 365-395°C, 370-390°C, and 375-385°C. The glass transition temperature of the above epoxy (meth)acrylate compound can be, for example, about 50-100°C, preferably 70-90°C, and more preferably 75-85°C.

[0358] The epoxy (meth)acrylate compound represented by formula (9) above has a high refractive index due to its specific chemical structure having an aromatic ring (benzene ring). The refractive index of the above epoxy (meth)acrylate compound can be, for example, about 1.64 to 1.69 at a temperature of 25°C and a wavelength of 589 nm, preferably in the following ranges: 1.65 to 1.695, 1.66 to 1.69, 1.67 to 1.685, and 1.675 to 1.68.

[0359] It should be noted that, in this specification and claims, the 5% weight reduction temperature, glass transition temperature and refractive index of the epoxy (meth)acrylate compound represented by formula (9) above can be determined by the methods described in the examples below.

[0360] [Method for manufacturing epoxy (meth)acrylate compounds represented by formula (9)]

[0361] The epoxy (meth)acrylate compound represented by formula (9) above can be prepared by reacting the epoxy compound represented by formula (8) above with (meth)acrylate or a derivative thereof. Examples of (meth)acrylate or a derivative thereof include: compounds similar to those exemplified in the [Method for manufacturing (meth)acrylate compounds represented by formula (7)] above, and salts of (meth)acrylate (e.g., alkali metal salts such as sodium). Among (meth)acrylate or its derivatives, (meth)acrylate or its salts are commonly used, and acrylic acid or its salts are preferred.

[0362] The proportion of (meth)acrylic acid or its derivatives relative to 1 mole of epoxy group (or glycidyl group) in the epoxy compound represented by the above formula (8) is, for example, 1 to 10 moles, preferably in the following ranges: 1 to 2 moles, 1.05 to 1.5 moles, and 1.1 to 1.2 moles.

[0363] The reaction can proceed in the presence of a catalyst. A base catalyst is preferred. The base catalyst can be an inorganic base or an organic base.

[0364] Examples of inorganic bases include: sodium hydroxide, potassium hydroxide, and other alkali metal hydroxides; calcium hydroxide and other alkaline earth metal hydroxides.

[0365] Examples of organic bases include: amines, quaternary ammonium salts, and phosphines. Salts, etc. 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-methylimidazolium, and 2-ethyl-4-methylimidazolium; 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. Salts, for example: n-butyltriphenyl bromide wait.

[0366] These catalysts can be used alone or in combination of two or more. Among these catalysts, quaternary ammonium salts are preferred, and tetramethylammonium bromide and other tetracarbon-containing catalysts are more preferred. 1-20 Alkyl ammonium halides.

[0367] The proportion of the catalyst relative to 100 moles of the epoxide compound represented by the above formula (8) is, for example, 0.01 to 10 moles, preferably 0.1 to 5 moles, more preferably 0.3 to 4 moles, even more preferably 0.5 to 3 moles, and most preferably 0.7 to 2 moles.

[0368] The reaction can be carried out in the presence of a polymerization inhibitor as needed. Examples of polymerization inhibitors include substances similar to those exemplified in the above item [meth)acrylate compound manufacturing method represented by formula (7)], with hydroquinones such as p-methoxyphenol being preferred.

[0369] The proportion of the polymerization inhibitor, relative to 100 parts by mass of (meth)acrylic acid or its derivatives, may be, for example, about 0.001 to 10 parts by mass, preferably 0.005 to 1 part by mass; relative to 100 parts by mass of the epoxy (meth)acrylic acid compound represented by the above formula (9) obtained from the reaction, may be, for example, about 0.0001 to 0.1 parts by mass.

[0370] The reaction can be carried out in a solvent-free environment or in a solvent. Examples of solvents include: aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as benzene and toluene; alcohols such as methanol, ethanol, n-propanol, and benzyl alcohol; dialkyl ethers such as diethyl ether; tetrahydrofuran (THF), 1,4-di(2 ... Cyclic ethers such as alkanes; aromatic ethers such as anisole; 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); chain ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); cyclic ketones such as cyclohexanone; acetates such as ethyl acetate; lactates such as methyl lactate, ethyl lactate, and 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), and ethyl 3-ethoxypropionate; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; and sulfoxides such as dimethyl sulfoxide.

[0371] These solvents can be used alone or in combination of two or more. Among them, ether esters are preferred, and alkylene glycol monoalkyl ether acetates such as PGMEA are particularly preferred.

[0372] The proportion of the solvent relative to 100 parts by mass of the epoxy compound represented by the above formula (8) 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.

[0373] The reaction temperature is, for example, 50~150°C, preferably 70~140°C, more preferably 90~130°C, and even more preferably 100~120°C. The reaction time is not particularly limited, for example, 30 minutes to 100 hours, preferably 1~50 hours. Furthermore, the reaction is usually carried out mostly in air or an inert gas atmosphere, at normal or pressurized conditions.

[0374] After the reaction is complete, the (meth)acrylate compound represented by the above formula (7) can be separated and purified by conventional methods, such as neutralization, washing, dehydration, filtration, adsorption, concentration, extraction, crystallization, recrystallization, reprecipitation, centrifugation, column chromatography, or a combination of these methods.

[0375] [Curing compositions and cured products thereof]

[0376] This disclosure includes a curable composition and its cured product, said curable composition containing at least one fluorene compound (polymer component or curable resin) selected from the (meth)acrylate compound (or first polyfunctional (meth)acrylate) represented by formula (7) above, the epoxy compound represented by formula (8) above, and the epoxy (meth)acrylate compound (or second polyfunctional (meth)acrylate) represented by formula (9) above. The curable composition may be a (meth)acrylate-based curable composition containing at least the (meth)acrylate compound represented by formula (7) above and / or the epoxy (meth)acrylate compound represented by formula (9) above, or an epoxy-based curable composition containing at least the epoxy compound represented by formula (8) above.

[0377] When it is a (meth)acrylate-based curable composition, it may contain at least a first polyfunctional (meth)acrylate. The (meth)acrylate-based curable composition may contain other polymeric components, such as a third polyfunctional (meth)acrylate different from those in formulas (7) and (9) above; monofunctional (meth)acrylates and other monofunctional polymeric components (or reactive diluents), etc., or may not contain these components.

[0378] There are no particular limitations on the third polyfunctional (meth)acrylate, as long as it is a compound having a plurality 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 especially preferably 2.

[0379] Examples of third-functional (meth)acrylates include: aliphatic epoxy (meth)acrylates, alicyclic epoxy (meth)acrylates, aromatic epoxy (meth)acrylates, poly(meth)acrylates of phenolic varnish-type epoxy resins, etc.; 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; alicyclic glycol di(meth)acrylates; di(meth)acrylates of biphenols or bisphenols or their epoxy alkylene carbonate (alkylene carbonate or haloalkanol) adducts; poly(meth)acrylates of low molecular weight polyol compounds having about 3 to 6 hydroxyl groups or their epoxy alkylene carbonate (alkylene carbonate or haloalkanol) adducts, etc. These third-functional (meth)acrylates can be used alone or in combination of two or more. These third-generation polyfunctional (meth)acrylates are available in commercially available products.

[0380] Examples of the aforementioned aliphatic epoxy (meth)acrylates include, for example, di(meth)acrylates of 1,6-hexanediol diglycidyl ether, di(meth)acrylates of polypropylene glycol diglycidyl ether, and di(meth)acrylates of (poly)alkylene glycol diglycidyl ether.

[0381] Examples of the aforementioned alicyclic epoxy (meth)acrylates include, for instance, di(meth)acrylates of 1,4-cyclohexanediethanol diglycidyl ether, etc., which have a C 5-10 Di(meth)acrylates of aliphatic ring epoxides.

[0382] Examples of the aforementioned aromatic epoxy (meth)acrylates include, for example, di(meth)acrylates of bisphenol A diglycidyl ether, or di(meth)acrylates of diglycidyl ethers of bisphenols or biphenols, or their epoxy alkylene carbonate (alkylene carbonate or haloalkanol) adducts. Examples of bisphenols include, for example, bisphenol A, bisphenol F, bisphenol AD, and bisphenol S. Examples of biphenols include, for example, p,p'-biphenol, m,m'-biphenol, and o,o'-biphenol.

[0383] Examples of alkylene glycol di(meth)acrylates include, for example, ethylene glycol di(meth)acrylate and butanediol di(meth)acrylate. 2-10 Alkyl glycol di(meth)acrylate.

[0384] Examples of the aforementioned polyalkylene glycol di(meth)acrylates include, for example, diethylene glycol di(meth)acrylates and other 2 to 6 C acrylates. 2-10 Alkyl glycol di(meth)acrylate.

[0385] Examples of di(meth)acrylates of the aforementioned alicyclic diols include, for instance, di(meth)acrylates of 1,4-cyclohexanediethanol, etc., which have a C 5-10 Di(meth)acrylates of aliphatic ring diol compounds.

[0386] Examples of poly(meth)acrylates that are low molecular weight polyol compounds having about 3 to 6 hydroxyl groups or their epoxide (alkylene carbonate or haloalkanol) adducts include: glycerol tri(meth)acrylate, diglycerol 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)acrylates.

[0387] The proportion of the first polyfunctional (meth)acrylate, as expressed in formula (7) above, relative to the total amount of the first and third polyfunctional (meth)acrylates, is, for example, 10% by mass or more. Specifically, it can be selected from a range of about 30% to 100% by mass, preferably in the following ranges: 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, more preferably 90% by mass or more, and particularly preferably essentially 100% by mass, that is, the polyfunctional polymer component is only the first polyfunctional (meth)acrylate. It should be noted that the above proportion can be selected from a range of about 60% to 99% by mass, specifically 80% to 97% by mass. If the proportion of the first polyfunctional (meth)acrylate is above the lower limit, there is a tendency to increase the refractive index and heat resistance.

[0388] The proportion of the second polyfunctional (meth)acrylate, as expressed in formula (9) above, relative to the total amount of the second and third polyfunctional (meth)acrylates, is, for example, 10% by mass or more. Specifically, it can be selected from a range of about 30% to 100% by mass, preferably in the following ranges: 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, more preferably 90% by mass or more, and particularly preferably essentially 100% by mass, meaning that the multifunctional polymer component is only the second polyfunctional (meth)acrylate. It should be noted that the above proportion can be selected from a range of about 60% to 99% by mass, specifically 80% to 97% by mass. If the proportion of the second polyfunctional (meth)acrylate is above the lower limit, it tends to improve the refractive index and heat resistance.

[0389] As a monofunctional polymerizable component (or reactive diluent), any compound having one polymerizable group (or polymerizable unsaturated bond), such as vinyl, allyl, or (meth)acryloyl groups, is acceptable. Examples include: monofunctional vinyl monomers; monofunctional (meth)acrylic monomers, etc. Examples of monofunctional vinyl monomers include: α-olefin monomers such as ethylene and propylene; styrene monomers such as styrene, α-methylstyrene, and vinyltoluene; vinyl ester monomers such as vinyl acetate; and N-vinylpyrrolidone, etc. Examples of monofunctional (meth)acrylic monomers include: (meth)acrylic acid; (meth)acrylamide; N-substituted (meth)acrylamides such as N-hydroxymethyl (meth)acrylamide and N,N-dimethyl (meth)acrylamide; (meth)acrylonitrile; and monofunctional (meth)acrylic esters.

[0390] These monofunctional polymers can be used alone or in combination of two or more. Among these monofunctional polymers, monofunctional (meth)acrylate monomers are commonly used, especially monofunctional (meth)acrylates.

[0391] Examples of monofunctional (meth)acrylates include: aliphatic monofunctional (meth)acrylates; alicyclic monofunctional (meth)acrylates; aromatic monofunctional (meth)acrylates; and sulfur-containing monofunctional (meth)acrylates. These monofunctional (meth)acrylates can be used alone or in combination of two or more.

[0392] Examples of aliphatic monofunctional (meth)acrylates include: methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc. (meth)acrylate C 1-20 Alkyl esters.

[0393] Examples of alicyclic monofunctional (meth)acrylates include: cyclohexyl (meth)acrylate, etc. (meth)acrylate C 5-10 Bridged cyclic (meth)acrylates such as cycloalkyl esters, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate.

[0394] 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 2-phenoxyethyl (meth)acrylate, 2-(2-naphthoxy)ethyl (meth)acrylate, and 2-(o-phenylphenoxy)ethyl (meth)acrylate. 6-12 Aryloxy C 2-4 Alkyl esters, etc.; mono(meth)acrylates of bisphenols or biphenols (or their epoxide adducts), etc.; (meth)acrylates with a fluorene skeleton, such as 9-(meth)acryloyloxymethylfluorene, etc.

[0395] Examples of monofunctional (meth)acrylates containing sulfur atoms include: alkyl thioacrylates, aryl thioacrylates, aryl alkyl thioacrylates, and aryl thioalkyl acrylates. Examples of alkyl thioacrylates include: methyl thioacrylate, etc. (Methacrylate C) 1-6 Alkyl thioesters. Examples of aryl thioesters of (meth)acrylate include: phenyl thioesters of (meth)acrylate, etc. (meth)acrylate C 6-10 Aryl thioesters. Examples of aryl thioesters of (meth)acrylate include: benzyl thioester of (meth)acrylate, etc. (meth)acrylate C 6-10 Aryl C 1-6 Alkyl thioesters. Examples of arylthioalkyl esters of (meth)acrylate include: phenylthioethyl (meth)acrylate, etc. (meth)acrylate C 6-10 ArylthioC 2-4Alkyl esters.

[0396] When the curable composition is an epoxy-based curable composition containing at least the epoxy compound represented by formula (8) above (first epoxy compound), it may contain other polymeric components different from formula (8) above (second epoxy compound), or it may not contain them.

[0397] As a second epoxy compound (epoxy resin) different from the above formula (8), examples include: glycidyl ether type epoxy resins, specifically bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, bisphenol AD ​​type, bisphenol S type, biphenol type, etc.; phenol novolac type, cresol type Phenolic varnish-type epoxy resins such as novolac, phenolic aralkyl type epoxy resins, triphenolic alkane type epoxy resins, tetra(glycidoxyphenyl)ethane and other tetraphenolic epoxy resins, 1,6-bis(glycidoxy)naphthalene and other fused-ring aromatic hydrocarbon modified epoxy resins, etc.; glycidyl ester type epoxy resins such as diglycidyl esters of aromatic dicarboxylic acids (or their hydrides); glycidylamine type epoxy resins such as tetraglycidyl diaminodiphenylmethane, tetraglycidyl bis(aminomethyl)cyclohexane, triglycidyl aminophenol, etc.; cyclic aliphatic type epoxy resins such as bis(3,4-epoxycyclohexylmethyl) adipate, (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexane carboxylate ester; Type 1 epoxy resin; Isocyanurate type epoxy resin, Hydantoin type epoxy resin, containing... Heterocyclic epoxy resins such as epoxy resins per ton unit; bromine-containing epoxy resins such as tetrabromobisphenol A type epoxy resin, etc.

[0398] Furthermore, the second epoxy compound may include a reactive diluent. This reactive diluent may be a low-viscosity epoxy compound, for example, with a viscosity of about 200 mPa·s or less at 25°C, preferably 100 mPa·s or less, and more preferably 30 mPa·s or less. Examples of monofunctional epoxy compounds include: alkyl glycidyl ethers such as 2-ethylhexyl glycidyl ether; alkenyl glycidyl ethers such as allyl glycidyl ether; aryl glycidyl ethers such as phenyl glycidyl ether and p-tert-butylphenyl glycidyl ether; glycidyl ethers of alkyl alkyl oxide adducts corresponding to these compounds; and olefinic compounds such as epoxy octane, styrene oxide, and 4-vinylcyclohexene monooxide.

[0399] Examples of multifunctional epoxy compounds include: diglycidyl ethers, polyol polyglycidyl ethers, diglycidyl aniline, and cycloalkenyl oxides. Examples of the aforementioned polyol polyglycidyl ethers include: butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and other (poly)alkanediol diglycidyl ethers; cyclohexanediol diglycidyl ether; trimethylolpropane di or triglycidyl ether; and glycerol di or triglycidyl ether. Examples of the aforementioned cycloalkenyl oxides include: vinylcyclohexene dioxide and methylated vinylcyclohexene dioxide.

[0400] These reactive diluents can be used alone or in combination of two or more. The proportion of the reactive diluent is, for example, 1 to 1000 parts by mass, preferably 5 to 500 parts by mass, and more preferably 10 to 200 parts by mass, relative to 100 parts by mass of the total amount of epoxy resin component (a compound having an epoxy group) in the epoxy curing agent composition.

[0401] The second epoxy compound can be a monomer, or a dimer, trimer, or other polymer. One type of second epoxy compound can be used alone, or two or more can be used in combination. Preferred second epoxy compounds are bisphenol A type epoxy resins or other bisphenol-type epoxy resins.

[0402] The proportion of epoxy compound represented by the above formula (8) relative to the total amount of epoxy resin in the epoxy-based curable composition can be, for example, about 10 to 100% by mass, preferably in the following ranges: 30% by mass or more, 50% by mass or more, 70% by mass or more, 90% by mass or more, and especially 100% by mass.

[0403] (Components other than polymers)

[0404] In addition to polymerizing components (or monomeric components), curable compositions may also contain free radical polymerization initiators, curing agents, curing accelerators, cationic polymerization initiators, solvents, additives, etc.

[0405] The free radical polymerization initiator can be a thermal polymerization initiator (thermal free radical generator) or a photopolymerization initiator (photofree radical generator). These can be included in (meth)acrylate-based curable compositions.

[0406] Examples of thermal polymerization initiators include organic peroxides and azo compounds. Examples of organic peroxides include dialkyl peroxides such as di-tert-butyl peroxide; diacyl peroxides such as lauroyl peroxide and benzoyl peroxide; peroxy acids (or peresters) such as tert-butyl hydroperoxide, cumene hydroperoxide, and tert-butyl peracetate; peroxide ketones; peroxy carbonates; and peroxy ketals. Examples of azo compounds include azonitrile compounds such as 2,2'-azobis(isobutyronitrile), azoamides, and azomides. These thermal polymerization initiators can be used alone or in combination of two or more.

[0407] Examples of free radical photopolymerization initiators include: benzoin derivatives, specifically benzoin alkyl ethers such as benzoin and benzoin ethyl ether; acetophenone derivatives such as 2-hydroxy-2-methyl-1-phenylpropane-1-one; aminoacetophenone derivatives such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoaminopropane-1-one; anthraquinone derivatives such as anthraquinone and 2-methylanthraquinone; thioxanthone derivatives such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; and benzophenone derivatives such as benzophenone. Tonketones, etc. These photopolymerization initiators can be used alone or in combination of two or more.

[0408] The proportion of polymerization initiator (thermal and / or photopolymerization initiator) relative to 100 parts by mass of the total amount of polymerization components 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.

[0409] In addition, photopolymerization initiators can be used in combination with photosensitizers. Representative photosensitizers include, for example, the following conventional photosensitizers: tertiary amines, such as trialkylamines; trialkylolamines such as triethanolamine; alkyl esters of dialkylaminobenzoates, specifically N,N-dimethylaminobenzoate such as ethyl p-(dimethylamino)benzoate, N,N-dimethylaminobenzoate such as amyl p-(dimethylamino)benzoate, etc.; bis(dialkylamino)benzophenone such as 4,4-bis(diethylamino)benzophenone; dialkylaminobenzophenone such as 4-(dimethylamino)benzophenone, etc. These photosensitizers can be used alone or in combination of two or more.

[0410] The proportion of photosensitizer relative to 100 parts by mass of the above-mentioned polymerization initiator 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.

[0411] Examples of curing agents include amine-based curing agents, polyaminoamide-based curing agents, acid anhydride-based curing agents, and phenolic resin-based curing agents. These can be included in epoxy-based curable compositions.

[0412] As an amine-based curing agent, it can be a primary amine, such as: chain aliphatic amines, specifically ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine and other chain aliphatic polyamines; cyclic aliphatic amines, specifically menthene diamine, isophorone diamine, bis(4-amino-3-methylcyclohexyl)methane, norbornene diamine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane and other monocyclic, bridged, or spirocyclic aliphatic polyamines; aromatic aliphatic polyamines such as phenylenediamine; and aromatic amines such as m-phenylenediamine, diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone.

[0413] Examples of polyaminoamide curing agents include condensates formed from polyethylene polyamines such as ethylenediamine, diethylenetriamine, and triethylenehexamine, with dimer acids and, optionally, fatty acids.

[0414] Examples of anhydride-based curing agents include: aliphatic anhydrides such as dodecenyl succinic anhydride and polyadipic anhydride; alicyclic anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl humic anhydride, and methylcyclohexene dicarboxylic anhydride; and aromatic anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic anhydride.

[0415] Examples of phenolic resin curing agents include: phenolic varnish resin, cresol varnish resin, and other phenolic varnish resins, as well as first-order phenolic resins.

[0416] 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 phenolic varnish resins such as phenolic varnish resins are more preferred.

[0417] The proportion of the curing agent, relative to 100 parts by mass of the total amount of epoxy resin component (a compound having epoxy groups) in the curable composition, 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. Furthermore, the proportion of the functional groups (or active hydrogens) of the curing agent, relative to 1 equivalent of the epoxy groups of the epoxy resin component, is, for example, 0.1 to 4 equivalents, preferably in the following ranges: 0.3 to 2 equivalents, 0.5 to 1.5 equivalents.

[0418] Examples of curing accelerators include: amines such as tertiary amines, imidazoles and their derivatives; alkali metal or alkaline earth metal alkoxides; phosphines, specifically triphenylphosphine and other triarylphosphines; amide compounds such as dimer acid polyamides; Lewis acid complexes such as boron trifluoride-ethylamine complexes; sulfur compounds such as polysulfides and thiols; boron compounds such as phenyl dichloroborane; and condensing organometallic compounds such as organotitanium compounds and organoaluminum compounds. Regarding the aforementioned amines, examples of tertiary amines include triethylamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo[5.4.0]-7-undecene. Examples of imidazoles include mono- or dialkyl imidazoles such as 2-methylimidazolium and 2-ethyl-4-methylimidazolium, and aryl imidazoles such as 2-phenylimidazolium. Examples of derivatives include phenol salts, phenolic varnish salts, carbonates, formates, and other salts. These curing accelerators can be used alone or in combination of two or more. Among these curing accelerators, phosphine-based accelerators are preferred, and triarylphosphine-based accelerators such as triphenylphosphine are more preferred. These curing accelerators can be included in epoxy-based curable compositions.

[0419] The proportion of the curing accelerator, relative to 100 parts by mass of the total amount of epoxy resin component (a compound having epoxy groups) in the curable composition, is, for example, 0.01 to 30 parts by mass, preferably in the following ranges: 0.05 to 20 parts by mass, 0.1 to 10 parts by mass, and 0.1 to 5 parts by mass. Furthermore, the proportion of the curing accelerator, relative to 100 parts by mass of the total amount of epoxy resin component and curing agent in the curable composition, 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.

[0420] Cationic polymerization initiators can be cationic photopolymerization initiators such as photoacid-producing agents. Cationic photopolymerization initiators can be included in epoxy-based curable compositions. Examples of cationic photopolymerization initiators include: aromatic diazonium salts, aromatic sulfonium salts, and aromatic iodine salts. Salts and other Brønsted acids Salt, etc.

[0421] Examples of aromatic diazonium salts include benzenediazo hexafluoroantimonate and benzenediazo hexafluorophosphate.

[0422] Examples of aromatic sulfonium salts include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, and other triphenylsulfonium salts, as well as 4,4'-bis(diphenylsulfonium)diphenylsulfide bis(hexafluorophosphate) and other 4,4'-bis(diphenylsulfonium)diphenylsulfide salts.

[0423] As aromatic iodine Salts, for example, include diphenyl iodine. Tetra(pentafluorophenyl)borate, diphenyliodide Diphenyliodide, such as hexafluorophosphate Class, di(4-nonylphenyl)iodine Di(4-nonylphenyl)iodide, such as hexafluorophosphate kind.

[0424] Cationic photopolymerization initiators can be used alone or in combination of two or more. The proportion of the cationic photopolymerization initiator relative to 100 parts by mass of the total amount of epoxy resin component (a compound having epoxy groups) in the curing agent composition can be about 0.1 to 10 parts by mass, preferably about 0.5 to 5 parts by mass.

[0425] The curable composition may be solvent-free, 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) above unexpectedly have high solubility, a solvent may be included as needed to adjust operability. There are no particular limitations on the solvent, but examples include: hydrocarbons, specifically aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons, specifically dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, etc.; ethers, specifically chain ethers such as diethyl ether, tetrahydrofuran, 1,4-dichloroethane, etc. Alkyl ethers and other cyclic ethers; ketones, specifically dialkyl ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and cyclic ketones such as cyclohexanone; esters, specifically acetates 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 sulfoxides; amides, specifically N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; and nitriles, specifically acetonitrile. These solvents can be used individually or in combination of two or more as a mixed solvent.

[0426] There are no particular restrictions on the proportion of solvent, and its content is such that the concentration of solid components (components other than solvent) is, for example, about 0.1 to 50% by mass relative to the whole curable composition.

[0427] The curable composition may contain conventional additives, such as colorants, stabilizers, fillers, antistatic agents, flame retardants, surfactants, plasticizers, curing agents, and polymerization inhibitors. Examples of stabilizers include heat stabilizers, antioxidants, and UV absorbers. These additives may be used individually or in combination of two or more.

[0428] The proportion of the additive, relative to the total curable composition, can be, for example, about 30% by mass or less, preferably in the following ranges: 20% by mass or less, 10% by mass or less, and 5% by mass or less. Note that the above proportions can be from 0.001 to 15% by mass, specifically from 0.01 to 3% by mass.

[0429] (cured material)

[0430] The curable composition disclosed herein can be readily cured by imparting active energy (or active energy rays) as needed, resulting in a cured product. The active energy can be thermal energy and / or light energy; for example, ultraviolet light, X-rays, etc., are useful.

[0431] When heat energy is used for heating treatment, the heating temperature is, for example, 50~200°C, preferably 60~150°C, and more preferably 70~120°C.

[0432] In addition, when using ultraviolet light or other light energy for irradiation, the irradiation energy can be appropriately selected according to the application, for example, 50~10000 mJ / cm². 2 The preferred value is 70~8000mJ / cm. 2 More preferably, it is 100~5000 mJ / cm 2 Further preferred values ​​are 200~3000mJ / cm 2 The optimal value is 300~1000mJ / cm. 2 .

[0433] There are no particular restrictions on the shape of the cured material. It can be a three-dimensional cured material with a lens-like or tubular shape, a two-dimensional cured material (or cured film) with a film-like, sheet-like, or plate-like shape, or a one-dimensional cured material with a linear, fibrous, or rod-like shape.

[0434] There are no particular limitations on the manufacturing method of the cured product. For example, depending on the shape of the cured product, the above-mentioned curable composition can be molded or cast (injected) into a specified mold, and then cured (heated and / or irradiated with light) to manufacture it. In addition, in the case of a two-dimensional structure cured product, for example, the above-mentioned curable composition can be coated onto a substrate or base material (e.g., metals such as aluminum; inorganic materials or ceramics such as titanium oxide, glass, or quartz; organic materials or plastics such as cyclic olefin resins or polycarbonate resins; porous materials such as wood, etc.) to form a film-like coating (or thin film), and then cured to manufacture it.

[0435] The cured product of this 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 of this disclosure at a temperature of 25°C and a wavelength of 589 nm can be, for example, about 1.6 to 1.8, preferably in the following ranges: 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 (especially 1.695 to 1.705).

[0436] In addition, the cured material also has high heat resistance. The glass transition temperature (Tg) of the cured material can be, for example, about 120~250°C, preferably in the following ranges: 130~200°C, 140~190°C, 150~180°C, 155~170°C, 160~165°C, and more preferably 165~170°C.

[0437] The 5% weight reduction temperature of the cured material can be, for example, about 300~450°C, preferably in the following ranges: 330~440°C, 340~430°C, 350~420°C, 360~410°C, 370~400°C, 375~395°C, and 380~390°C.

[0438] The pencil hardness of the aforementioned cured material (especially the cured film) is, for example, HB or higher, preferably F or higher, and more preferably H or higher.

[0439] It should be noted that, in this specification and claims, the refractive index, 5% weight reduction temperature, glass transition temperature, and pencil hardness of the cured product can be determined by the methods described in the examples described later.

[0440] (Compositions comprising the various fluorene compounds disclosed herein)

[0441] The fluorene compounds disclosed herein, namely the fluorene compound (diol compound) represented by formula (1) above, the (meth)acrylate compound represented by formula (7) above, the epoxy compound represented by formula (8) above, and the epoxy (meth)acrylate compound represented by formula (9) above, although having an aromatic ring (benzene ring) in their chemical structure, unexpectedly exhibit high solubility and excellent solvent solubility, and can easily or efficiently form compositions or mixtures with solvents. The above compositions can be homogeneous compositions (homogeneous mixtures or solutions) such as solutions, or heterogeneous compositions (heterogeneous mixtures) such as suspensions or colloidal dispersions. In addition, the above compositions readily dissolve the fluorene compounds of this disclosure, such as the fluorene compound represented by formula (1) above, even at high concentrations.

[0442] Examples of solvents used to form compositions with fluorene compounds of this disclosure, such as those represented by formula (1) above, 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, tetrahydrofuran (THF), and 1,4-di(2 ...2-di(2-2-di(2-2-2-di(2-2-2-di(2-2-2-di(2-2-2-di(2-2-2-2-di(2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2-2 Cyclic ethers such as alkanes, aromatic ethers such as anisole; 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); ketones, specifically chain ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK), and cyclic ketones such as cyclohexanone; esters, such as acetates such as ethyl acetate, methyl lactate, and ethyl lactate. Lactates such as esters 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.

[0443] These solvents can be used alone or in combination of two or more. Preferably, at least one of these solvents is selected from ketones, esters, ethers, ether esters, amides, and aromatic hydrocarbons. In the case of a fluorene compound represented by formula (1) above, ketones, esters, ethers, and aromatic hydrocarbons are preferred, with ketones such as acetone, MEK, and MIBK being particularly preferred; tetrahydrofuran, 1,4-dihydrofuran, etc. Alkane and other ethers, the above-mentioned fluorene compounds are readily soluble in these solvents. Furthermore, in the case of (meth)acrylate compounds represented by formula (7) above, 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. In the case of epoxy compounds represented by formula (8) above, ketones, ethers, ether esters, amides, and aromatic hydrocarbons are preferred, and they appear to exhibit higher solubility in any solvent. In the case of epoxy (meth)acrylate compounds represented by formula (9) above, ketones, ethers, ether esters, amides, and aromatic hydrocarbons are preferred, with ketones such as acetone, MEK, and MIBK, and 1,4-diethyl-2-ethylhexylene compounds being more preferred. Ethers such as alkanes, ether esters such as PGMEA, and amides such as DMF.

[0444] 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) above, and a solvent, the proportion of the fluorene compound [the fluorene compound represented by formula (1), formula (7), formula (8), and / or formula (9) above] relative to the total composition is, for example, 1 to 70% by mass, preferably 2 to 60% by mass, more preferably 3 to 50% by mass, and particularly 5 to 45% by mass. Furthermore, the proportion of the fluorene compound relative to the total amount of the fluorene compound and the solvent is, for example, 1 to 70% by mass, preferably 2 to 60% by mass, more preferably 3 to 50% by mass, and particularly 5 to 45% by mass.

[0445] It should be noted that the above composition may also be a reaction solution (reaction mixture) containing other reactive components and / or catalysts, for example, a reaction solution for solution polymerization of the fluorene compound represented by formula (1) above as a monomer.

[0446] Thus, the aforementioned fluorene compounds or compositions can simultaneously satisfy high levels of solubility, refractive index, and heat resistance (or heat decomposition resistance). Therefore, as described above, the aforementioned fluorene compounds or compositions can not only be effectively utilized as reactants such as monomers (resin raw materials), but can also be easily or efficiently mixed into resins through melt mixing and other methods, and effectively utilized as resin modifiers.

[0447] Example

[0448] The present disclosure will now be described in more detail based on embodiments, but the present disclosure is not limited to these embodiments. Details of the evaluation method are shown below.

[0449] [Evaluation Method]

[0450] (HPLC)

[0451] Using the "LC-2030" manufactured by Shimadzu Corporation as the HPLC (High Performance Liquid Chromatography, also known as LC) instrument and the "ODS-80TM" manufactured by Tosoh Corporation as the column, the sample was dissolved in acetonitrile for determination, and the HPLC purity [area %] was calculated.

[0452] ( 1 H-NMR and 13 C-NMR)

[0453] The sample was dissolved in a heavy solvent (CDCl3) containing tetramethylsilane as an internal standard, and the results were determined using a nuclear magnetic resonance (NMR) apparatus (BRUKER "AVANCE III HD"). 1 H-NMR spectrum and 13C-NMR spectra. It should be noted that the DNBBzOPPFG and DNBBzOPPFGA obtained in Examples 5 and 6 were dissolved in DMSO-d6 without tetramethylsilane, and otherwise measured in the same manner.

[0454] (IR)

[0455] The measurements were performed using a Fourier transform infrared spectrophotometer (FT / IR-4100 manufactured by Nippon Spectrophotometer Co., Ltd.) via the ATR method (total reflectance measurement).

[0456] (LC-MS)

[0457] The sample was dissolved in a mixed solvent of acetonitrile and THF (acetonitrile / THF = 90 / 10 (mass ratio)) and analyzed using a Shimadzu Nexera XR HPLC (high performance liquid chromatography, also known as LC) instrument, an LCMS-2020 MS unit, and a Phenomenex Kinetex C-18 column.

[0458] (MALDI TOF-MS)

[0459] Mass spectrometry (MS) analysis was performed using the following measuring apparatus and conditions.

[0460] Equipment used: Shimadzu Corporation's "AXIMA Assurance" TM "

[0461] Ionization method: MALDI (Matrix Assisted Laser Desorption / Ionization)

[0462] Detection of ions: cations

[0463] Matrix: α-cyano-4-hydroxycinnamic acid (CHCA)

[0464] (Refractive index nD)

[0465] The refractive index was measured using a refractometer at a temperature of 25°C and a wavelength of 589 nm (D-rays). It should be noted that the refractive index before curing (refractive index of the (meth)acrylate compound) was measured using ATAGO Corporation's "RX-7000i", and the refractive index of the cured product was measured using ATAGO Corporation's "DR-M2 / 1410". Furthermore, the refractive index before curing was calculated as follows: the sample was dissolved in cyclohexanone to prepare solutions with concentrations (mass%) of 10% and 15% (mass%). The refractive index was obtained by extrapolating the concentration to 100% (approximately a straight line) from a calibration curve (approximately a straight line) constructed by measuring the refractive index of the obtained solutions and the refractive index at a concentration of 0% (i.e., cyclohexanone only).

[0466] (5% weight reduction in temperature Td5)

[0467] Using a thermogravimetric-differential thermal analysis (TG-DTA) apparatus (Rigaku Corporation "TG-DTA8122"), under a nitrogen atmosphere and a heating rate of 10 °C / min, the temperature at which the mass of the sample decreases by 5% was determined.

[0468] (Melting point)

[0469] The measurements were performed using a differential scanning calorimeter (DSC) (TA Instruments "Discovery DSC25") under a nitrogen atmosphere, at a measurement temperature of 30–280 °C, and a heating rate of 10 °C / min. The peak temperature of the endothermic peak was read from the obtained DSC plot.

[0470] (Glass transition temperature Tg)

[0471] The glass transition temperature of the sample was determined using a differential scanning calorimeter (DSC6220, manufactured by SII Nanotechnology) at a temperature of 30–350 °C and a heating time of 10 °C / min.

[0472] (Pencil hardness)

[0473] According to the pencil hardness method (JIS K-5600-5-4 (1999)), a pencil hardness tester (HEIDON-14 manufactured by Shin-To Science Co., Ltd.) was used to apply a 750g load to a 10μm thick cured film formed on a polyethylene terephthalate plate for measurement.

[0474] (Solubility)

[0475] Relative to 100 mg of sample, each of the solvents described below was added to a concentration of 10%, 20%, 30%, or 50% by mass. The solubility of the sample in each solvent was confirmed after stirring at room temperature (25°C) for 1 hour. If the sample was insoluble at room temperature (25°C), the temperature was gradually increased to 50°C. After reaching 50°C, the sample was stirred for 1 hour, or the stirring time at room temperature (25°C) was extended to 2 hours. The solubility was confirmed according to the evaluation criteria below.

[0476] ◎: Dissolves at 25°C within 1 hour.

[0477] ○: If it does not dissolve within 1 hour at 25°C, it will dissolve within 1 hour after the temperature is raised to 50°C, or it will dissolve within 2 hours at 25°C.

[0478] ×: If it does not dissolve after being heated to 50℃ for more than 1 hour or after being heated to 25℃ for more than 2 hours.

[0479] (Epoxy equivalent)

[0480] According to JIS K 7236:2001, titration was performed using an automatic titration apparatus (Mitsubishi Chemical Co., Ltd. GT-100) with perchloric acid solution (acetic acid).

[0481] [Example 1]

[0482] [Synthesis of 9,9-bis[(3-benzyl-4-hydroxy-5-phenyl)phenyl]-2,7-dibromofluorene (hereinafter also referred to as DBrBBzOPPF)]

[0483] [Chemistry 18]

[0484]

[0485] In a separable flask, add 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. Stir under reflux (110℃~120℃) until the peak of 2,7-dibromo-9-fluorenone disappears in LC (liquid chromatography). Cool to 80℃, then add 566 g of N,N-dimethylformamide (DMF) and 102 g of toluene until homogeneous. Wash the resulting solution with 300 g of deionized water and remove the aqueous layer. After repeating the water washing operation four times, the organic layer was concentrated under reduced pressure and crystallized with 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%. The obtained DBrBBzOPPF... 1 The results of H-NMR are shown below.

[0486]

[0487] [Synthesis of 9,9-bis[(3-benzyl-4-hydroxy-5-phenyl)phenyl]-2,7-diphenylfluorene (hereinafter also referred to as DPBBzOPPF)]

[0488] [Chemistry 19]

[0489]

[0490] In a flask equipped with a stirrer, cooler, and thermometer, 27.6 g (0.03 mol) of DBrBBzOPPF synthesized in Example 1 ([Synthesis of 9,9-bis[(3-benzyl-4-hydroxy-5-phenyl)phenyl]-2,7-dibromofluorene (hereinafter also referred to as DBrBBzOPPF)], 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 deionized water were added and dissolved. Then, 16.4 mg of palladium acetate and 37.3 mg of triphenylphosphine were added and the mixture was stirred. The mixture was heated to reflux and stirred for 7 hours. After confirming that the starting material had disappeared from the HPLC, the aqueous layer was removed, and the washing process was repeated twice with 22 g of deionized water. 4 g of activated carbon was added to the organic layer, and the mixture was stirred for 1 hour. After filtration, the resulting solution was concentrated under reduced pressure and crystallized from methanol to obtain 17.0 g of white crystals of DPBBzOPPF (yield 62%, HPLC purity 99.2%). The obtained DPBBzOPPF has a refractive index nD of 1.679, a melting point of 200℃, and a 5% weight reduction temperature of 408.3℃. 1 The results of H-NMR are shown below.

[0491]

[0492] [Example 2]

[0493] [Synthesis of 9,9-bis[(3-benzyl-4-hydroxy-5-phenyl)phenyl]-2,7-dibromofluorene (hereinafter also referred to as DBrBBzOPPF)]

[0494] DBrBBzOPPF was synthesized according to the method described in Example 1.

[0495] Synthesis of [9,9-bis[(3-benzyl-4-hydroxy-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene (hereinafter also referred to as DNBBzOPPF)]

[0496] [Chemistry 20]

[0497]

[0498] In a flask equipped with a stirrer, cooler, and thermometer, 29.31 g (0.035 mol) of DBrBBzOPPF, 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 deionized water, synthesized according to the method described in Example 1, were added and dissolved. Then, 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 that the starting material had disappeared from the HPLC, the aqueous layer was removed, and the washing process was repeated twice with 45 g of deionized water. 12 g of activated carbon was added to the organic layer, and the mixture was stirred for 1 hour. After filtration, 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 obtained DNBBzOPPF has a refractive index nD of 1.717, a melting point of 203℃, and a 5% weight reduction temperature of 410.2℃. 1 The results of H-NMR are shown below.

[0499]

[0500] [Comparative Example 1]

[0501] 9,9-bis(4-hydroxy-3,5-diphenylphenyl)fluorene (hereinafter also referred to as BDPPF) was prepared according to the method described in Reference Example 1 of Japanese Patent Application Publication No. 2017-155131, and the refractive index, melting point, and 5% weight reduction temperature were measured. The refractive index nD of BDPPF was 1.687, the melting point was 320°C, and the 5% weight reduction temperature was 400°C.

[0502] [Chemistry 21]

[0503]

[0504] Next, the evaluation results of the solubility (solubility) of the fluorene compounds (final products) obtained in Examples 1, 2 and Comparative Example 1 when dissolved in each solvent at concentrations of 10%, 20%, and 30% by mass, respectively, are shown in Table 1.

[0505] [Table 1]

[0506]

[0507] Examples 1 (DPBBzOPPF) and 2 (DNBBzOPPF) exhibit high refractive indices. In particular, Example 2 (DNBBzOPPF), due to its greater benzene ring backbone, shows a higher refractive index than Example 1 (DPBBzOPPF). The 5% weight reduction temperature of Examples 1 (DPBBzOPPF) and 2 (DNBBzOPPF) is higher than that of Comparative Example 1 (BDPPF), and both Examples 1 and 2 exhibit excellent heat resistance.

[0508] On the other hand, since Examples 1 (DPBBzOPPF) and 2 (DNBBzOPPF) contain many benzene ring skeletons, their solubility was expected to be significantly reduced. However, as shown in Table 1, the solvents that Comparative Example 1 (BDPPF) can dissolve are very limited, while Examples 1 (DPBBzOPPF) and 2 (DNBBzOPPF), which contain more benzene ring skeletons than Comparative Example 1 (BDPPF), unexpectedly showed high solubility and were soluble in a variety of solvents. In particular, Example 1 (DPBBzOPPF) was not only soluble in a variety of solvents, but also soluble in a variety of solvents even at high concentrations. In addition, Example 2 (DNBBzOPPF) showed a very high refractive index and, although it contained more benzene ring skeletons than Example 1 (DPBBzOPPF), it unexpectedly dissolved in a variety of solvents even at high concentrations.

[0509] That is, the compounds of Example 1 (DPBBzOPPF), Example 2 (DNBBzOPPF), and Comparative Example 1 (BDPPF) contain a large number of benzene ring (aromatic ring) skeletons. All three compounds have high heat resistance and high refractive index, and it is expected that the presence of a large number of aromatic ring skeletons will reduce solubility. However, the high solubility of Example 1 (DPBBzOPPF) and Example 2 (DNBBzOPPF) in a variety of solvents is an unexpected result. Example 1 (DPBBzOPPF) and Example 2 (DNBBzOPPF) are able to simultaneously satisfy refractive index, heat resistance, and solubility at a high level.

[0510] [Example 3]

[0511] Synthesis of 9,9-bis[(3-benzyl-4-(2-acryloyloxyethoxy)-5-phenyl)phenyl]-2,7-bis(2-naphthyl)fluorene (hereinafter also referred to as DNBBzOPPEFA)]

[0512] In a separable flask, add 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. Stir under reflux (110–120 °C) until the peak of 2,7-dibromo-9-fluorenone disappears in LC (liquid chromatography). Cool to 80 °C, then add 68 g of N,N-dimethylformamide (DMF) and dissolve thoroughly. Add 68 g of deionized water to the resulting solution for washing, then remove the aqueous layer. Repeat this washing operation twice. The organic layer was dehydrated by azeotropic extraction to obtain 171.73 g of a solution containing 9,9-bis[(3-benzyl-4-hydroxy-5-phenyl)phenyl]-2,7-dibromofluorene (DBrBBzOPPF).

[0513] Add 20.14 g (0.22 mol, 2.2 eq) of ethylene carbonate, 10.06 g (0.7 mol) of potassium carbonate, and 59 g of DMF to the resulting solution. Stir under nitrogen atmosphere and reflux (110–120 °C) until the monosubstituted compound (the compound obtained by reacting DBrBBzOPPF with only one molecule of ethylene carbonate) is less than 3% in LC (liquid chromatography). Cool to 80 °C. Add 71.1 g of 24% NaOH aqueous solution, stir at 80 °C for 2 hours, then add 67 g of DMF, 80 g of toluene, and 102 g of deionized water to dissolve and remove the aqueous layer. Add 50 g of deionized water and remove the aqueous layer. Repeat this operation 5 times. Concentrate the organic layer and add methanol to obtain 124.7 g of crude crystals. 166g of MIBK was dissolved in the crude crystals, and then ion exchange resins (+) K1221 and (-) K1261 were added. After stirring at 85°C for 2 hours, the solution was poured onto diatomaceous earth covered with activated carbon and filtered. The solution was concentrated under reduced pressure and crystallized from methanol to obtain 64.7g of 9,9-bis[(3-benzyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-2,7-dibromofluorene (DBrBBzOPPEF) (yield 69.7%).

[0514] Add 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 deionized 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. Degas under reduced pressure, replace with nitrogen, and stir under reflux (90–100 °C). The endpoint is set at the point where the peak of the monosubstituted product (the compound obtained by reacting DBrBBzOPPEF with only one molecule of 2-naphthylboronic acid) disappears in LC. Cool to 80 °C and remove the lower layer. Wash with 18 g of deionized water to remove the aqueous layer. Repeat this operation three times. Add 3.1 g of activated carbon to the organic layer, stir at 70 °C for 1 hour, and then filter. Add 18 g of ion-exchanged water to the obtained solution and remove the aqueous layer. Repeat this operation twice. Concentrate the solution under reduced pressure and crystallize it through methanol to obtain 24.5 g of 9,9-bis[(3-benzyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene (DNBBzOPPEF) (yield 79.8%).

[0515] Add 100.02 g (0.1 mol) of DNBBzOPPEF, 17.39 g (0.51 mol, 2.46 eq) of acrylic acid, 0.214 g (2.3 mmol, 0.02 eq) of p-methoxyphenol (methoxyquinone), 98.21 g of toluene, and 2.8 g (0.014 mol) of p-toluenesulfonic acid monohydrate. Stirring while removing the generated water under reflux (110–120 °C), the mixture was stirred until the monosubstituted product (the compound obtained by reacting DNBBzOPPEF with only one molecule of acrylic acid) reached less than 20% in LC. Toluene was then added. The mixture was washed once with 35 g of 20% physiological saline, once with a mixture of 20% physiological saline and 10% NaOH aqueous solution, twice with 35 g of 20% physiological saline, and twice with 35 g of deionized water. 25 g of activated carbon was added to the solution and stirred at room temperature for 1 hour. The solution was filtered with diatomaceous earth. 0.012 g of p-methoxyphenol was added to the diatomaceous earth-filtered solution and the solution was concentrated under reduced pressure to obtain 90.1 g of 9,9-bis[(3-benzyl-4-(2-acryloyloxyethoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene (DNBBzOPPEFA) (yield 81.0%, HPLC purity 82.8%).

[0516] [Chemistry 22]

[0517]

[0518] The obtained DNBBzOPPEFA 1 H-NMR and 13 The C-NMR results are shown below. 1 The H-NMR spectrum is shown in Figure 1 , 13 The C-NMR spectrum is shown in Figure 2 .

[0519]

[0520]

[0521] The obtained DNBBzOPPEFA has a refractive index nD of 1.668, a glass transition temperature Tg of 163℃, and a 5% weight reduction temperature of 399.3℃.

[0522] (Preparation of curable composition)

[0523] Relative to 100 parts by weight (3.00 g) of DNBBzOPPEFA, add 3 parts by weight of photopolymerization initiator A (BASF Japan's "Irgacure 184") and 2 parts by weight of photopolymerization initiator B (BASF Japan's "Darocure TPO"), dilute and mix with 101 parts by weight (3.02 g) of N,N-dimethylformamide (DMF), heat on a hot plate at 80°C for 3 minutes, and then irradiate with a high-pressure mercury lamp using UV irradiation (500 mJ / cm). 2 ), to obtain a cured film.

[0524] The obtained DNBBzOPPEFA cured product has a refractive index of 1.685, a Tg of 167℃, a 5% weight reduction temperature of 385.8℃, and a pencil hardness of H.

[0525] [Example 4]

[0526] [Synthesis of 9,9-bis[(3-benzyl-4-(2-acryloyloxyethoxy)-5-phenyl)phenyl]-2,7-diphenylfluorene (hereinafter also referred to as DPBBzOPPEFA)]

[0527] 41.9 g (0.045 mol) of DBrBBzOPPEF obtained in Example 3, 12.3 g (0.99 mol, 2.2 eq) of phenylboronic acid, 74.8 g of MIBK, 10.7 g (0.99 mol) of sodium carbonate, 30.4 g of deionized 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. After degassing under reduced pressure and purging with nitrogen, the mixture was stirred under reflux (90-100 °C) until the peak of the monosubstituted compound (the compound obtained by reacting DBrBBzOPPF with only one molecule of phenylboronic acid) disappeared in LC. The mixture was cooled to 80 °C and the lower layer was removed. 28 g of deionized water was added for washing to remove the aqueous layer. This operation was repeated 3 times. 3.1 g of activated carbon was added to the organic layer and 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).

[0528] Add 49.1 g (0.045 mol) of DPBBzOPPEF solution, 10.3 g (0.14 mol, 3.15 eq) of acrylic acid, 0.101 g (0.79 mmol, 0.0175 eq) of p-methoxyphenol, 61.6 g of toluene, and 1.45 g (0.008 mol) of p-toluenesulfonic acid monohydrate. Stirring while removing the generated water under reflux (110–120 °C), the mixture was stirred until the monosubstituted product (the compound obtained by reacting DPBBzOPPEF with only one molecule of acrylic acid) reached less than 20% in LC. Toluene was then added. The mixture was washed once with 16.3 g of 20% physiological saline, once with a mixture of 20% physiological saline and 10% NaOH aqueous solution, twice with 16.3 g of 20% physiological saline, and twice with 16 g of deionized water. Add 8.9 g of activated carbon to the solution, stir for 1 hour at room temperature, filter with diatomaceous earth, add 5.9 mg of p-methoxyphenol to the filtered solution, concentrate under reduced pressure to obtain 18.0 g of 9,9-bis[(3-benzyl-4-(2-acryloyloxyethoxy)-5-phenyl)phenyl]-2,7-diphenylfluorene (DPBBzOPPEFA) represented by the following formula (yield 39%, HPLC purity 76.7%).

[0529] [Chemistry 23]

[0530]

[0531] The obtained DPBBzOPPEFA 1 H-NMR and 13 The C-NMR results are shown below.

[0532]

[0533] The obtained DPBBzOPPEFA has a refractive index nD of 1.6276, a glass transition temperature Tg of 160℃, and a 5% weight reduction temperature of 395.8℃.

[0534] (Preparation of curable composition)

[0535] Compared to 100 parts by weight (5.00 g) of DPBBzOPPEFA, add 3 parts by weight of photopolymerization initiator A (BASF Japan's "Irgacure 184") and 2 parts by weight of photopolymerization initiator B (BASF Japan's "Darocure TPO"), dilute and mix with 100 parts by weight (5.00 g) of methyl ethyl ketone (MEK), heat on a hot plate at 100°C for 3 minutes, and then irradiate with a high-pressure mercury lamp using UV irradiation (500 mJ / cm). 2 ), to obtain a cured film.

[0536] The obtained cured DPBBzOPPEFA has a refractive index of 1.655, a Tg of 166℃, a 5% weight reduction temperature of 369.4℃, and a pencil hardness of HB.

[0537] [Comparative Example 2]

[0538] According to the method described in Example 1 of WO2021 / 131942, 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.

[0539] [Chemistry 24]

[0540]

[0541] The refractive index nD of the obtained DNFPA (according to the method described in Example 1 of WO2021 / 131942) is 1.682.

[0542] (Preparation of curable composition)

[0543] The cured film was obtained according to the method described in Example 1 of WO2021 / 131942. The resulting cured DNFPA had a refractive index of 1.701, a glass transition temperature (Tg) of 23°C, a 5% weight reduction temperature of 382°C, and a pencil hardness of HB.

[0544] Table 2 shows the evaluation results of the solubility of the (meth)acrylate compounds obtained in Examples 3-4 and Comparative Example 2 when dissolved in each solvent at a concentration of 50% by mass.

[0545] [Table 2]

[0546]

[0547] In Table 2, “×※” is the evaluation benchmark equivalent to “×”, meaning that at a concentration of approximately 10% by mass, it can dissolve at 25°C within 1 hour.

[0548] Although the (meth)acrylate compounds of Examples 3 (DNBBzOPPEFA) and 4 (DPBBzOPPEFA) contain many benzene rings, their solvent solubility remains excellent. Furthermore, the (meth)acrylate compounds of Examples 3 and 4 exhibit high solvent solubility in various solvents, even at high concentrations such as 50% by mass.

[0549] The evaluation results of the refractive index, thermal properties, and mechanical properties of the (meth)acrylate compounds obtained in Examples 3-4 and Comparative Example 2 before and after curing are shown in Table 3.

[0550] [Table 3]

[0551]

[0552] The (meth)acrylate compounds of Examples 3 (DNBBzOPPEFA) and 4 (DPBBzOPPEFA) have high refractive indices and excellent heat resistance.

[0553] Furthermore, regarding the cured product, compared to the (meth)acrylate compound of Comparative Example 2 (DNFPA), the (meth)acrylate compound of Example 3 exhibits a higher refractive index, superior optical properties, a higher glass transition temperature and 5% weight loss temperature, superior thermal properties, and higher pencil hardness. In contrast, the (meth)acrylate compound of Comparative Example 2 has a lower glass transition temperature, lower heat resistance, and lower pencil hardness.

[0554] That is, in the embodiments, even if the chemical structure contains many benzene rings, it can still have both high refractive index and high solubility.

[0555] [Example 5]

[0556] [Synthesis of 9,9-bis[(3-benzyl-4-glycidoxy-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene (hereinafter also referred to as DNBBzOPPFG)]

[0557] Add 28.1 g (0.03 mol) of DNBBzOPPF, 130.1 g (1.42 mol) of epichlorohydrin, and 15.3 g of dimethyl sulfoxide (DMSO), and heat to 50 °C. Add 2.71 g of sodium hydroxide, stir at 70 °C, and concentrate under reduced pressure at 85 °C to remove residual epichlorohydrin and DMSO, using the point where the peak of DNBBzOPPF disappears in LC (liquid chromatography) as the endpoint. Add 100 g of methyl isobutyl ketone (MIBK) and dissolve thoroughly. Add 0.8 g of 30% (w / w) sodium hydroxide aqueous solution, stir at 75 °C for 1 hour, and filter out insoluble components using diatomaceous earth. Add 50 g of MIBK to the resulting solution, wash with 80 g of deionized water, and remove the aqueous layer. Repeat this washing operation 5 times. The solution was concentrated under reduced pressure and then precipitated with methanol to obtain 29.8 g of 9,9-bis[(3-benzyl-4-glycidoxy-5-phenyl)phenyl]-2,7-bis(2-naphthyl)fluorene (DNBBzOPPFG) (yield 95%).

[0558] [Chemistry 25]

[0559]

[0560] The obtained DNBBzOPPFG 1 H-NMR and 13 The C-NMR results are shown below. 1 The H-NMR spectrum is shown in Figure 3 , 13 The C-NMR spectrum is shown in Figure 4 .

[0561]

[0562] In the LC-MS spectrum of the obtained DNBBzOPPFG, a peak was confirmed at m / z = 1088 (= 1046 (DNBBzOPPFG) + 41 [acetonitrile] + 1 [e+]). Additionally, in... Figure 6 The IR spectrum of DNBBzOPPFG is shown below. Figure 5 The peak originating from OH (3518 cm⁻¹) is visible in the DNBBzOPPF sample. -1 and 3477cm -1 The peak disappears, and a peak from the ether bond appears (1254 cm⁻¹). -1 and 1217cm -1 The peak (1011 cm⁻¹) is presumed to originate from the epoxide ring. -1 These results support the successful synthesis of DNBBzOPPFG.

[0563] The obtained DNBBzOPPFG has a refractive index nD of 1.6988, a melting point of 105.04℃, a 5% weight reduction temperature of 370.02℃, and an epoxy equivalent of 547.41 g / eq.

[0564] [Example 6]

[0565] [Synthesis of 9,9-bis[(3-benzyl-4-(3-acryloyloxy-2-hydroxypropoxy)-5-phenyl)phenyl]-2,7-bis(2-naphthyl)fluorene (hereinafter also referred to as DNBBzOPPFGA)]

[0566] 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 p-methoxyphenol, and 43.1 mg of tetramethylammonium bromide were added and stirred at 110 °C for 30 hours. Then, 15.85 g of PGMEA was added to obtain a 50.0% by mass solution 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. PGMEA was removed from the resulting solution to obtain DNBBzOPPFGA.

[0567] [Chemistry 26]

[0568]

[0569] The obtained DNBBzOPPFGA 1 H-NMR and 13 The C-NMR results are shown below. 1 The H-NMR spectrum is shown in Figure 7 , 13 The C-NMR spectrum is shown in Figure 8 .

[0570]

[0571]

[0572] In the obtained LC-MS spectrum of DNBBzOPPFGA, a peak was confirmed at m / z = 1191 (= 1190 (DNBBzOPPFGA) + 1 [e+]), and a peak was confirmed at m / z = 1190 in the MALDI TOF-MS spectrum. Additionally, in... Figure 9 The IR spectrum of DNBBzOPPFGA shown below shows... Figure 6The peak from OH not observed in the DNBBzOPPFG shown (3440 cm⁻¹) -1 ), the peak from C=O (1724 cm) -1 ) and the peak from C=C (1633cm) -1 These results support the successful synthesis of DNBBzOPPFGA.

[0573] The obtained DNBBzOPPFGA has a refractive index nD of 1.6776, a glass transition temperature Tg of 80.46℃, and a 5% weight reduction temperature of 377.45℃.

[0574] (Preparation of curable composition)

[0575] Compared to 100 parts by weight (2.00 g) of DNBBzOPPFGA, 3 parts by weight of photopolymerization initiator A (BASF Japan "Irgacure 184") and 2 parts by weight of photopolymerization initiator B (BASF Japan "Darocure TPO") were added, diluted and mixed with 101 parts by weight (2.01 g) of PGMEA, heated on a hot plate at 80°C for 3 minutes, and then irradiated with UV light (500 mJ / cm²) using a high-pressure mercury lamp. 2 ), to obtain a cured film.

[0576] The obtained DNBBzOPPFGA cured product has a refractive index of 1.701, a glass transition temperature (Tg) of 158.22℃, a 5% weight reduction temperature of 355.24℃, and a pencil hardness of H.

[0577] The evaluation results of the solubility of the epoxy compounds (epoxy resins) and epoxy (meth)acrylate compounds obtained in Examples 5-6 when dissolved in each solvent at a concentration of 50% by mass are shown in Table 4.

[0578] [Table 4]

[0579]

[0580] In Examples 5 and 6, the epoxy compounds (epoxy resins) or epoxy (meth)acrylate compounds not only exhibited high refractive index and excellent heat resistance, but also, as shown in Table 4, excellent solvent solubility in various solvents, even at high concentrations of 50% by mass.

[0581] Thus, the fluorene compounds of this disclosure [diol compounds represented by formula (1), (meth)acrylate compounds represented by formula (7), epoxy compounds (epoxy resins) represented by formula (8) and epoxy (meth)acrylate compounds represented by formula (9)] can still achieve both high refractive index and high solubility despite containing many benzene ring (aromatic ring) skeletons in their chemical structures.

[0582] Industrial practicality

[0583] The fluorene compound represented by formula (1) of this disclosure exhibits a high refractive index and excellent heat resistance, and therefore can be effectively used as a resin raw material, for example, as a monomer component of thermoplastic resins such as polyester resins, polycarbonate resins, polyether resins, polyetherketone resins, and polyetheretherketone resins, or as a raw material for curable resins such as (meth)acrylate 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 reduction temperature, exhibits high heat resistance, and also has excellent solubility, and therefore can be used as a monomer for melt polymerization or solution polymerization.

[0584] Furthermore, the fluorene compound represented by formula (1) above can be effectively used as an additive (or resin additive) such as a refractive index improver, a heat resistance improver, and a curing agent [e.g., a curing agent for epoxy resins such as an epoxy compound represented by formula (8)]. The fluorene compound represented by formula (1) above also has excellent solubility (compatibility), so a homogeneous composition can be easily or efficiently prepared by melt mixing or the like.

[0585] Resins made from fluorene compounds represented by formula (1) of this disclosure, or compositions containing such fluorene as an additive, are suitable for use in optical components (optical materials or transparent materials), membranes for fuel cells, etc. Examples of such optical components include: optical lenses such as reflow lenses, pickup lenses, and microlenses; optical films such as polarizing films, anti-reflective films, films for touch screens, films for flexible substrates, and films for displays; OCR or OCA (optical adhesives or pressure-sensitive adhesives); optical fibers; optical waveguides; holograms, etc.

Claims

1. A fluorene compound represented by the following formula (1), In the formula, Y 1a and Y 1b Independently represent the monovalent group represented by the following formula (Y1), In the formula, Z 1 R represents an aromatic ring. 1 This represents a substituent, and m1 represents an integer greater than or equal to 0 or 1. R 2a and R 2b The substituents are represented independently, and m2a and m2b independently represent integers from 0 to 3. Y 2a and Y 2b Independently represent the monovalent group represented by the following formula (Y2), In the formula, A 1 Indicates an alkylene group, n1 represents an integer of 0 or higher. R 3 This represents a substituent, and m3 represents an integer from 0 to 5. A 2 Indicates alkylene, R 4 This represents a substituent, and m4 represents an integer from 0 to 5. R 5 represents a substituent, and m5 represents an integer from 0 to 2.

2. The fluorene compound according to claim 1, wherein, In the above equation (1), Z 1 Indicate C 6-12 In an aromatic ring, m1 represents an integer from 0 to 2, m2a and m2b independently represent integers from 0 to 2, and m3, m4, and m5 independently represent integers from 0 to 2. R 1 ~R 5 Independently representing a hydrocarbon group, A 1 Indicate C 2-6 Alkylene, n1 represents 0 or an integer from 1 to 6, A 2 Indicate C 1-4 Alkylene.

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

4. The fluorene compound according to claim 1 or 2, wherein it is a crystal and has a melting point of 195~210°C.

5. The fluorene compound according to claim 1 or 2, wherein it is selected from at least one monomer used for melt polymerization or solution polymerization and resin additives used for modifying resins.

6. The method for producing the fluorene compound according to claim 1 or 2, comprising the reaction steps described in (i) and (ii) below: (i) A process for reacting the compound represented by formula (2) with the compound represented by formula (3a) and the compound represented by formula (3b), (ii) A step of coupling the compound represented by formula (4) with the compound represented by formula (5a) and the compound represented by formula (5b), In the formula, X 1a and X 2a and X 1b and X 2b Y represents a pair of reactive groups that can form a carbon-carbon bond through a coupling reaction. 1a and Y 1b R 2a and R 2b m2a and m2b, and Y 2a and Y 2b Same as Equation (1).

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

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

9. A (meth)acrylate compound represented by the following formula (7), In the formula, Y 1a and Y 1b Independently represent the monovalent group represented by the following formula (Y1), In the formula, Z 1 R represents an aromatic ring. 1 This represents a substituent, and m1 represents an integer greater than or equal to 0 or 1. R 2a and R 2b The substituents are represented independently, and m2a and m2b independently represent integers from 0 to 3. Y 3a and Y 3b Independently represent the monovalent group represented by the following formula (Y3), In the formula, A 1 Indicates an alkylene group, n1 represents an integer of 0 or higher. R 3 This represents a substituent, and m3 represents an integer from 0 to 5. A 2 Indicates alkylene, R 4 This represents a substituent, and m4 represents an integer from 0 to 5. R 5 Indicates a substituent, m5 represents an integer from 0 to 2. R 6 It represents a hydrogen atom or a methyl group.

10. The (meth)acrylate compound according to claim 9, wherein, In the above equation (7), Z 1 Indicate C 6-12 In an aromatic ring, m1 represents an integer from 0 to 2, m2a and m2b independently represent integers from 0 to 2, and m3, m4, and m5 independently represent integers from 0 to 2. R 1 ~R 5 Independently representing a hydrocarbon group, A 1 Indicate C 2-6 Alkylene, n1 represents 0 or an integer from 1 to 6, A 2 Indicate C 1-4 Alkylene.

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

12. An epoxy compound represented by the following formula (8), In the formula, Y 1a and Y 1b Independently represent the monovalent group represented by the following formula (Y1), In the formula, Z 1 R represents an aromatic ring. 1 This represents a substituent, and m1 represents an integer greater than or equal to 0 or 1. R 2a and R 2b The substituents are represented independently, and m2a and m2b independently represent integers from 0 to 3. Y 4a and Y 4b Independently represent the monovalent group represented by the following formula (Y4), In the formula, A 1 Indicates an alkylene group, n1 represents an integer of 0 or higher. R 3 This represents a substituent, and m3 represents an integer from 0 to 5. A 2 Indicates alkylene, R 4 This represents a substituent, and m4 represents an integer from 0 to 5. R 5 Indicates a substituent, m5 represents an integer from 0 to 2. R 7 It represents a hydrogen atom or a methyl group.

13. The epoxy compound according to claim 12, wherein, In equation (8), Z 1 Indicate C 6-12 In an aromatic ring, m1 represents an integer from 0 to 2, m2a and m2b independently represent integers from 0 to 2, and m3, m4, and m5 independently represent integers from 0 to 2. R 1 ~R 5 Independently representing a hydrocarbon group, A 1 Indicate C 2-6 Alkylene, n1 represents 0 or an integer from 1 to 6, A 2 Indicate C 1-4 Alkylene.

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

15. An epoxy (meth)acrylate compound represented by the following formula (9), In the formula, Y 1a and Y 1b Independently represent the monovalent group represented by the following formula (Y1), In the formula, Z 1 R represents an aromatic ring. 1 This represents a substituent, and m1 represents an integer greater than or equal to 0 or 1. R 2a and R 2b The substituents are represented independently, and m2a and m2b independently represent integers from 0 to 3. Y 5a and Y 5b Independently represent the monovalent group represented by the following formula (Y5), In the formula, A 1 Indicates an alkylene group, n1 represents an integer of 0 or higher. R 3 This represents a substituent, and m3 represents an integer from 0 to 5. A 2 Indicates alkylene, R 4 This represents a substituent, and m4 represents an integer from 0 to 5. R 5 Indicates a substituent, m5 represents an integer from 0 to 2. R 7 Indicates a hydrogen atom or a methyl group. R 8 It represents a hydrogen atom or a methyl group.

16. The epoxy (meth)acrylate compound according to claim 15, wherein, In equation (9), Z 1 Indicate C 6-12 In an aromatic ring, m1 represents an integer from 0 to 2, m2a and m2b independently represent integers from 0 to 2, and m3, m4, and m5 independently represent integers from 0 to 2. R 1 ~R 5 Independently representing a hydrocarbon group, A 1 Indicate C 2-6 Alkylene, n1 represents 0 or an integer from 1 to 6, A 2 Indicate C 1-4 Alkylene.

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

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

19. A cured product formed by curing the curable composition of claim 18.

20. An optical component comprising the cured material of claim 19.

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

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

Images