Fluorene compounds and methods for producing the same

Abstract

To provide a fluorene compound exhibiting a high refractive index.SOLUTION: A fluorene compound of the present invention is represented by a formula (1E). [In the formula, Y1a and Y1b each represent a group of a specific structure having an arene ring; k1a and k1b each represent an integer of 0 to 4, at least one of which is 1 or more; R2a and R2b each represent a substituent; m2a and m2b each represent an integer of 0 to 4; k1a+m2a and k1b+m2b each represent 4 or less; and Y3a and Y3b each represent a group of a specific structure having a glycidyl group].SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a compound having a fluorene skeleton and a method for producing the same. [Background technology]

[0002] Compounds containing a fluorene skeleton possess excellent optical properties due to their chemical structure. It is used as a resin material (optical material) for forming optical components.

[0003] Patent Document 1 describes an optical material for forming optical components such as lenses, as shown in the following formula (1) A thermoplastic resin containing repeating units is disclosed.

[0004] [ka]

[0005] (In the formula, ring Z represents an aromatic hydrocarbon ring, R 1 and R 2 These are hydrogen atoms, halogen atoms, and aromatics. This indicates a hydrocarbon group having 1 to 12 carbon atoms, which may contain an aromatic group, Ar 1 and Ar 2 This represents an aromatic group having 6 to 10 carbon atoms, which may contain substituents, and L 1 and L 2 teeth This indicates a divalent linking group, where j and k are non-negative integers, and m and n are 0 or 1. W is at least one selected from the group represented by the following equation (2) or (3).

[0006] [ka]

[0007] (In the formula, X represents a divalent linking group).

[0008] Patent Document 1 describes a diol component represented by the following formula (a ) as a raw material monomer for forming the above thermoplastic resin.

[0009] [Chemical formula]

[0010] (In the formula, ring Z, R 1 and R 2 , Ar 1 and Ar 2 , L 1 and L 2 , j and k, m and n are the same as those in the above formula (1) respectively). [Prior Art Documents] [Patent Documents]

[0011] [Patent Document 1] International Publication No. 2019 / 044214 [Summary of the Invention] [Problems to be Solved by the Invention]

[0012] Patent Document 1 describes that it is more preferable that ring Z is a benzene ring (or a 1,4-phenylene group). Also, among the numerous diol components represented by the above formula (a) exemplified, the diol components represented by formulas (a1) to (a24) in which ring Z is a benzene ring are described as preferable. Furthermore, in the examples of Patent Document 1, as the diol component represented by the above formula (a), 9,<000045②>9-bis[4-(2-hydroxyethoxy)phenyl]-2,7-diphenylfluorene is described.

[0013] ​​(BPDP2), 9,9-bis[4-(2-hydroxyethoxy)phenyl]-3,6- Diphenylfluorene (BPDP3), 9,9-bis[4-(2-hydroxyethoxy) Phenyl]-4,5-diphenylfluorene (BPDP4), 9,9-bis[4-(2- [Hydroxyethoxy)phenyl]-2,7-di(2-naphthyl)fluorene (BPDN2 ), 9,9-bis[4-(2-hydroxyethoxy)phenyl]-2,7-di(1-naph Various polycarbonate resins and the like are prepared using chill fluorene (BPDN1). It is also stated that it is effective in increasing refractive index and heat resistance.

[0014] However, even these polycarbonate resins may not have sufficient refractive index or heat resistance depending on the application. This is not always the case, and further improvements are needed.

[0015] Therefore, the object of the present invention is a fluorene compound exhibiting a high refractive index and a method for producing the same. The objective is to provide a composition containing the aforementioned compound. [Means for solving the problem]

[0016] The present inventors, after diligent research to achieve the above objective, have found a f having a specific chemical structure. We discovered that ruolene compounds exhibit a high refractive index, thus completing the present invention.

[0017] In other words, the fluorene compound of the present invention is represented by the following formula (1).

[0018] [ka]

[0019] [In the formula, Y 1a and Y 1b Each of these independently corresponds to the following equation (Y1)

[0020] [ka]

[0021] (In the formula, Z 1 This shows an arene ring, R 1 (where represents a substituent, and m1 represents an integer of 0 or greater than or equal to 1.) This represents a monovalent base, where k1a and k1b independently represent integers from 0 to 4. At least one of k1a and k1b is 1 or more. R 2a and R 2b Each of these independently represents a substituent, and m2a and m2b are respectively Independently, they represent integers from 0 to 4. k1a+m2a and k1b+m2b are each independently less than or equal to 4. Y 2a and Y 2b Each of these independently corresponds to the following equation (Y2)

[0022] [ka]

[0023] (In the formula, Z 2 This shows a polycyclic arene ring, R 3 represents a substituent, and m3 represents an integer of 0 or greater than or equal to 1. A 1 n1 represents a linear or branched alkylene group, and n1 represents an integer of 0 or greater. .) [This represents a monovalent group represented by ].

[0024] In the above equation (1), Y 1a and Y 1b In the equation (Y1) that represents Z 1 is a benzene ring, It may be a naphthalene ring or a biphenyl ring, and k1a and k1b are approximately 0 to 2. It can also be a number, Y 2a and Y 2b In the equation (Y2) that represents Z 2 is a naphthalene ring or It may also be a biphenyl ring. Furthermore, the fluorene compound represented by formula (1) is crystalline. It can be in any form.

[0025] Furthermore, in equation (1) above, Y 1a and Y 1b In the equation (Y1) that represents Z 1 is a condensed polynomial Polycyclic arene rings such as cyclic arene rings, and among them, condensed polycyclic C1 rings such as naphthalene rings. 0-14 The arene ring may also be used. The fluorene compound is subjected to melt polymerization or solution polymerization. At least selected from monomers for the purpose of modifying the resin, and resin additives for the purpose of modifying the resin. One type is fine.

[0026] Furthermore, the present invention relates to a composition (liquid composition or solvent) comprising the fluorene compound and a solvent. It contains (liquid).

[0027] Furthermore, the present invention relates to the fluorene compound comprising the reaction step described in (i) or (ii) below. It includes methods for manufacturing goods.

[0028] (i) A compound represented by the following formula (2), a compound represented by the following formula (3a), and formula ( A step of coupling reaction with the compound represented in 3b).

[0029] [ka]

[0030] [where, X 1a and X 2a and X 1b and X 2b Each is independently, cup It exhibits a pair of reactive groups capable of forming a carbon-carbon bond via a ring reaction, Y 1a and Y 1 b , k1a and k1b, R 2a and R 2b , m2a and m2b, and Y 2a oh Yobi Y 2b [This is the same as in equation (1) above].

[0031] (ii) A compound represented by the following formula (6), and a compound represented by the following formula (5a) and formula ( A step of reacting with the compound represented in 5b)

[0032] [ka]

[0033] [In the formula, Y 1a and Y 1b , k1a and k1b, R 2a and R 2b , m2a and m2b, and Y 2a and Y 2b [This is the same as in equation (1) above].

[0034] The above manufacturing method involves using the fluorene compound obtained in the reaction step as a solvent, for example, ( a) Solvents containing aromatic hydrocarbons and aliphatic hydrocarbons, and (b) Solvents containing ketones Precipitation (crystallization) occurs from at least one solvent selected from the solvents (crystallization solvent or reprecipitation solvent). The process may further include a purification step (crystallization step or reprecipitation step) to induce precipitation.

[0035] The present invention includes fluorene compounds represented by the following formula (1E).

[0036] [ka]

[0037] [In the formula, Y 3a and Y 3b Each of these independently corresponds to the following equation (Y3)

[0038] [ka]

[0039] (In the formula, R 4 This indicates a hydrogen atom or a methyl group. Z 2 , R 3 , m3, A 1 n1 and n1 are the same as in equation (Y2) above. This represents a monovalent group, Y 1a and Y 1b This is the same as equation (Y1) above, k1a and k1b, R 2a and R 2b , m2a and m2b, k1a + m2a and k1b + m2b are each independently equivalent to equation (1) above.

[0040] The present invention involves reacting a compound represented by formula (1) with an epihalohydrin component. The present invention includes a method for producing a compound represented by formula (1E). A curable composition containing the compound represented by E), a cured product obtained by curing this curable composition, and This also includes optical components containing this cured material.

[0041] Furthermore, the present invention may also address the following problems as a secondary objective.

[0042] In other words, another object of the present invention is to produce fluorene that exhibits high heat resistance (or heat decomposition resistance). The objective is to provide a compound, a method for producing the same, and a composition containing the compound.

[0043] Another object of the present invention is that even if the chemical structure contains many benzene rings (aromatic rings) , fluorene compounds having high solubility (or compatibility) and methods for producing the same, and the preceding The objective is to provide a composition containing the compound.

[0044] Another object of the present invention is that even if the chemical structure contains many benzene rings (aromatic rings), the low A fluorene compound having a melting temperature (melting temperature), a method for producing the same, and the compound The objective is to provide a composition containing the following:

[0045] Furthermore, in this specification and the claims, the number of carbon atoms in the substituent is C1, C6, C 10 These are sometimes used to indicate this. For example, an alkyl group with 1 carbon atom is indicated as "C1 alkyl". Furthermore, aryl groups with 6 to 10 carbon atoms are "C 6-10 It is indicated by "Ariel". [Effects of the Invention]

[0046] The fluorene compound of the present invention exhibits a high refractive index due to its specific chemical structure. Furthermore, the fluorene compound exhibits high heat resistance (or heat decomposition resistance). Although ole compounds contain many benzene rings (aromatic rings) in their chemical structure, Furthermore, it exhibits high solubility (or miscibility), thus combining high solubility with high refractive index and high heat resistance. It can also be erected. Therefore, the fluorene compound can be used as a solvent or a curing agent, or as a remedial agent. A homogeneous composition can also be easily or efficiently prepared with the corresponding components. Ruolene compounds exhibit unexpectedly low melting temperatures (initiation or termination temperature of melting), and are easily Since it can also be melted, it can be effectively used as a monomer for melt polymerization. Furthermore, it can be easily or efficiently mixed into the resin by melt kneading, and can also be used as a resin modifier. It can be used for its intended purpose. [Modes for carrying out the invention]

[0047] [Fluorene compounds (or diol compounds) represented by formula (1)] In formula (1) above, the monovalent group Y 1a and Y 1b The Z in the above equation (Y1) represents 1 in Examples of arene rings (aromatic hydrocarbon rings) that can be represented include monocyclic arenes such as benzene rings. Examples include lane rings and polycyclic arene rings. Polycyclic arene rings include fused polycyclic rings. Arene ring (condensed polycyclic aromatic hydrocarbon ring), ring-assembled arene ring (ring-assembled polycyclic aromatic hydrocarbon ring) Examples include hydrogenated rings.

[0048] Examples of condensed polycyclic arene rings include condensed bicyclic arene rings and condensed tricyclic arenes. Examples include fused bi- or tetra-ring arene rings. Examples include fused bicyclic carbon atoms such as naphthalene rings and indene rings. 10-16 arene rings etc. Examples include the anthracene ring and phenanthrene ring. Condensed tricyclic rings such as C 14-20 Examples include arene rings. Preferred arene rings are polycyclic fused rings. The naphthalene ring is a condensed polycyclic C ring, such as the naphthalene ring. 10-14 It is an arene ring.

[0049] Examples of ring-assembled arene rings include biphenyl rings, phenylnaphthalene rings, and binaphthi rings. Examples include bialene rings such as the 'L' ring and telarene rings such as the terphenyl ring. The beautiful ring assembly, the arene ring, is a C ring such as a biphenyl ring. 12-18 It is a Bialen ring.

[0050] In this specification and in the claims, "ring-assembled arene ring" means two or more rings. The ring system (arene ring system) is directly connected by single or double bonds, and the bonds that directly connect the rings This means that the number is one less than the number of rings in the system, for example, as mentioned above, phenylnaphtha. Lenne rings, binaphthyl rings, etc., have a condensed polycyclic arene ring framework, but they are ring-assembled arene rings. They are classified as "condensed polycyclic arene rings" such as naphthalene rings (acyclic aggregate arene rings) and are clearly defined as such. They are clearly distinguishable.

[0051] Preferred ring Z 1 C 6-14 An arene ring is an example, and more preferably a benzene ring. C rings, naphthalene rings, biphenyl rings, etc. 6-12 Arene ring, more preferably benz C such as the naphthalene ring and naphthalene ring. 6-10 This refers to an arene ring, particularly a naphthalene ring. 1 If it is a polycyclic arene ring, especially a condensed polycyclic arene ring such as a naphthalene ring, then the refractive index and Not only is it easy to effectively improve heat resistance, but it also has a low melting point and high solubility (miscibility). It is sometimes preferable to show it.

[0052] Also, monovalent group Y 1a and Y 1b Ring Z in 1 These are the fluorene skeletons 1- It may be substituted in any of the 4th, 5th through 8th positions, but not in the 2nd, 3rd, and / or 7th positions. These are some examples. 1a and Y 1b If the number of substitutions k1a and k1b is 1, Possible substitution (or bonding) positions include the 1,8-position, 2,7-position, 3,6-position, and 4 , in the formula (1) such as the 5-position, it is a position symmetric about the left and right on the paper surface, and in particular, the 2,7-positions are preferred.

[0053] In addition, for the ring Z with respect to the fluorene skeleton 1 The bonding position on is the ring Z 1 When is a naphthalene ring Case, it may be either the 1-position or the 2-position of the naphthalene ring, and the 2-position of the naphthalene ring is preferred.

[0054] R 1 Examples of the substituent (non-reactive substituent or non-polymerizable substituent) represented by are, for example, ha logen atom, hydrocarbon group (or group [-R h ), group [-OR h [[ID=Z6]]](wherein, R [[ID=Z7]]<00000Z5>represents the above-mentioned carbon hydrocarbon group), group [-SR h (wherein, R h represents the above-mentioned hydrocarbon group), acyl group, nitro group, cyano group, mono- or di-substituted amino group, etc.

[0055] Examples of the halogen atom include, for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc. are mentioned.

[0056] Examples of the hydrocarbon group represented by the above R h ​​​​​​​​​​​​​​​​​It is an alkyl group.

[0058] Examples of the cycloalkyl group include C5 cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. -10 A cycloalkyl group is exemplified.

[0059] Examples of the aryl group include C aryl groups such as a phenyl group, an alkylphenyl group, a biphenylyl group, and a naphthyl group. Aryl group. 6-12 An aryl group is exemplified. Examples of the alkylphenyl group include a methylphenyl group (or tolyl group), a dimethylphenyl group (or xylyl group), and any mono- to tri-C alkyl-phenyl group. 1-4

[0060] Examples of the aralkyl group include C aralkyl groups such as a benzyl group and a phenethyl group. 6-10 aryl -C 1-4 alkyl group.

[0061] Examples of the group [-OR h include an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, etc. Specifically, groups corresponding to the examples of the hydrocarbon group R are exemplified. Examples of the alkoxy group include linear or branched C alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group. h of Examples of the cycloalkyloxy group include C cycloalkyloxy groups such as a cyclohexyloxy group. Examples of the aryloxy group include C aryloxy groups such as a phenoxy group. cycloalkyloxy group. 1-10 Examples of the aralkyloxy group include C aralkyloxy groups such as a benzyloxy group. <00007,46>cycloalkyloxy group. 5-10 A cycloalkyloxy group is exemplified. Examples of the aryloxy group include C aryloxy groups such as a phenoxy group. 6-10 aryloxy group is exemplified. Examples of the aralkyloxy group include C aralkyloxy groups such as a benzyloxy group.6-10 Aryl-C 1-4 Alkyloxy groups are one example.

[0062] The aforementioned base [-SR h Examples of these include alkylthio groups, cycloalkylthio groups, and ali groups. Examples include the hydroxylthio group and the aralkylthio group, and specifically the hydrocarbon group R h Examples Examples of corresponding groups include alkylthio groups such as methylthio and ethylthio. C groups such as o-group, propylthio group, n-butylthio group, t-butylthio group, etc. 1-10 Alkyl A thio group is one example. A cycloalkylthio group is, for example, a cyclohexylthio group. Which C 5-10 Examples include cycloalkylthio groups. Examples of arylthio groups include, C such as thiophenoxy group (phenylthio group) 6-10 An example is the arylthio group. Examples of the alkylthio group include the benzylthio group and other C groups. 6-10 Aryl-C 1-4 Alkylthio groups are one example.

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

[0064] Examples of mono- or disubstituted amino groups include dialkylamino groups and bis(alkylamino groups). Examples include dimethyl amino groups. Dialkylamino groups include, for example, dimethyl DiC groups such as amino groups 1-4 Examples include alkylamino groups. Bis(alkylcarbonyl) Examples of amino groups include bis(C) groups such as diacetylamino groups. 1-4 Alkyl-carb Examples include the (nyl)amino group.

[0065] These base R 1 Among these, representative groups include hydrocarbon groups, alkoxy groups, and acyl groups. Examples include nitro groups, cyano groups, and substituted amino groups. It is preferable when m1 is 1 or greater. i base R 1 Examples include alkyl groups and alkoxy groups, specifically linear groups such as methyl groups. C-shape or branched chain shape 1-6 Linear or branched C such as alkyl groups and methoxy groups 1-4 Examples include alkoxy groups, and among them alkyl groups, particularly linear or branched groups such as methyl groups. Chain C 1-4 Alkyl groups are preferred. 1 When the group R is an aryl group, 1 is a ring Z 1 They may together form the aforementioned ring-assembled arene ring.

[0066] The number of substitutions m1 is in the ring Z. 1 You may choose depending on the type, for example, from integers ranging from 0 to 7. The following ranges are possible and preferable: integers from 0 to 6, integers from 0 to 5, and integers from 0 to 4. An integer, an integer between 0 and 3, an integer between 0 and 2, more preferably 0 or 1, and especially 0 That is the case.

[0067] Furthermore, if the number of substitutions m1 is 2 or more, ring Z 1 Substituting two or more groups R 1 The types are mutual They may be the same or different. Also, base R 1 The substitution position is not particularly restricted, ring Z 1 You may choose depending on the type.

[0068] The typical monovalent group Y represented by the above formula (Y1) 1a , Y 1b For example, a phenyl group, 1 -Examples include naphthyl groups such as naphthyl groups and 2-naphthyl groups, and biphenylyl groups. A nyl group or a naphthyl group is preferred, a naphthyl group is more preferred, and a 2-naphthyl group is particularly preferred. It seems so.

[0069] monovalent base Y 1a , Y 1b The number of substitutions k1a and k1b are integers, for example, between 0 and 3. Preferably 0 to 2, more preferably 1 or 2, even more preferably 1. k1a and k1b may be different from each other, but it is preferable that they be the same. Of these, at least one is an integer of 1 or more, preferably both are integers of 1 or more. More preferably, both are 1.

[0070] Furthermore, if k1a and k1b are each 1 or greater, 2 will form the fluorene skeleton. Group Y is substituted on a different benzene ring among the two benzene rings. 1a and Y 1b The types are mutual They may be different, but it is preferable that they be the same. Also, k1a and k1b are 2 or more. In this case, one of the two benzene rings forming the fluorene skeleton is substituted on the same benzene ring. 2 or more base Y 1a , Y 1b The types may be the same as or different from each other.

[0071] R 2a , R 2b A substituent represented by (non-reactive substituent or non-polymerizable substituent) is the same as the group Y 1a , Y 1b Any substituent other than alkyl groups is acceptable, and typical examples include carbides such as alkyl groups. Hydrogen groups (excluding aryl groups), fluorine atoms, chlorine atoms, bromine atoms, and other halogens. Examples include atoms and cyano groups. Alkyl groups include methyl groups, ethyl groups, and t-butyl groups. Linear or branched chain C such as C groups 1-6 Examples include alkyl groups. Number of substitutions m2a, If m2b is 1 or greater, the preferred R 2a , R 2b For example, linear groups such as methyl groups or branched chain C 1-4 It is an alkyl group.

[0072] R 2a and R 2b For the number of substitutions m2a and m2b, for example, integers between 0 and 3. It is preferably an integer between 0 and 2, more preferably 0 or 1, and especially 0. m2a and m2b may be different from each other, but it is preferable that they be the same. If 2a and m2b are each 1 or greater, two benzases form the fluorene skeleton. Among the benzene rings, R is substituted with a different benzene ring. 2a and R 2b The types are different from each other. They may be present, but it is preferable that they be the same. Also, if m2a and m2b are 2 or more, full Of the two benzene rings forming the orene skeleton, two or more R substituted on the same benzene ring. 2a , R 2b The types may be the same or different from each other. 2a oh Call R 2b The substitution position of is not particularly restricted, base Y 1a , Y 1b Replace at a position other than the replacement position. That's all you need to do.

[0073] The sum of the number of substitutions in the two benzene rings forming the fluorene skeleton is k1a + m2a. k1b + m2b are, for example, integers from 0 to 4, preferably integers from 1 to 3, more preferably The value is 1 or 2, more preferably 1. The sum of k1a + m2a and k1b + m2 b may be different from b, but it is preferable that they be the same.

[0074] A monovalent group (or hydroxyl group-containing group) Y bonded to the 9,9-position of the fluorene skeleton. 2 a and Y 2b The Z in equation (Y2) above represents 2 As for polycyclic arene rings represented by, Examples include fused polycyclic arene rings and ring-assembled arene rings. As for the compound arene ring, Z in the aforementioned equation (Y1) 1 Similar reductions, including preferred embodiments. Examples include polycyclic arene rings and ring-assorted arene rings.

[0075] Preferred ring Z 2 C 10-14 An example is an arene ring, more preferably naphtha. C such as the len ring and biphenyl ring 10-12 arene rings, more preferably naphthalene rings be.

[0076] Furthermore, ring Z at position 9 of the fluorene skeleton. 2 The bond position above is ring Z. 2 is a naphthalene ring In some cases, it may be either position 1 or 2 of the naphthalene ring, and position 2 of the naphthalene ring Preferably, ring Z 2 If it is a biphenyl ring, then the 3rd position of the biphenyl ring is preferable.

[0077] R 3 Substituents represented by the above formula (non-reactive substituents or non-polymerizable substituents) include the above formula ( R in Y1) 1 Similar groups are examples. When the number of substitutions m3 is 1 or more, Substituent R 3 Examples include halogen atoms; alkyl groups, cycloalkyl groups, aryl groups, aryl groups. Hydrocarbon groups such as lucyl groups; alkoxy groups; acyl groups; nitro groups; cyano groups; substituted amino acids. Examples include groups such as alkyl groups, cycloalkyl groups, aryl groups, and aryl groups. Coxy groups are examples, and more preferably linear or branched C groups such as methyl groups. 1-6 a C such as lucyl group, cyclohexyl group, etc. 5-8 Cycloalkyl groups, phenyl groups, etc. 6- 14 Linear or branched C such as aryl groups and methoxy groups 1-4 Examples include alkoxy groups. Among these, alkyl groups and aryl groups are preferred, and linear groups such as methyl groups are particularly preferred. C-shape or branched chain shape 1-4 C such as alkyl groups and phenyl groups 6-10 Aryl groups are preferred i. Note that the base R 3 When the group R is an aryl group, 3 is ring Z 2 along with the aforementioned ring array A ring may be formed.

[0078] base R 3 The number of permutations m3 can be any integer greater than or equal to 0 or 1, and the ring Z 2 Depending on the type You can choose as you like, for example, an integer of about 0 to 6, and a preferred range is as follows: In terms of hierarchical order, integers from 0 to 4, integers from 0 to 3, integers from 0 to 2, and 0 or 1 are even more preferred. In particular, 0 is preferred. Furthermore, if m3 is 2 or more, then 2 or more base R 3 The types are relative to each other They may be the same or different. In particular, when m3 is 1, ring Z 2 is a naphthalene ring or Biphenyl ring, group R 3 It may also be a methyl group.3 The substitution position is not particularly restricted. Rezu, Ring Z 2 And, base [-O-(A 1 O) n1 -H] and the bond position with the 9th position of the fluorene ring It is sufficient to substitute in any position other than the ring Z. 2 In this case, base [-O-(A 1 O) n1 -H] For the ortho position (group [-O-(A 1 O) n1 -H] (the carbon atom adjacent to the bond position) Substitution is common.

[0079] Alkylene group A 1 Examples include ethylene groups and propylene groups (1,2-propanedi Linear groups such as yl groups, trimethylene groups, 1,2-butanediyl groups, and tetramethylene groups or branched chain C 2-6 Examples include alkylene groups, and when the number of repetitions n1 is 1 or more. Preferably linear or branched C 2-4 Alkylene group, more preferably ethylene group , linear or branched C such as propylene groups 2-3 It is an alkylene group, especially ethylene The base is preferable.

[0080] Oxyalkylene group (-A 1 The number of repeats (number of added moles) n1 of O-) is 0 or 1 or less. Any of the above is acceptable; for example, you can choose from an integer range of about 0 to 15, and a preferred range is The subsequent steps are 0-10, 0-8, 0-6, 0-4, 0-2, and 0-1. The number of repetitions n1 may be 1 or more, for example, 1 You can choose from an integer range of approximately 15, and the preferred range is 1 to 10 in stages. , it is 1 to 8, 1 to 6, 1 to 4, 1 to 3, 1 to 2, and particularly preferably 1. In addition, In this specification and the claims, the "number of repetitions (number of added moles)" may be an average value (arithmetic average value, additive average value) or an average number of added moles, and a preferred embodiment is the same as the above preferred range (the above integer range). If the number of repetitions n1 is too large, there is a risk that the refractive index and heat resistance may decrease.

[0081] When n1 is 2 or more, the types of two or more oxyalkylene groups (-A 1 O-) may be different from each other and are preferably the same.

[0082] The substitution position of the group [-O-(A 1 O) n1 -H] with respect to the ring Z 2 is, when the ring Z 2 is a naphthalene ring it may be substituted at any position of the 5th to 8th positions of the naphthyl group bonded to the 9th position of the fluorene ring. For example, the 1st or 2nd position of the naphthalene ring is substituted with respect to the 9th position of the fluorene ring (substituted in the relationship of 1-naphthyl or 2-naphthyl), and the relationship of 1,5 -position, 2,6-position, etc. is preferable, and particularly preferably substituted in the relationship of 2,6-position . Further, when the ring Z is a ring assembly arene ring, it may be substituted on the arene ring bonded to the 9th position of fluorene 2 or the arene ring adjacent to this arene ring, and it is preferable to substitute on the arene ring bonded to the 9th position of fluorene. For example, when the ring Z is a biphenyl ring, the 3rd position of the biphenyl ring (3-biphenylyl group) is bonded to the 9th position of fluorene, and the group [-O-(A 2 O) is at the 6th position of this biphenyl ring ( 3-biphenylyl group), and at the 53rd position of 1 O) n1-H] substitution is preferable. .

[0083] The monovalent group (or hydroxyl group-containing group) Y represented by the above formula (Y2) 2a and Y 2 b Typical groups include hydroxypolycyclic aryl groups where n1 is 0, and groups where n1 is 1 or greater. Examples include certain hydroxy(poly)alkoxy polycyclic aryl groups. And in the claims, "(poly)alkoxy" means an alkoxy group, polyalkoxy It is used to mean both xy groups.

[0084] Examples of the hydroxypolycyclic aryl group include hydroxycondensed polycyclic aryl groups. Examples include hydroxyl ring-assembled aryl groups.

[0085] Examples of hydroxy-condensed polycyclic aryl groups include hydroxynaphthyl groups and other hydroxy groups. Roxy C 10-14 Examples include fused polycyclic aryl groups, and specific examples include hydroxynaphthyl Examples of these groups include the 6-hydroxy-2-naphthyl group and the 5-hydroxy-1-naphthyl group. Among these, the 6-hydroxy-2-naphthyl group is preferred.

[0086] Examples of hydroxy ring-assembled aryl groups include the hydroxybiphenylyl group (or hydroxybiphenyl group). Hydroxy C (such as phenyl-hydroxyphenyl group) 12-16 Ring-assembled aryl groups, etc. Examples of specific hydroxybiphenylyl groups include 6-hydroxy-3-biphenyl Examples include the lyl group (or 4-hydroxy-3-phenylphenyl group).

[0087] Examples of the hydroxy(poly)alkoxy polycyclic aryl group include hydroxy( Polyalkoxy condensed polycyclic aryl group, hydroxy(poly)alkoxy ring aggregated aryl Examples include the base.

[0088] Examples of hydroxy(poly)alkoxy condensed polycyclic aryl groups include hydroxy( Hydroxy(poly)alkoxy C groups such as poly)alkoxynaphthyl groups 10-14 Condensed polyring Examples include the aryl group, and specific examples of the hydroxy(poly)alkoxynaphthyl group include This is a 6-(2-hydroxyethoxy)-2-naphthyl group, 6-(2-hydroxypropoxy (C)-2-naphthyl group, 6-(2-(2-hydroxyethoxy)ethoxy)-2-naphthyl 6-(mono or deca)C such as the ru group 2-4 Alkoxy-2-naphthyl group; 5-(2-H 5-(mono or deca)C groups such as droxyethoxy)-1-naphthyl group 2-4 Alkoxy Examples include the -1-naphthyl group, and the 6-(2-hydroxyethoxy)-2-naphthyl group. Which 6-(mono or hexa)C 2-3 An alkoxy-2-naphthyl group is preferred.

[0089] Examples of hydroxy(poly)alkoxy ring-assembled aryl groups include hydroxy(poly )alkoxybiphenylyl group [or phenyl-hydroxy(poly)alkoxyphenyl Hydroxy(poly)alkoxyC groups such as [group] 12-16 Examples include ring-assembled aryl groups. Specific examples of hydroxy(poly)alkoxybiphenylyl groups include 6-(2-hydroxy 9ethoxy)-3-biphenylyl group [or 4-(2-hydroxyethoxy)-3-fe 6-(2-hydroxypropoxy)-3-biphenylyl group, etc. Hydroxy(mono or deca)C 2-4Examples include an alkoxy-3-biphenylyl group and the like.

[0090] Among these monovalent groups (or hydroxyl group-containing groups) Y 2a and Y 2b of these, Z 2 is a hydroxycondensed polycyclic aryl group, a hydroxy(poly)alk oxycondensed polycyclic aryl group in which Z is a condensed polycyclic arene ring is preferred; Z 2 is a naphthalene ring, a hydroxynaphthyl group, a hydroxy(poly)alkoxynaphthyl group is more preferred; 6-hydroxy-2-na phthyl group, 6-hydroxy(mono to deca)C 2-4 alkoxy-2-naphthyl group is even more preferred; among them, 6-hydroxy-2-naphthyl group, 6-(2-hydroxyethoxy )-2-naphthyl group and the like, 6-hydroxy(mono to hexa)C 2-3 alkoxy- 2-naphthyl group is preferred; particularly, 6-hydroxy-2-naphthyl group is preferred.

[0091] Y 2a and Y 2b The types of may be the same as or different from each other. Y 2a and Y 2b ​​​​​​​​​​​​​​​​​​​​​​​​​1a and Y 1b Ring Z in 1 They are identical, Y 2a and Y 2b in Ring Z 2 Examples include compounds that are identical. Examples of such fluorene compounds include For example, Y 1a and Y 1b Ring Z in 1 is a benzene ring, naphthalene ring or biphenyl A ring, preferably a naphthalene ring, and Y 2a and Y 2b Ring Z in 2 ga naftare Examples include compounds that have a naphthalene ring or biphenyl ring, preferably a naphthalene ring. In such a fluorene compound, m1, m2a, m2b, and m3 are 0. This is also common, and n1 may be 0 or greater than 1. Among such fluorene compounds, , Z 1 is a naphthalene ring, and Z 2 Compounds in which the ring is a naphthalene ring are preferred.

[0093] Said Z 1 The naphthalene ring is Z 2 Compounds in which the ring is a naphthalene ring (i.e., k1a And k1b is 1, Y 1a and Y 1b Ring Z in 1 This is a naphthalene ring, and Y 2a and Y 2b Ring Z in 2 Examples of compounds in which the ring is a naphthalene ring include, for example, 9, 9-Bis(hydroxynaphthyl)-dinaphthylfluorene, 9,9-Bis[hydroxy( Examples include poly)alkoxynaphthyl]-dinaphthylfluorene.

[0094] Examples of 9,9-bis(hydroxynaphthyl)-dinaphthylfluorene include, 9-Bis(6-hydroxy-2-naphthyl)-2,7-di(2-naphthyl)fluorene, 9,9-Bis(6-hydroxy-2-naphthyl)-2,7-di(1-naphthyl)fluore 9,9-bis(5-hydroxy-1-naphthyl)-2,7-di(2-naphthyl) Oren, 9,9-bis(5-hydroxy-1-naphthyl)-2,7-di(1-naphthyl) 9,9-bis(hydroxynaphthyl)-2,7-dinaphthylfluorene, such as fluorene. These are some examples.

[0095] As 9,9-bis[hydroxy(poly)alkoxynaphthyl]-dinaphthylfluorene For example, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2, 7-di(2-naphthyl)fluorene, 9,9-bis[6-(2-hydroxypropoxy) -2-naphthyl]-2,7-di(2-naphthyl)fluorene,9,9-bis[6-(2- (2-hydroxyethoxy)ethoxy)-2-naphthyl]-2,7-di(2-naphthyl) Fluorene, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7 -di(1-naphthyl)fluorene, 9,9-bis[5-(2-hydroxyethoxy)-1 -Naphthyl]-2,7-di(2-naphthyl)fluorene, 9,9-bis[5-(2-hydr [Loxyethoxy)-1-naphthyl]-2,7-di(1-naphthyl)fluorene, etc. 9, 9-Bis[Hydroxy(mono or deca)C 2-4 [alkoxy-naphthyl]-2,7-di Examples include naphthylfluorene.

[0096] Of these fluorene compounds, 9,9-bis(6-hydroxy-2-naphthyl)- 2,7-di(2-naphthyl)fluorene, 9,9-bis[6-(2-hydroxyethoxy )-2-naphthyl]-2,7-di(2-naphthyl)fluorene is preferred, and 9,9-bis (6-hydroxy-2-naphthyl)-2,7-di(2-naphthyl)fluorene is even better. It seems so.

[0097] The fluorene compound represented by formula (1) has a high refractive index. The refractive index of the compound is, for example, 1.75 to 1.85 at a temperature of 25°C and a wavelength of 589 nm. It can be to a certain degree, and preferred ranges are, in order, 1.76 to 1.82, and 1. The ranges are 77-1.81 and 1.78-1.8.

[0098] Furthermore, the fluorene compound represented by formula (1) has high heat resistance. The 5% mass loss temperature of the ruolene compound may be, for example, around 350-500°C. The appropriate temperature ranges are, in stages, 400-480°C, 420-470°C, and 430-470°C. The temperatures are 60°C and 440-450°C.

[0099] The fluorene compound represented by formula (1) exhibits a high 5% mass loss temperature, however Surprisingly, it has a low melting temperature (melting temperature), and the melting start temperature is, for example, 100°C. It may be around 250°C, preferably in stages as follows: 120-230°C, 150-2 The melting temperatures are 10°C, 160-200°C, and 170-190°C. The melting termination temperature is, for example, The temperature can be around 130-280°C, preferably in stages from 150-260°C, 1 The optimal temperatures are 80-250°C, 200-240°C, and 210-230°C. Therefore, melt polymerization occurs. These monomer components are used, or mixed with resin through melt kneading, etc., as resin additives (resin modifiers). It can also be used.

[0100] Furthermore, in this specification and the claims, the fluorene formulation represented by formula (1) is used. The refractive index, 5% mass loss temperature, and melting temperature of the composite are described in the examples below. It can be measured by the method described.

[0101] Furthermore, the fluorene compound represented by formula (1) also exhibits excellent solubility (compatibility). , together with organic compounds such as solvents and / or resins, a homogeneous composition can be easily or efficiently formed. It can also be formed in the form of a fluorene compound represented by formula (1). Even when a substance is dissolved (miscibly mixed) at a high concentration, it is less likely to precipitate after dissolution (miscibility), and furthermore, after dissolution (miscibility) Furthermore, it is less likely to precipitate even when exposed to low-temperature environments, maintains a stable dissolved (miscible) state, and is stable for storage. It also has excellent properties (solution stability or low-temperature stability).

[0102] The solvent for forming the composition with the fluorene compound represented by formula (1) is For example, hydrocarbons, specifically aliphatic hydrocarbons such as hexane and heptane, and benz Aromatic hydrocarbons such as ethanol and toluene; methanol, ethanol, n-propano Alcohols such as benzyl alcohol; ethers, specifically diethyl ether Dialkyl ethers such as 1,4-dioxane, tetrahydrofuran, and cyclic ethers such as 1,4-dioxane Aromatic ethers such as ethers, anisole, etc.; ethylene glycol monomethyl ether Tel, ethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME), ethylene glycol dimethyl ether, diethylene glycol monomethyl Glycol ethers such as diethylene glycol monoethyl ether; Tones, specifically acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone Chain ketones such as β-(MIBK), cyclic ketones such as cyclohexanone, etc. Calcium compounds, acetate esters such as ethyl acetate, methyl lactate, ethyl lactate, butyl lactate, etc. Acid esters, lactones such as γ-butyrolactone, etc.; ether esters, specific It contains methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol. Alkylene glycol monoalkylene, such as monomethyl ether acetate (PGMEA) Alkoxycarboxylic acids such as ether acetates and ethyl 3-ethoxypropionate Esters, etc.; N,N-dimethylformamide, N,N-dimethylacetamide, N- Amides such as methyl-2-pyrrolidone; sulfoxides such as dimethyl sulfoxide. Anything is fine.

[0103] These solvents can be used individually or in combination of two or more. The medium may be an ether ester, or an alkylene glycol monoalkylate Telacetates are preferred, and C such as PGMEA is preferred. 2-4 Alkylene glycol mono-C1 -4 Alkyl ether acetates are preferred.

[0104] A composition comprising a fluorene compound represented by formula (1) and a solvent (liquid composition or solvent) When forming a liquid, the proportion of the fluorene compound is, for example, 1 to 1 of the total composition. 80% by mass, preferably 10-70% by mass, more preferably 20-60% by mass, especially 3 It is between 0 and 50% by mass.

[0105] The above composition may also be used as a reaction solution (reaction mixture) containing other reaction components or catalysts. For example, the fluorene compound represented by formula (1) above is often used as a monomer for solution polymerization. It may also be used as a reaction solution for that purpose.

[0106] [Method for producing fluorene compounds (diol compounds) represented by formula (1)] (Reaction process) The fluorene compound represented by formula (1) above is, for example, the following reaction process formula (first reaction process) It may be prepared according to the formula.

[0107] [ka]

[0108] (In the formula, X 1a and X 2a and X 1b and X 2b Each is independently, cup It exhibits a pair of reactive groups capable of forming a carbon-carbon bond (or direct bond) via a ring reaction. , Y 1a and Y 1b , k1a and k1b, R 2a and R 2b , m2a and m2b , and Y 2a and Y 2b (This is the same as formula (1) above, including preferred embodiments).

[0109] (Preparation of the compound represented by formula (2) in the first reaction step) The compound represented by formula (2) is the compound represented by formula (4) and the compound represented by formula (5a) It can be prepared by reacting a compound represented by formula (5b) with a compound represented by formula (5b), for example. For example, as described in Japanese Patent Publication No. 2011-68624, Japanese Patent Publication No. 2020-75904, etc. It may be prepared according to the method.

[0110] In equation (4) above, X 1a and X 1b As an example, the coupling reaction described later (formula) (2) The compound represented by formula (3a) and the compound represented by formula (3b) Examples include the reactive groups described in the section on reactions with composites.

[0111] Examples of compounds represented by formula (4) include 2,7-dibromo-9-fluoreno Examples include dihalo-9-fluorenone. The compound represented by formula (4) is... It may be used alone or in combination of two or more types, but it is preferable to use it alone. Preferred compounds represented by formula (4) include 2,7-dibromo-9-fluorenone and others. It is 7-dihalo-9-fluorenone.

[0112] The compound represented by formula (5a) and the compound represented by formula (5b) are the monovalent group (hydroxyl group containing) Y 2a and Y 2b Corresponding hydroxypolycyclic arenes ( (The compound corresponding to n1=0) or hydroxy(poly)alkoxy polycyclic arenes (n The compound corresponding to 1≧1 is also the Y 2a and Y 2b In response to the same It appears that...Specific examples of hydroxy-polycyclic arenes include 1-naphthol and 2-naphthol Examples include naphthol (such as 2-hydroxybiphenyl) and hydroxybiphenyl (such as 2-hydroxybiphenyl). Examples of specific hydroxy(poly)alkoxy polycyclic arenes include 1-(2- Hydroxyethoxy)naphthalene, 2-(2-hydroxyethoxy)naphthalene, 2-( 2-hydroxypropoxy)naphthalene, 2-[2-(2-hydroxyethoxy)ethoxy Hydroxy(mono or deca)C such as cyanphthalene 2-4 Alkoxy-naphthalene, Hydroxy(mono or deca)C such as 2-(2-hydroxyethoxy)biphenyl 2- Examples include 4-alkoxy-biphenyls. These compounds represented by formula (5a) are examples of the compounds represented by formula (5a). The compounds represented by formula (5b) may be used alone or in combination of two or more. However, it is preferable to use it alone. Note that the compound represented by formula (5a) and formula (5 It is preferable that the compounds represented by b) are the same compound. Among the compounds represented by formula (5b), naphthol such as 2-naphthol , such as hydroxy(mono or hexa)C 2-(2-hydroxyethoxy)naphthalene 2-3 Alkoxynaphthalene is preferred.

[0113] The compound represented by formula (4), the compound represented by formula (5a), and formula (5b) The ratio of the total amount of the compounds represented by the formula is, for example, former / latter (molar ratio) = 1 / 2 to 1 / 1 It can be as low as 0, and a preferred range is, in stages, 1 / 2.2 to 1 / 5, 1 The ranges are / 2.5 to 1 / 4 and 1 / 2.7 to 1 / 3.3.

[0114] The reaction may be carried out in the presence of an acid catalyst. Examples of acid catalysts include inorganic acids, organic acids, and solid acids. Examples include body acids. Examples of inorganic acids include sulfuric acid, hydrogen chloride, and phosphoric acid. Inorganic acids may be in the form of aqueous solutions, such as hydrochloric acid. Organic acids include, for example, Examples of sulfonic acids include methanesulfonic acid and triglycerides. (Halo)alkanesulfonic acids such as fluoromethanesulfonic acid, p-toluenesulfonic acid Examples include arene sulfonic acids. Examples of solid acids include inorganic solid acids, In terms of physical properties, metal oxides include metal oxides, complex metal oxides, metal sulfides, metal sulfates, and polyacids. Compounds, nonmetallic sulfates, clay minerals, zeolites, kaolin, etc.; organic solid acids, specifically, Examples of cation exchange resins include strongly acidic cation exchange resins and weakly acidic cation exchange resins. Examples of strongly acidic cation exchange resins include sulfones such as Nafion manufactured by DuPont. Examples include ion exchange resins having acidic groups. Examples of weakly acidic cation exchange resins include For example, an ion having a carboxylic acid group, such as (meth)acrylic acid-divinylbenzene copolymer. Examples include replacement resins.

[0115] These acid catalysts can be used individually or in combination of two or more. The acid catalyst is an inorganic acid such as sulfuric acid, or a cation exchange resin, and the water produced as the reaction progresses... Sulfuric acid, particularly concentrated sulfuric acid, is preferred because it also acts as a dehydrating agent.

[0116] The sulfuric acid mentioned above includes, for example, dilute sulfuric acid with a concentration of about 30-90% by mass, and concentrated sulfuric acid with a concentration of 90% by mass or more. If sulfuric acid, fuming sulfuric acid, etc. are included and can be converted to sulfuric acid in the reaction system, they can be used as a sulfuric acid precursor. Sulfuric acid can be used. The sulfuric acid should be concentrated to 80-99% of H2SO4. You may choose from a range of approximately mass percent, and preferred ranges are, in stages, 90 to 9 The concentrated sulfuric acid is 9% by mass, 93-99% by mass, or 96-99% by mass, and more preferably 97% by mass. The sulfuric acid is concentrated to approximately 98.5% by mass, and 98% by mass is particularly preferred.

[0117] The proportion of the acid catalyst is, for example, 10 parts by mass of the compound represented by formula (4) above. The range can be selected from approximately 1000 parts by mass, and preferred ranges are as follows, in stages: The amounts are 0-700 parts by mass, 300-500 parts by mass, and 350-450 parts by mass. (Proportion of acid catalyst) If there is too little of it, the reaction may not proceed efficiently.

[0118] Furthermore, the reaction may be carried out in the presence of thiols. Examples of thiols include Mel Captocarboxylic acid, aminoalkanethiol, thiocarboxylic acid, alkyl mercaptan, Examples include Alalquilmercaptan and its salts.

[0119] Examples of mercaptocarboxylic acids include 3-mercaptopropionic acid (or β-mercaptopropionic acid). 3-mercaptoalkanoic acid, 2-mercaptoalkanoic acid, such as lucaptopropionic acid Examples include mercaptosuccinic acid and mercaptobenzoic acid. 2-mercaptoalkanoic acid For example, thioglycolic acid (mercaptoacetic acid or mercaptoethaneic acid), Lactic acid (or α-mercaptopropionic acid), 2-mercaptobutyric acid (or 2-mercaptopropionic acid) Puto-n-butanoic acid), 2-mercaptoisobutyric acid (or 2-mercapto-isobutanoic acid) ) and other 2-mercaptoC 2-6 Examples include alkanic acids.

[0120] Examples of aminoalkanethiols include 2-aminoethanethiol (or cyste Amine), 2-aminopropanethol, 3-aminopropanethol, 2-aminobuta 3-aminobutanethiol, 4-aminobutanethiol, 6-aminohexa Nthiol, 8-aminooctanthiol, 11-aminoundecanethiol, 16-A Amino C such as minohexadecanethiol 2-20 Examples include alkanthiols.

[0121] Examples of thiocarboxylic acids include thioacetic acid and thiooxalic acid.

[0122] Examples of alkyl mercaptans include methyl mercaptan and ethyl mercaptan. Propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, dodecyl C such as mercaptan 1-16 Examples include alkyl mercaptans.

[0123] Examples of aralkyl mercaptans include benzyl mercaptan.

[0124] Examples of these salts include, for example, inorganic salts such as hydrochloride and sulfate; and acetate. Organic acid salts such as sodium salts, alkali metal salts such as potassium salts, calcium salts, magnesium salts Alkaline earth metal salts such as nesium salts; ammonium salts, tetramethylammonium salts, etc. Examples include any tetraalkylammonium salt; or double salts thereof. Preferably Examples include alkali metal salts such as sodium salts, and specific compounds include, for example, methyl Examples include sodium mercaptan and sodium ethyl mercaptan.

[0125] These thiols can be used individually or in combination of two or more. Among these thiols, 3-mercaptopropionic acid, thioglycolic acid, thiolactic acid, etc. Mercaptoalkanoic acid and aminoalkanethiols such as cysteamine are preferred.

[0126] The proportion of thiols is, for example, 0 parts by mass of the compound represented by formula (4) above. 0.1 parts by mass or more, specifically, it may be selected from a range of about 1 to 50 parts by mass, which is preferable. The ranges are, in stages, 2-20 parts by mass, 3-10 parts by mass, and 4-6 parts by mass. Furthermore, the proportion of thiols is, for example, 0.5% of the compound represented by formula (4) above. The range can be selected from approximately 0.1 to 0.5 moles, and the preferred range is, in stages, 0. These are 0.5-0.4 moles, 0.1-0.3 moles, and 0.15-0.2 moles. The proportion of the type is, for example, in the range of about 0.001 to 50 parts by mass per 100 parts by mass of the acid catalyst. The range can be selected from the following, and preferred ranges are 0.005 to 10 parts by mass, and 0. The amounts are 0.01 to 1 part by mass and 0.01 to 0.1 parts by mass. If the proportion of thiols is too low, the reaction will occur. The reaction may not proceed efficiently, and if there is too much thiols, impurities such as sulfur components may be present. There is a risk that they will remain in the area.

[0127] The reaction may be carried out in a solvent. Suitable solvents include, for example, ethers, specifically diene. Diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether Chain ethers such as ethers, tetrahydrofuran (THF), 1,4-dioxane, etc. Cyclic ethers, etc.; ketones, specifically acetone, methyl ethyl ketone, methyl Chain ketones such as isobutyl ketones, cyclic ketones such as cyclohexanone, etc. Tel compounds, specifically chain esters such as methyl acetate, ethyl acetate, and butyl acetate, γ- Butyrolactone, γ-valerolactone, γ-caprolactone (or γ-hexanolactone) Cyclic esters (lactones), such as dimethyl carbonate; carbonates, specifically dimethyl carbonate. Carbonate (or dimethyl carbonate), diethyl carbonate (or diethyl carbonate) Which chain carbonates, ethylene carbonate (or ethylene carbonate), propylene carbonate Cyclic carbonates such as hydroxypropyl carbonate (or propylene carbonate); amides, specific examples. It contains N,N-dimethylformamide (DMF), N,N-diethylformamide, N, Chain amides such as N-dimethylacetamide (DMAc), N-methyl-2-pyrrolide Cyclic amides such as NMP; ureas, specifically tetramethylurea, tetramethylurea, etc. Chain-like ureas such as ethylurea, 1,3-dimethyl-2-imidazolidinone (DMI or N,N'-dimethylethylene urea, N,N'-dimethyl-N,N'-trimethylene urea (Or cyclic ureas such as N,N'-propylene urea); nitriles, specifically, Cyanide hydrocarbons such as acetonitrile, propiononitrile, and benzonitrile; Nitrated hydrocarbons such as tromethane, nitroethane, nitropropane, and nitrobenzene ;Phosphoramides such as hexamethylphosphoramide;Sulfones, specifically eth Chain sulfones such as methylsulfone, cyclic sulfones such as sulfolane, etc. Sulfoxides such as hexane (DMSO); hydrocarbons, specifically hexane. aliphatic hydrocarbons such as heptane, octane, and decane, and alicyclic carbons such as cyclohexane. Hydrogen compounds, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, etc. ;Halogenated hydrocarbons, specifically methylene chloride, chloroform, carbon tetrachloride, 1, Haloalkanes such as 2-dichloroethane, chlorobenzene, and dichlorobenzene Examples include benzene.

[0128] These solvents can be used individually or in combination of two or more. The solvent includes at least one selected from ethers, sulfones, and ureas. Preferably, and in particular, a cyclic compound having a cyclic structure within the molecule (having a cyclic structure) aprotic polar solvents, among them cyclic ethers such as 1,4-dioxane, At least one selected from cyclic sulfones such as horane and cyclic ureas such as DMI It is preferable that it contains seeds.

[0129] The proportion of the solvent is, for example, 100~ per 100 parts by mass of the compound represented by formula (4) above. The range may be selected from approximately 10,000 parts by mass, and preferred ranges are as follows: These are 300-2000 parts by mass, 400-1500 parts by mass, and 500-1000 parts by mass. If the proportion of solvent is too high, the concentration of the raw materials may be too low, which may reduce the reactivity. If the proportion is too low, the viscosity may become too high, potentially reducing its reactivity.

[0130] The reaction temperature can be selected from a range of approximately 0 to 200°C, and a preferred range is as follows: The temperature ranges are, in stages, 10-100°C, 20-80°C, and 30-60°C. The reaction time is as follows: For example, you can choose from a range of about 30 minutes to 48 hours, and the preferred ranges are as follows: The available timeframes are 1-24 hours, 2-12 hours, and 4-8 hours.

[0131] The reaction may be carried out with stirring, in air, or in an inert atmosphere such as nitrogen gas or a noble gas. The reaction may be carried out in air, at atmospheric pressure, or under pressurized pressure. Furthermore, the reaction may be carried out while dehydrating. That's fine.

[0132] Furthermore, the reaction mixture (reaction solution or reaction mixture) after the reaction is complete can be disposed of by conventional methods, for example, Filtration, concentration, extraction, neutralization, washing, drying, crystallization, column chromatography, and combinations thereof They may be separated (or purified) by a combination of means.

[0133] (Preparation of the compound represented by formula (1) in the first reaction step) The fluorene compound (diol compound) represented by formula (1) above is represented by formula (2) above. The compound and the compound represented by formula (3a) and the compound represented by formula (3b) It can be prepared by coupling reaction (or cross-coupling reaction).

[0134] As for coupling reactions, there are conventional coupling reactions, such as the Suzuki-Miyaura coupling reaction. G reaction, Migita-Kosugi-Stille coupling reaction, Negishi coupling reaction, Hinoki Coupling reactions such as the Yama coupling reaction, which are catalyzed by palladium (or palladium(0)) catalysts. Nickel catalysts for ring reactions, Kumada-Tamao-Corriu coupling reactions, etc. Examples include coupling reactions using nickel(0) catalysts. Among the coupling reactions, the Suzuki-Miyaura coupling reaction is preferred.

[0135] In equation (2) (or equation (4)) above, X 1a and X 1b Each is independent of the others. It exhibits a reactive group capable of forming a carbon-carbon bond (or direct bond) via a plucking reaction; In equations (3a) and (3b) above, X 2a The reactive group X 1a And, X 2b The above Reactive group X 1b In addition, each capable of forming a carbon-carbon bond through a coupling reaction. This indicates a reactive group. Reactive group X 1a and X 1b and X 2a and X 2b That was, The appropriate method can be selected depending on the type of coupling reaction. The Suzuki-Miyaura coupling reaction When synthesizing, one of the reactive groups, for example, group X 1a and X 1b For example, halogen atoms Examples include alkanesulfonyloxy groups of fluoride. Examples of halogen atoms include Examples include iodine atoms, bromine atoms, and chlorine atoms. Alkanesulfonyl fluoride Examples of xy groups include the trifluoromethanesulfonyloxy group (or the group [-OTf ]) and other fluoride C 1-4 Examples include alkanesulfonyloxy groups. The reactive groups may be used individually or in combination of two or more. Halogen atoms are preferred, iodine atoms and bromine atoms are more preferred, and bromine atoms are even more preferred. It is preferable.

[0136] The reactive group X in the Suzuki-Miyaura coupling reaction 1a and X 1b and cup Ringable other reactive group X 2a and X 2b For example, a boronic acid group (dihydrogen Examples include the roxyboryl group or group [-B(OH)2]), boronic acid ester group, etc. Examples of boronic acid ester groups include dimethoxyboryl group and diisopropoxyboryl group. , dialkoxyboryl groups such as dibutoxyboryl groups; pinacolateboryl groups (or groups [ -Bpin]), 1,3,2-dioxaborinan-2-yl group, 5,5-dimethyl-1, Examples include cyclic boronic acid ester groups such as the 3,2-dioxaborinan-2-yl group. These other reactive groups may be used individually or in combination of two or more. Of the groups, the group [-B(OH)2] is preferred.

[0137] Note that base X 1a and X 1b And, base X 2a and X 2b This means that each of them is a couple Any pair of reactive groups capable of performing a reaction may be used, and group X 1a Oh biX 1b The other reactive group is a boronic acid group, and group X 2a and X 2b Haroge The reactive group may be one of the above, such as an atom, but the group X 1a and X 1b is halogen The reactive group X is one of the aforementioned reactive groups, such as the child. 2a and X 2b The other, such as a boronic acid group. It is preferable that it is a reactive group.

[0138] As for the compound represented by formula (2), a preferred fluorene compound represented by formula (1) is Compounds corresponding to the desired configuration, for example, 9,9-bis(6-hydroxy-2-naphthyl) 9,9-bis(hydroxynaphthyl)-dihalofluorene, such as -2,7-dibromofluorene Oren; 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-di 9,9-bis[hydroxy(poly)alkoxy-naphthyl]-di such as bromofluorene Examples include halofluoren.

[0139] The compounds represented by formula (3a) and formula (3b) are, Compounds corresponding to preferred embodiments of the fluorene compound represented in (1), for example, phenyl Examples include boronic acid, 1-naphthylboronic acid, and 2-naphthylboronic acid, and 2-naphthyl Boronic acids are preferred. Compounds represented by formula (3a) and compounds represented by formula (3b) The substances are preferably the same compound. The compound represented by formula (3a) and formula (3 The compound represented in b) can be a commercially available product or similar.

[0140] The compound represented by formula (2), the compound represented by formula (3a), and formula (3b) The ratio of the total amount of the compounds represented by the formula is, for example, former / latter (molar ratio) = 1 / 2 to 1 / 1 It can be as low as 0, and the preferred range is, in stages, 1 / 2.1 to 1 / 5, 1 It can also be 2.2 to 1 / 3 or 1 / 2.3 to 1 / 2.5, allowing for more efficient preparation. More preferably, it is 1 / 2.1 to 1 / 2.3.

[0141] The coupling reaction may be carried out in the presence of a catalyst. The Suzuki-Miyaura coupling reaction is an example. When synthesizing, the reaction may be carried out in the presence of a palladium catalyst, and the palladium catalyst is Conventional coupling catalysts, such as palladium(O) catalysts and palladium(II) catalysts. Some examples include:

[0142] Examples of palladium(O) catalysts include tetrakis(triphenylphosphine)para Dium(0) [or Pd(PPh3)4], bis(tri-t-butylphosphine)para Palladium(O)-phosphorus such as Dium(O) [or Pd(P(t-Bu)3)2] Examples include complexes.

[0143] Examples of palladium(II) catalysts include [1,2-bis(diphenylphosphinone) Ethane]palladium(II) dichloride [or PdCl2(dppe)], [1,3- Bis(diphenylphosphino)propane]palladium(II) dichloride [or PdC l2(dppp), [1,1'-bis(diphenylphosphino)ferrocene]paradiu Mu(II) dichloride [or PdCl2(dppf)], bis(triphenylphosphoric acid) Palladium(II) dichloride [or PdCl2(PPh3)2], bis(tri- o-Tolylphosphine)palladium(II) dichloride [or PdCl2(P(ot Examples include palladium(II)-phosphine complexes such as [olyl)3)2]. When using a palladium(II) catalyst, for example, phosphine, amine, organometallic reagents The reaction is initiated when any reducing compound in the reaction system reduces the complex to a zero-valent state.

[0144] The palladium catalyst may be, for example, tris(dibenzylideneacetone)dipalladium Mu(0)chloroform complex [or Pd2(dba)3·CHCl3], palladium acetate (II) Catalyst precursors such as triphenylphosphine, phosphines such as triphenylphosphine, and carbenes The catalyst precursor may be prepared in the reaction system by adding ligands such as the above. The ratio may be, for example, the former / latter (molar ratio) = approximately 1 / 4 to 1 / 10, and is preferable. The probability is 1 / 4 to 1 / 5.

[0145] These catalysts can be used individually or in combination of two or more. Among the catalysts, palladium(0)-phosphine complexes such as Pd(PPh3)4 and palladium acetate Catalyst precursors such as um(II) and vinegar are particularly suitable due to their excellent handling properties (stability in air). Palladium(II) acid is preferred. The proportion of the catalyst is 1 mole of the compound represented by formula (2) above. In contrast, the amount may be, for example, around 0.0001 to 0.1 moles in terms of metal, and is preferable. This may be 0.01 to 0.07 moles, more preferably 0.04 to 0.06 moles. Particularly preferable for more efficient preparation is the following stepwise process: 0.0001 to 0.001 mo The amount is 0.0003 to 0.0007 moles, and before the catalyst such as palladium(II) acetate. When using a casing, it is particularly preferable to use 0.0005 to 0.0015 moles.

[0146] The Suzuki-Miyaura coupling reaction may be carried out in the presence of a base. Examples of bases include, for example... Metal carbonates or bicarbonates, metal hydroxides, metal fluorides, metal phosphates, metal organic compounds Examples include salts and metal alkoxides.

[0147] Examples of metal carbonates or bicarbonates include sodium carbonate, potassium carbonate, and carbonic acid. Cesium, alkali metal carbonates such as sodium bicarbonate or bicarbonates, thalium carbonate Examples include Mu (I).

[0148] Examples of metal hydroxides include sodium hydroxide, potassium hydroxide, and cesium hydroxide. Alkali metal hydroxides such as barium hydroxide, alkaline earth metal hydroxides such as hydroxide Examples include thallium(I).

[0149] Examples of metal fluorides include alkali metals such as potassium fluoride and cesium fluoride. Examples include fluorides.

[0150] Examples of metal phosphates include alkali metal phosphates such as tripotassium phosphate. It can be listed.

[0151] Examples of metal organic acid salts include alkali metal acetates such as potassium acetate. It can be done.

[0152] Examples of metal alkoxides include sodium methoxide and sodium ethoxide. Examples include alkali metal alkoxides such as potassium t-butoxide.

[0153] These bases can be used individually or in combination of two or more. As the base, metal carbonates such as potassium carbonate are preferred. The proportion of the base is given by formula (2) above. For 1 mole of the compound represented by , the amount may be, for example, around 0.1 to 50 moles, and is preferred. Alternatively, the amounts can be in stages, such as 0.5-5 moles, 1-3 moles, or 1.5-2.5 moles. More preferably, in terms of being able to prepare more efficiently, the following steps are used: 5-10 moles, 6-8 moles. It is 6.5 to 7.5 moles.

[0154] The coupling reaction may be carried out with or without the presence of a phase transfer catalyst. Examples of catalysts include tetrabutylammonium bromide (TBAB) and trioctyl Examples include tetraalkylammonium halides such as methylammonium chloride. These phase transfer catalysts can be used individually or in combination of two or more types. .

[0155] Coupling reactions may be carried out in the absence or presence of a solvent inert to the reaction. Examples of media include water; alcohols such as methanol and ethanol; and cyclic ethers. Ethers such as chain ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as benzoyl benzoate (MIBK); esters such as ethyl acetate; acetonitrile, benzoyl benzoate Nitriles such as nitriles; N,N-dimethylformamide, dimethylacetamide, N Amides such as methyl-2-pyrrolidone; sulfoxides such as dimethyl sulfoxide. Examples include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and other types of hydrocarbons. It can be done.

[0156] Examples of cyclic ethers include dioxane and tetrahydrofuran. Examples of linear ethers include diethyl ether, diisopropyl ether, and other dialkyl ethers. Examples include glycol ethers and glycol ethers. The glycol ethers include: For example, (poly)alkylene glycols such as methyl cellosolve and methyl carbitol (Poly)alkylene glycol dialkyl, such as noalkyl ethers and dimethoxyethane. Examples include ether.

[0157] Examples of aliphatic hydrocarbons include hexane and dodecane. Examples of hydrogen compounds include cyclohexane. Examples of aromatic hydrocarbons include... Examples include toluene and xylene.

[0158] These solvents can be used individually or in combination of two or more. Among the media, a mixture of water and aromatic hydrocarbons such as toluene or ketones such as MIBK. A solvent is preferred.

[0159] Coupling reactions occur under an inert gas atmosphere, such as nitrogen gas; helium, argon, etc. The reaction can be carried out under any noble gas atmosphere. The reaction temperature is preferably, for example, 50-200°C. The temperature is 60-100°C, more preferably 70-90°C, and particularly 75-83°C. The reaction time may be, for example, 0.5 to 24 hours, preferably 10 to 20 hours. It is acceptable, and even more preferable for more efficient preparation, it is about 0.5 to 8 hours. It takes 5 to 1.5 hours.

[0160] After the reaction is complete, the reaction mixture may be separated and purified using conventional methods, such as neutralization and washing, if necessary. Extraction, filtration, dehydration, concentration, decantation, drying, crystallization, reprecipitation, column chromatography Separation and purification may also be performed by methods such as filtration, adsorption, or a combination of these.

[0161] Furthermore, the fluorene compound represented by formula (1) can be obtained by a method different from the above method, for example... Alternatively, it may be prepared according to the following reaction sequence (second reaction sequence).

[0162] [ka]

[0163] (In the formula, Y 1a and Y 1b , k1a and k1b, R 2a and R 2b , m2a and m2b, and Y 2a and Y 2b This is the same as formula (1) above, including preferred embodiments. , X 1a and X 2a and X 1b and X 2b The first reaction process formula and the preferred state (Including the honorific prefix, it is the same.)

[0164] In the second reaction step formula, the compound represented by formula (5a) and the compound represented by formula (5b) The compound reacts to form group Y 2a and Y 2b The process of introducing and the expression represented by formula (3a) The compound and the compound represented by formula (3b) are reacted to form group Y 1a and Y 1b To introduce The order of the steps is reversed compared to the first reaction step equation. Therefore, the second reaction step The preparation of the compound represented by formula (6) in the formula is as follows (in the first reaction step formula) In the section on preparation of the compound represented by (1), the compound represented by formula (2) Alternatively, use the compound represented by formula (4) (or read formula (2) as formula (4) It can be prepared by (substituting). Also, the second reaction step formula is represented by formula (1) Similarly, for the preparation of the compound, the chemical (represented by formula (2) in the first reaction step formula) In the section on preparation of the compound, replace the compound represented by formula (4) with the compound represented by formula (6). By using a compound represented by (or by replacing formula (4) with formula (6) above) It can be manufactured.

[0165] As described above, the production of the fluorene compound (diol compound) represented by formula (1) The method is as follows: (i) the compound represented by formula (2) above and the compound represented by formula (3a) below (ii) A step of coupling reaction with a compound represented by formula (3b); or (ii) the above formula ( 6) The compound represented by formula (5a) and the compound represented by formula (5b) below The process only needs to include one of the steps of reacting the compound with the reaction intermediate of formula (2 The compounds represented by (6) and (6) are prepared using the methods described above or other conventional methods. That's good too.

[0166] (purification process) The fluorene compound (diol compound) represented by formula (1) above is separated using the conventional separation method described above. Although purification may be carried out by the manufacturing method, due to the influence of the reaction conditions mentioned above, the separation may not be sufficient or efficient. It may not be possible to separate and purify it, making it difficult to prepare it with relatively high purity and high yield. However The fluorene compound obtained in the above reaction step is then dissolved in a solvent, for example, in the solution of formula (1) As a solvent for forming a composition (liquid composition or solution) with the fluorene compound. A solvent similar to the example solvent, preferably (a) aromatic hydrocarbons and aliphatic hydrocarbons. (b) a solvent containing at least (a) a (b) a solvent containing at least (a) ketones (a) Precipitation (crystallization, recrystallization, or reprecipitation) from at least one solvent selected from the precipitation solvents. The material is separated and purified through a purification process (crystallization, recrystallization, or reprecipitation). Compared to other separation and purification methods such as column chromatography, it is possible to obtain high-purity and efficient results. The fluorene compounds described appear to be easy to prepare.

[0167] (a) In a solvent containing at least aromatic hydrocarbons and aliphatic hydrocarbons, Examples of aromatic hydrocarbons used as a medium include benzene, toluene, xylene, etc. Examples include, and toluene is preferred. Examples of the aliphatic hydrocarbons that are poor solvents include, C such as hexane, heptane, and decane 5-12 Examples include alkanes, and heptanes. C 6-8 Alkanes are preferred.

[0168] The ratio of aromatic hydrocarbons such as toluene to aliphatic hydrocarbons such as heptane For example, the ratio of the former to the latter (volume ratio) can be selected from a range of approximately 10 / 90 to 90 / 10. Also, the preferred ranges are, in stages, 10 / 90 to 90 / 10, 20 / 80 to The ratios are 70 / 30, 30 / 70, and 50 / 50. Note that the above volume ratios are based on a temperature of 20-25°C and 1 gas. The volume ratio during reduction may also be acceptable.

[0169] The proportion of the total amount of aromatic hydrocarbons and aliphatic hydrocarbons is: aromatic hydrocarbons and aliphatic hydrocarbons For example, 50% by mass or more, preferably in steps below, relative to the total amount of the solvent containing aliphatic hydrocarbons. The content is 70% by mass or more, 90% by mass or more, and more preferably substantially 100% by mass. be.

[0170] Furthermore, (b) a crystallization solvent containing at least ketones, the ketones include, for example, C, such as acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), etc. 3- Examples include 6 ketones. The proportion of ketones is relative to the total amount of the crystallization solvent containing ketones. For example, 50% by mass or more, preferably in stages, 70% by mass or more, 90% by mass or more. Yes, and more preferably substantially 100% by mass.

[0171] Purification using solvent (a) yields an amorphous (non-crystalline) substance, while purification using solvent (b) yields crystals. It appears that, among solvents (a) and (b), while maintaining high purity and yield, Crystallization solvent (b) is preferred because it is easier to reduce discoloration, and in particular C such as MIBK. 5-6 Ke It is preferable to crystallize using a crystallization solvent containing tonides.

[0172] In the purification process, particularly the crystallization process, for example, the solution is concentrated to a concentration of 10-60% by mass, preferably 20%. The concentration may be adjusted to ~50% by mass, more preferably 30-50% by mass. Also, stirring and Alternatively, crystallization may be carried out while cooling, for example, at about 100-500 rpm, preferably 2 Stirring at approximately 00-300 rpm, for example, at 40-100°C, preferably 50-70°C. The temperature is then lowered, and crystallization occurs at a precipitation temperature of, for example, 30-60°C, preferably 40-50°C. Alternatively, the mixture may be allowed to cool while standing without stirring, for example, in a room at around 20-30°C. The crystallization may be performed after the temperature has been lowered to a moderate level.

[0173] The HPLC purity of the resulting fluorene compound represented by formula (1) is, for example, 75% or less. It may be above, preferably 80% or more, more preferably 85% or more, and even more preferably The percentage is over 90%, particularly over 95%, and especially over 98%. Within the scope of the claims, HPLC purity can be measured by the method described in the examples below.

[0174] Furthermore, the yield of the fluorene compound represented by formula (1) obtained is, for example, 40% or more. The preferred ranges are, in order, 50% or more, 60% or more, and 70% or more. More preferably, it is 80% or more.

[0175] [Fluorene compounds represented by formula (1E) (epoxy compounds or epoxy resins)] The fluorene compound represented by formula (1E) has an odor similar to the compound represented by formula (1). The group Y is attached to the 9,9 position of the fluorene skeleton. 2a and Y 2b [Represented by the above formula (Y2) Instead of the hydroxyl group-containing group, the group Y 3a and Y 3b [Represented by the above formula (Y3) It is an epoxy compound (or epoxy resin) having an epoxy group-containing group.

[0176] The epoxy group Y represented by the formula (Y3) 3a and Y 3b In R 4 is hydrogen It is preferable that it be an atom. Also, in the above formula (Y3), R 3 , m3, A 1 and n1 These are the same as formula (Y2) above, including preferred embodiments.

[0177] Therefore, a typical epoxy group containing Y 3a and Y 3b This is illustrated in the term of formula (1) above. Hydroxyl group containing Y 2a and Y 2b In response, the hydroxyl group is glycidyl Examples include groups replaced with an oxy group or a β-methylglycidyloxy group. Epoxy group containing Y 3a and Y 3b Also contains a hydroxyl group Y 2a and Y 2b against The same applies, and among them, 6-glycidyloxy-2-naphthyl group, 6-(2-glyc 6-glycidyloxy(mono or hex) groups such as cydyloxyethoxy-2-naphthyl groups Sa)C 2-3 An alkoxy-2-naphthyl group is preferred; in particular, a 6-glycidyloxy-2- A naphthyl group is preferred. Note that epoxy group-containing group Y is also preferred. 3a and Y 3b The types are the same as each other. They may be one or different, but identical is preferred.

[0178] Furthermore, in the above formula (1E), Y 1a and Y 1b , k1a and k1b, R 2a oh Call R2b m2a and m2b, as well as k1a+m2a and k1b+m2b, These are the same as formulas (1) and (Y1) above, including preferred embodiments. Note that Y 1a and Y 1b The inner ring Z 1 However, especially with condensed polycyclic arene rings such as naphthalene rings, fluorescein Not only is it easy to effectively improve folding ratio and heat resistance, but it also has a surprisingly low melting onset temperature and high melting rate. It is preferable because it can also exhibit compatibility.

[0179] Therefore, the epoxy compounds represented by the aforementioned formula (1E) are also considered representative. Corresponding to the diol compound represented by the above formula (1), the two hydroxyl groups are glycerin Examples include compounds in which a zyloxy group or a β-methylglycidyloxy group has been replaced. The epoxy compound represented by the preferred formula (1E) is also represented by the formula (1). The same applies to preferred embodiments of the diol compounds, and among them, 9,9-bis(6- 9, such as glycidyloxy-2-naphthyl)-2,7-di(2-naphthyl)fluorene 9-Bis(glycidyloxynaphthyl)-2,7-dinaphthylfluorene; 9,9-bis [6-(2-(glycidyloxy)ethoxy)-2-naphthyl]-2,7-di(2-naphthyl) 9,9-bis[glycidyloxy(mono or dec)C] such as fluorene (C) 2-4 a Lucoxynaphthyl]-2,7-dinaphthylfluorene is preferred, and 9,9-bis(6- Hydroxy-2-naphthyl)-2,7-di(2-naphthyl)fluorene is even more preferred. .

[0180] The epoxy compound represented by formula (1E) has a high refractive index. The refractive index of the compound is, for example, 1.67 to 1.8 at a temperature of 25°C and a wavelength of 589 nm. Physically, a value of around 1.67 to 1.77 is acceptable, and the preferred range is as follows: , 1.69-1.75, 1.7-1.74, 1.71-1.73 may also be; further Preferably, the following steps: 1.72-1.79, 1.73-1.78, 1.74-1.7 The values ​​are 75, 1.75-1.77.

[0181] Furthermore, the epoxy compound represented by formula (1E) has high heat resistance. The 5% mass loss temperature of the phenyl compound may be, for example, around 300-500°C, and is preferred. The recommended temperature ranges are, in stages, 350-450°C, 370-430°C, and 380-42°C. It is 0℃.

[0182] Although the epoxy compound represented by the above formula (1E) exhibits a high 5% mass loss temperature, Surprisingly, it exhibits a low melting temperature, with the melting onset temperature being, for example, 100-25°C. It may be around 0°C, preferably in stages, 120-200°C, 130-180°C The temperature is 140-160°C. Therefore, it can be easily mixed with other components, as described later, through melting and kneading. Alternatively, a uniform curable composition can be prepared efficiently.

[0183] Furthermore, in this specification and the claims, the fluorene represented by formula (1E) is used. The refractive index, 5% mass loss temperature, and melting temperature of the compound were determined by the method described in the examples below. It can be measured.

[0184] Furthermore, the epoxy equivalent of the epoxy compound (or epoxy resin) is, for example, 300~ You may select a range of approximately 1500 g / eq, preferably 350 to 1000 g / eq More preferably, it may be 400-500 g / eq; particularly preferably, 350- 480 g / eq, particularly 370-450 g / eq. (Note: This specification and patent application) Within the range of the request, the epoxy equivalent of the epoxy compound is as specified in JIS K 7236:20 It can be measured by the method described in the examples below, in accordance with 01.

[0185] The epoxy compound (or the curable composition described later) is represented by the formula (1E) above. This includes not only the monomers of the compounds, but also their polymers, such as dimers, trimers, tetramers, etc. It may be a mixture containing dimers to decamers. The polymer may be used alone or in combination of two or more types. It may be included in the formula.

[0186] In this specification and in the claims, unless otherwise specified, the epoxy compound The "multimer" is a structure derived from the starting compound [the diol compound represented by formula (1) above] ( This refers to epoxy compounds that have two or more diols (skeletons) in their chemical structure, and these two or more diols The structure derived from the compound is a linking group derived from the epihalohydrin component described later, for example, 2-hydrox They are linked (connected) via cypropane-1,3-diyl groups, etc. Such polymers This is unavoidable in the manufacturing process of the compound (monomer) represented by formula (1E) described later, or It is acceptable for it to be introduced as an impurity, and one-stage (taffy method or direct method) or two-stage method may be used as needed. The monomers prepared by conventional methods such as the Advanced method, melting method, or indirect method are intentionally converted into monomers. It may be added to it.

[0187] The proportion of the aforementioned polymer is, for example, 0 to 50 moles relative to the total number of moles of the monomer and polymer. It may be around 0% of mol, specifically around 0 to 20 mol%, preferably 0 to 10 mol. More preferably, it is 0 to 5 mol%. The aforementioned percentage is, for example, 0.1 to 8 mol%, preferably The amount may be 0.2 to 3 mol%.

[0188] Furthermore, the HPLC purity of the fluorene compound (monomer) represented by formula (1E) is, for example, It may be around 75% or more, preferably 85% or more, and more preferably 90% or more. In this specification and in the claims, HPLC purity is defined as the implementation described later. It can be measured using the method shown in the example.

[0189] [Method for producing fluorene compounds (epoxy compounds) represented by formula (1E)] The method for producing the epoxy compound represented by formula (1E) is not particularly limited, for example, By reacting the diol compound represented by formula (1) with the epihalohydrin component, It may be prepared.

[0190] Epihalohydrin components (epihalohydrins) include epihalohydrin and β-methionine. Examples include epihalohydrins. For example, epichloro Examples include hydrins, epibromohydrins, and epiiodohydrins. β-methylepi Examples of halohydrins include β-methylepichlorohydrin and β-methylepibromohydrin. Examples include β-methylepiiodohydrin. These epihalohydrin components are These epihalohydrin components can be used individually or in combination of two or more. Of these, epihalohydrins such as epichlorohydrin and β-methylepichlorohydrin This is preferred, and epichlorohydrin is even more preferred.

[0191] The proportion of the epihalohydrin component is given by the ratio of 1 mole of the diol compound represented by formula (1) above. For example, it is sufficient if it is 2 moles or more, but an excess amount relative to the diol compound, for example 5 moles or more, is acceptable. The amount is 100 moles, preferably 10 to 50 moles, and more preferably 15 to 30 moles.

[0192] Furthermore, the reaction may be carried out in the presence or absence of a catalyst, as needed. As a catalyst, for example, a quaternary ammonium salt, specifically tetramethylammonium Tetramethylammonium bromide and other tetramethylammonium bromide 1-20 Alkyl Benzyltrimethylammonium chloride and other benzyltrimethylammonium chloride 1-4 Alkylammonium halides, etc.; trimethylamine boranes, etc. 1-4 Examples include alkylamine boranes, crown ethers, phosphonium salts, and pyridinium salts. The catalyst may be used alone or in combination of two or more types.

[0193] When a catalyst is used, the proportion is not particularly limited, but it is the diol represented by formula (1) above. For every mole of the compound, for example, 0.001 to 1 mole, preferably 0.01 to 0.2 moles. More preferably, it is 0.05 to 0.1 moles.

[0194] Furthermore, in order to trap the hydrogen halides produced by the reaction, the reaction is carried out in the presence of a base. It may be used. The base is an inorganic salt such as a metal hydroxide, metal carbonate, or bicarbonate. Examples of bases include organic bases such as amines. Examples of metal hydroxides include sodium hydroxide. Alkali metal hydroxides such as potassium hydroxide, alkaline earth metals such as calcium hydroxide Examples include metal hydroxides. Sodium carbonate is an example of a metal carbonate or bicarbonate. Examples include alkali metal carbonates such as sodium bicarbonate, or alkaline earth metal salts. Examples of amines include trialkylamines such as triethylamine and benzyldimethylamine. Examples include aromatic tertiary amines such as amines, and heterocyclic tertiary amines such as pyridine. The bases may be used alone or in combination of two or more. Among these bases, the strong bases ( A strong alkali is preferred, and a metal hydroxide such as sodium hydroxide is even more preferred.

[0195] The proportion of the base is not particularly limited, but for example, the hydrox of the compound represented by formula (1) above. For every mole of sil group, for example, 0.01 to 20 moles, preferably in stages, 0.05 moles. These are approximately 10 moles, 1-5 moles, and 2-4 moles.

[0196] The reaction may be carried out in an inert solvent or without a solvent. For example, aprotic solvents can be used, such as hydrocarbons, specifically hexane. aliphatic hydrocarbons such as heptane, aromatic hydrocarbons such as benzene and toluene, etc. Halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; ethyl acetate, etc. Esters; ethers, specifically dialkyl ethers such as diethyl ether. , cyclic ethers such as tetrahydrofuran; acetone, methyl ethyl ketone (ME K), ketones such as methyl isobutyl ketone (MIBK); dimethylformamide (D MF), amides such as dimethylacetamide; sulfoxys such as dimethyl sulfoxide Examples include solvents such as ions. The solvent may be used alone or in combination of two or more. Among the media, in terms of reactivity, ketones such as MEK and MIBK, amides, and sulfoxides are preferred. The following are preferred, and amides such as DMF and sulfoxides such as dimethyl sulfoxide are preferred. It is preferable.

[0197] The reaction may be carried out in air or in an inert atmosphere such as nitrogen gas or a noble gas, with stirring. The reaction may be carried out under normal pressure, pressurized pressure, or reduced pressure.

[0198] The reaction temperature and reaction time may be appropriately selected depending on the type of raw materials, etc. For example, the reaction temperature is... For example, 30-150°C, preferably in stages, 50-140°C, 100-130°C, and so on. The process may also be carried out under reflux (at reflux temperature); more preferably at 30-50°C. Furthermore, the reaction time is, for example, 30 minutes to 48 hours, preferably 2 to 6 hours.

[0199] After the reaction is complete, the reaction mixture may be separated and purified using conventional methods, such as washing and extraction, if necessary. Filtration, dehydration, concentration, decantation, drying, crystallization, reprecipitation, column chromatography The material may be separated and purified by methods such as adsorption or a combination of these methods.

[0200] [Curable composition] If the curable composition contains at least the epoxy compound represented by formula (1E), Often, thermosetting or photocurable compositions may also be used. Furthermore, if necessary, the aforementioned E Other epoxy compounds (epoxy resins) different from epoxy compounds, curing agents, curing accelerators, light It may also contain other components such as polymerization initiators, reactive diluents, solvents, and additives. It is not necessary. The epoxy compound represented by formula (1E) above is particularly Y 1a and Y 1b Medium Ring Z1 If it is a polycyclic arene ring such as a condensed polycyclic arene ring, then the chemical structure contains many Despite having a benzene ring skeleton, it surprisingly exhibits excellent solubility (compatibility), therefore, Even if other components are present, a uniform curable composition and cured product can be easily or efficiently prepared. can.

[0201] (Other epoxy compounds) Other epoxy compounds (epoxy resins) different from those of formula (1E) include, for example, G Lysidyl ether type epoxy resins, specifically bisphenol A and bisphenol F Biphenol type, such as bisphenol AD ​​type, bisphenol S type, biphenol type, etc. Phenolic epoxy resins, phenol novolac type, cresol novolac type, and other novolacs Rack-type epoxy resin, phenol aralkyl-type epoxy resin, triphenolalkane Epoxy resins such as tetrakis(glycidyloxyphenyl)ethane, etc. Nol-type epoxy resins, condensed ring aromas such as 1,6-bis(glycidyloxy)naphthalene Hydrocarbon-modified epoxy resins, 9,9-bis(glycidyloxyaryl)fluorenes , 9,9-bis[glycidyloxy(poly)alkoxyaryl]fluorenes and others epoxy resins having a 9,9-bisarylfluorene skeleton, etc.; aromatic dicarboxylic acids Glycidyl ester type epoxy resins such as diglycidyl esters (or their hydrogenated derivatives) Tetraglycidyldiaminodiphenylmethane, tetraglycidylbisaminomethylmethyl Glycidylamine-type epoxy resins such as hydroxyhexane and triglycidylaminophenol; Bis(3,4-epoxycyclohexylmethyl)adipate, (3,4-epoxycyclo Cyclic aliphatic compounds such as hexyl)methyl-3,4-epoxycyclohexanecarboxylate. epoxy resins; stilbene-type epoxy resins; isocyanurate-type epoxy resins, hydan Heterocyclic epoxy resins such as toin-type epoxy resins and epoxy resins containing xanthene units Examples include bromine-containing epoxy resins such as tetrabromobisphenol A type epoxy resin. It can be done.

[0202] These other epoxy resins may be monomers, or polymers such as dimers and trimers. These other epoxy resins may be present. They may be used individually or in combination of two or more types. Other preferred epoxy resins include bisphenol A type epoxy resins and other bi or bisphenol A epoxy resins. It is an enolic epoxy resin.

[0203] If other epoxy resins are included, the epoxy resin (the epoxy represented by formula (1E)) The proportion of the compound is, for example, 50 to 99% by mass relative to the total epoxy resin in the curable composition. The mass is preferably 60-98% by mass, and more preferably 70-95% by mass.

[0204] (Curing agent, curing accelerator, photopolymerization initiator) At least one selected from curable compositions, curing agents, curing accelerators, and photopolymerization initiators It may or may not contain seeds. As a hardening agent, for example, an amine-based hardening agent can be used. Examples include curing agents, polyaminoamide-based curing agents, acid anhydride-based curing agents, and phenolic resin-based curing agents. It is possible.

[0205] The amine-based curing agent may be a primary amine, for example, a chain-like aliphatic amine. Specifically, ethylenediamine, hexamethylenediamine, diethylenetriamine, Chain-like aliphatic polyamines such as triethylenetetramine; cyclic aliphatic amines, specific examples. It contains mensendiamine, isophoronediamine, and bis(4-amino-3-methylcyclohex Xyl(methane), norbornanediamine, 3,9-bis(3-aminopropyl)-2,4 Monocyclic, bridging-cyclic, or sulfate-like compounds such as ,8,10-tetraoxaspiro[5.5]undecane Pyrocyclic aliphatic polyamines, etc.; aromatic aliphatic polyamines such as xylylenediamine; meta Phenylenediamine, diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfon Examples include aromatic amines such as ammonium compounds.

[0206] Examples of polyaminoamide-based curing agents include ethylenediamine and diethylenetriamine. Polyethylene polyamines such as triethylenehexamine, dimer acid, and as needed Examples include condensates with fatty acids.

[0207] Examples of acid anhydride-based curing agents include dodecenyl succinic anhydride and polyadipic anhydride. Aliphatic acid anhydrides such as tetrahydrophthalic anhydride and methyltetrahydrophthalic anhydride. Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl hymic anhydride Acids, alicyclic acid anhydrides such as methylcyclohexenedicarboxylic acid anhydride; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, etc. Examples include aromatic acid anhydrides.

[0208] Examples of phenolic resin curing agents include phenol novolac resin and cresol novolac resin. Examples include novolac resins such as volac resins and resol-type phenolic resins.

[0209] These hardeners can be used individually or in combination of two or more types. Among the curing agents, phenolic resin-based curing agents are preferred, such as phenol novolac resin. Novolac resin is even more preferable.

[0210] The proportion of the hardener is the epoxy resin component (compound having an epoxy group) in the curable composition. For example, 0.1 to 500 parts by mass, preferably 1 to 300 parts by mass, per 100 parts by mass of the total amount. More preferably, 10 to 150 parts by mass of the curing agent. Also, the functional group (or active hydrogen) of the curing agent. The ratio of ) is, for example, 0.1 to 4 equivalents per equivalent of epoxy groups of the epoxy resin component. The amounts are, in stages, 0.3 to 2 equivalents and 0.5 to 1.5 equivalents.

[0211] Examples of curing accelerators include tertiary amines, imidazoles, and their derivatives. Amines; alkali metal or alkaline earth metal alkoxides; phosphines, specific These include triarylphosphines such as triphenylphosphine; dimer acid polyamides. Which amide compounds; Lewis acid complex compounds such as boron trifluoride-ethylamine complexes; poly Sulfur compounds such as sulfides and mercaptan compounds (thiol compounds); phenyl glycerides Boron compounds such as loloborane; condensation compounds such as organotitanium compounds and organoaluminum compounds. Examples include hydroxyorganometallic compounds. With respect to the amines, tertiary amines include Ethylamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol Nol, tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4 Examples include .0]-7-undecene, and among the imidazoles, 2-methylimi mono- or dialkylimidazoles such as dazole and 2-ethyl-4-methylimidazole Examples include arylimidazoles such as 2-phenylimidazole, and the derivatives Examples include phenolic salts, phenol novolac salts, carbonates, and formate salts. These hardening accelerators may be used individually or in combination of two or more. Among the ionization accelerators, phosphines are preferred, and triaryl phosphines such as triphenylphosphine are preferred. Phosphines are even more preferred.

[0212] The proportion of the curing accelerator is determined by the epoxy resin component (compound having an epoxy group) in the curable composition. For every 100 parts by mass of the total amount of ), for example, 0.01 to 30 parts by mass, preferably in the following steps The amounts are 0.05 to 20 parts by mass, 0.1 to 10 parts by mass, and 0.1 to 5 parts by mass. Also, curing accelerator The ratio of the curing agent is based on the total amount of epoxy resin components and curing agent in the curable composition, per 100 parts by mass. For example, 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, more preferably 0 It is 0.5 to 2 parts by mass.

[0213] The curable composition includes, for example, a photopolymerization initiator such as a cationic polymerization initiator or a photoacid generator. It may also be a photocurable composition. Examples of photopolymerization initiators include aromatic diazonium salts. , onium salts of Brønsted acids such as aromatic sulfonium salts and aromatic iodonium salts Some examples include:

[0214] Examples of aromatic diazonium salts include benzenediazonium hexafluoroanti Benzenediazonium hexafluorophosphate, such as monate Examples include the Mu type.

[0215] Examples of aromatic sulfonium salts include triphenylsulfonium hexafluorocarbon Triphenyl Sulfonium compounds, 4,4'-bis(diphenylsulfonio)diphenylsulfide bis 4,4'-bis(diphenylsulfonio)diphenyls such as hexafluorophosphate Examples include sulfides.

[0216] Examples of aromatic iodonium salts include diphenyliodonium tetrakis(penta) Fluorophenyl borate, diphenyliodonium hexafluorophosphate, etc. Diphenyliodonium compounds, di(4-nonylphenyl)iodonium hexafluorophosphate Examples include di(4-nonylphenyl)iodonium compounds such as phosphate.

[0217] These photopolymerization initiators can be used individually or in combination of two or more. The proportion of these photopolymerization initiators is determined by the epoxy resin component (containing epoxy groups) in the curing agent composition. For every 100 parts by mass of the total amount of the compound, add 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass. A small quantity is acceptable.

[0218] (Reactive diluent) As a reactive diluent, a low viscosity is preferred, for example, a viscosity of about 200 mPa·s at 25°C. The following are preferably monofunctional or polyfunctional epoxy compounds with a pressure of 30 mPa·s or less. This may also be the case. Examples of monofunctional epoxy compounds include 2-ethylhexylglycidyl ester. Alkyl glycidyl ethers such as glycidyl ethers, alkyl glycidyl ethers, etc. Glycidyl ethers, phenyl glycidyl ethers, pt-butylphenylglycidyl Arylglycidyl ethers such as zyl ethers, and alkylates corresponding to these compounds Glycidyl ethers such as glycidyl ethers of oxide adducts; octylene oxide Alkene oxides such as sides, styrene oxide, and 4-vinylcyclohexene monooxide Examples include the D type.

[0219] Examples of polyfunctional epoxy compounds include diglycidyl ethers and polyols. Examples include lysidyl ethers, diglycidylaniline, and cycloalkene oxides. The polyol polyglycidyl ether is butanediol diglycidyl ether , neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl Polyethylene glycol diglycidyl ether, polypropylene glycol (Poly)alkanediol diglycidyl ethers such as diglycidyl ethers, cyclo Hexanedimethanol diglycidyl ether, trimethylolpropanedi or triglyceride Examples include dil ethers, glycerin diethers, or triglycidyl ethers. Examples of alkene oxides include vinylcyclohexene dioxide and methylated vinylcyclohexene. Examples include xendioxide.

[0220] These reactive diluents may be used individually or in combination of two or more. The ratio is 100% of the total amount of epoxy resin components (compounds having epoxy groups) in the curing agent composition. For example, 1 to 1000 parts by mass, preferably 5 to 500 parts by mass, more preferably Or it is 10 to 200 parts by mass.

[0221] (solvent) As a solvent, for example, a fluorene compound represented by formula (1) and the composition (liquid composition The solvent may be similar to the solvent exemplified as the solvent for forming the substance or solution.

[0222] These solvents may be used individually or in combination of two or more. They can be used individually or in combination of two or more. Among these solvents, alkyl C glycol monoalkyl ether acetates are preferred, such as PGMEA. 2-4 Alkylene glycol mono C 1-4 Alkyl ether acetates are preferred. The ratio is 100% of the total amount of epoxy resin components (compounds having epoxy groups) in the curing agent composition. For the mass portion, you may select from a range of, for example, 0 to 500 mass portions, preferably the following steps The amounts are, in order, 10-400 parts by mass, 20-300 parts by mass, and 30-200 parts by mass. When a solvent is present, the solid content concentration of the curable composition is not particularly limited, and the curable composition is as desired. The material may be adjusted to exhibit dynamism, for example, to about 0.1 to 70% by mass.

[0223] (Additives) As additives, conventional additives include, for example, colorants such as dyes and pigments, stabilizers, fillers, Conductive agents, antistatic agents, flame retardants, flame retardant additives, flexible agents, plasticizers, surfactants, dispersants, compatible compounds Examples include conditioning agents, flow regulators, leveling agents, defoamers, surface modifiers, antibacterial agents, and preservatives. Examples of the stabilizers include heat stabilizers, antioxidants, and ultraviolet absorbers. Examples of fillers include silica, talc, and mica. Examples of flame retardants include phosphorus. Examples include halogenated flame retardants, halogenated flame retardants, and inorganic flame retardants. These additives can be used individually. They may be used individually or in combination of two or more. The total proportion of these additives is the total solid content. It may be, for example, 10% by mass or less, preferably 0 to 3% by mass, relative to the body; for example 0 It may be approximately 0.01 to 5% by mass, preferably 0.1 to 1% by mass.

[0224] The curable composition comprises an epoxy compound represented by formula (1E) and, if necessary, the aforementioned It may also be prepared by mixing and dispersing the ingredients with other components using a mixer or stirrer. Examples of blenders or mixers include ball mills, tumble mixers, and ribbon blenders. Examples include Henschel mixers, mixing rolls, kneaders, and Banbury mixers. The temperature during mixing (kneading) or stirring can be, for example, around 50-250°C. The temperature is preferably 100-200°C.

[0225] [Cured product] The cured product can be prepared by curing the curable composition (curing treatment). The curing treatment is This can be done by using a catalyst, heating, or light irradiation (irradiation with active energy rays), and You may also combine these methods.

[0226] When curing by heating, the heating temperature is preferably, for example, 50 to 250°C. The following ranges may be used: 70-220°C, 80-200°C, 90-170°C, and so on. More preferably, the temperature is 150-200°C, and particularly 170-180°C. The curing treatment is performed in stages. It may also be done at a relatively low temperature, for example, around 50-130°C, preferably 70°C. After heat treatment at ~120°C, a relatively high temperature, specifically around 140~350°C, is preferred. Alternatively, it may be heat-treated at 150-300°C. Such hardening treatments depend on the shape of the hardened product. The curable composition may be applied during and / or after molding (or pre-molding). For example, if necessary, the curable composition may be heated and melted, poured into a predetermined mold, and then heated to harden. This process allows for the creation of a molded body with a desired shape. The molding method and curing conditions are not particularly limited. For example, when molding using a predetermined mold, there are methods such as molding by heating and pressurizing or cold molding. A low-temperature molding method called "less" may also be used. Alternatively, a curable composition may be applied to the bonding site. It may also be cured by coating the substrate with a curable composition and curing it, for example, by light as described later. It may be cured by irradiation or other means.

[0227] When curing by light irradiation, the wavelength of light is appropriately selected depending on the type of acid generator and other factors. It may be done, and ultraviolet light or visible light may also be used. The amount of light irradiation (exposure) is The concentration can be selected according to the thickness of the curable composition (coating film), for example, from 10 to 10,000 mJ / cm². 2 It may be in the range of 100 to 5000 mJ / cm², preferably 100 to 5000 mJ / cm². 2 , more preferably 5 00-3000 mJ / cm² 2 As a light source, for example, a high-pressure mercury lamp, a deuterium lamp... Lamps, halogen lamps, metal halide lamps, xenon lamps, LED lasers, etc. Laser light and other technologies can be used. In order to accelerate the curing of curable compositions, not only light irradiation but also other methods can be used. The aforementioned heat treatment may be performed.

[0228] The shape of the cured product is not particularly limited; it can be one-dimensional (e.g., rod-shaped) or two-dimensional (e.g., sheet-shaped). (e.g., film-like, plate-like), three-dimensional shapes [for example, block-like, rod-like, hollow (tubular or It may be in any form such as (tubular), etc. Such a cured product is given by the above formula (1E) Because it contains the compounds shown, it exhibits a high refractive index and high heat resistance.

[0229] The temperature at which the cured product loses 5% of its mass may be, for example, around 350 to 500°C, and is preferable. The following are the stages: 400-450°C, 410-430°C. Also, the thermomechanical components of the cured product The glass transition temperature Tg(TMA) measured by a glass analysis device (TMA) is, for example, 150~ It may be around 300°C, preferably in stages, 200-250°C, 200-2 The temperature is 20°C. Furthermore, the glass transition was measured using a dynamic viscoelasticity analyzer (DMA) for the cured material. The temperature Tg(DMA) may be, for example, around 150-300°C, and preferably the following steps The temperature ranges are 200-250°C and 210-230°C.

[0230] The 5% mass loss temperature, Tg(TMA), and Tg(DMA) of the cured product are as described below. Measurement can be performed according to the method described in the example. [Examples]

[0231] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. Therefore, it is not limited to this. Details of the evaluation method are shown below.

[0232] [Evaluation Method] (HPLC) As an HPLC (High Performance Liquid Chromatography) instrument, we use the "L" manufactured by Shimadzu Corporation. "C-2010A HT", using Tosoh Corporation's "ODS-80TM" as the column, The sample was dissolved in acetonitrile and measured, and the HPLC purity [area %] was calculated.

[0233] ( 1 (H-NMR) The sample is dissolved in a deuterated solvent (CDCl3) containing tetramethylsilane as an internal standard. Using a nuclear magnetic resonance spectrometer (BRUKER's "AVANCE III HD"), 1 H -NMR spectra were measured.

[0234] (Refractive index nD) The refractive index was measured using a refractometer (ATAGO RX-7000i) at a temperature of 25°C. The measurement was performed at a wavelength of 589 nm (D line). The refractive index was calculated using dimethyl sulfoxyester. Dissolve in , and concentrates of 5.0% by mass, 10.0% by mass, and 30.0% by mass (obtained in Example 4) Solutions of DPBNFG only (5.0% by mass, 10.0% by mass, and 14.7% by mass) Prepare the solution and measure the refractive index of the resulting solution and the solution at a concentration of 0% by mass (dimethyl sulfoxide only). The concentration was obtained by extrapolating it to 100% by mass in the calibration curve (approximate straight line) created using this method.

[0235] (Melting or melting temperature) The melting point was measured using a melting point measuring device (BUCHI "Melting Point M-565") under the following conditions. Then, the melting start temperature and melting end temperature were read. The melting was measured three times. The average values ​​of the melting start temperature and melting end temperature were calculated.

[0236] Measurement start temperature: 100℃ Heating rate: 10℃ / min Melting initiation detection condition: 15% (Melting initiation is defined as the point at which the rate of change in the transmittance of the sample exceeds 15%). (Assuming it was temperature) Measurement mode: Local method mode Number of measurements: n=3

[0237] (5% mass reduction temperature) Thermogravimetric Analysis - Differential Thermal Analysis (TG-DTA) (SII Nanotechnology Co., Ltd.) Using the "TG / DTA6200" manufactured by [company name], under conditions of a nitrogen atmosphere and a heating rate of 10°C / min. Below, the temperature at which the sample mass decreased by 5% by mass was measured.

[0238] (Glass transition temperature Tg) The glass transition temperature Tg(TMA) of the cured product is determined according to JIS K 7197, based on thermomechanical components. Measurements were taken using a TMA (TMA 8311) analyzer (manufactured by Rigaku Corporation) under the following conditions. did.

[0239] Test dimensions: Approximately 10mm x 5mm x 3mm Heating rate: 5°C / min Measurement temperature range: Room temperature to 300℃ Measurement mode: Compression (Load 49mN) Atmosphere: Nitrogen stream (100 mL / min) Number of measurements: n=1

[0240] Furthermore, the glass transition temperature Tg (DMA, tanδ) of the cured product is specified in JIS K 7244. Accordingly, the dynamic viscoelasticity (DMA) measuring device (Rheogel-E4, manufactured by UBM Co., Ltd.) The measurement was performed using "000") under the following conditions.

[0241] Heating rate: 4°C / min Frequency: 1Hz Atmosphere: Air current Measurement mode: bending Number of measurements: n=1

[0242] (Solubility) For 200 mg of sample, add each solvent described below to a concentration of 30% or 50% by mass. The solubility of each sample in the respective solvent was confirmed after adding sea urchin to each solvent and stirring at room temperature (25°C). If it does not dissolve at room temperature (25°C), gradually heat it up to 50°C or 80°C. Solubility was confirmed using the evaluation criteria below.

[0243] ○(25℃): Dissolved at 25℃ ○(50℃): Did not dissolve at 25℃, but dissolved when the temperature was raised to 50℃. ○(80℃): Did not dissolve at 50℃, but dissolved when the temperature was raised to 80℃. ×: Did not dissolve even when heated to 80°C.

[0244] (Storage stability) The sample was mixed with propylene glycol monomethyl ether acetate (PGM) at a concentration of 30% by mass. Store the solution completely dissolved in EA at 5°C and observe the state of the solution after 24 hours. Storage stability (solution stability or low-temperature stability) was confirmed according to the evaluation criteria.

[0245] ○: No precipitation was observed in the sample. ×: Precipitation of the sample was confirmed.

[0246] (Epoxy equivalent) In accordance with JIS K 7236:2001, an automatic titrator (GT-10 manufactured by Mitsubishi Chemical Corporation) was used. The sample was titrated with perchloric acid solution (acetic acid) using (0).

[0247] [Synthesis Example 1] 9,9-bis(6-hydroxy-2-naphthyl)-2,7-dibromoful Synthesis of oren (hereinafter also referred to as DBrBNF)

[0248] [ka]

[0249] 12.5 g (0.037 mol) of 2,7-dibromo-9-fluorenone in the reaction vessel, 2 - Naphthol 16.0g (0.11mol), 1,4-dioxane 90mL, 3-Mercato Prepare 0.5 mL (5.8 mmol) of putopropionic acid and 26 mL of 98% by mass concentrated sulfuric acid. The mixture was stirred under a nitrogen atmosphere and reacted at 60°C for 24 hours. After cooling to room temperature, it was heated and reduced pressure to dissolve. After removing the medium, add 300 mL of dichloromethane and 300 mL of deionized water and perform liquid-liquid extraction. After adjusting the pH to 7 with a sodium bicarbonate solution, 300 mL of deionized water was added. Then it was rinsed again with water. After repeating this rinsing operation with deionized water three times, it was heated under reduced pressure. After removing dichloromethane, yellow crude crystals were obtained. The obtained yellow crude crystals were subjected to column chromatography. - Purified with silica gel support (eluent: dichloromethane), and dried under reduced pressure. 6.01 g of DBrBNF (slightly brownish solid, yield 24%, HPLC purity 95.2%) was obtained. The obtained DBrBNF 1 The results of the 1H-NMR spectrum are shown below.

[0250] 1 H-NMR (CDCl3, 300MHz): δ(ppm)5.2(s, 2H), 7. 0-7.1(m,4H), 7.3(d,2H), 7.5(m,12H).

[0251] [Example 1A] 9,9-bis(6-hydroxy-2-naphthyl)-2,7-di(2-na Synthesis of phthal(fluorene) (hereinafter also known as DNBNF)

[0252] [ka]

[0253] 0.78g (1.3 mmol) of DBrBNF and 0.25mg of 2-naphthylboronic acid were added to the reactor. 54 g (3.1 mmol), 10 mL of toluene, and 2.6 mL of 1 M potassium carbonate aqueous solution. L (2.6 mmol) was added, and under a nitrogen atmosphere, tetrakis(triphenylphosphine) was added. Add 75 mg (0.065 mmol) of radium (0) [or Pd(PPh3)4]. The reaction was carried out by heating under reflux at an internal temperature of 85°C for 15 hours. 50 mL of deionized water was added to the reaction solution. After adding 75 mL of chloromethane and stirring, liquid-liquid extraction was performed. Washing with deionized water followed. After repeating the procedure three times, the organic layer was concentrated to obtain a light brown crude material. The obtained light brown crude material was then processed. Chromatography [Silica gel support, developing solvent: dichloromethane / ethyl acetate (volume) After purification at a ratio of 100 / 1, DNBNF 351 mg ( A pale yellow solid was obtained, with a yield of 49.9% and an HPLC purity of 97.4%. The refractive index nD is 1.79, and the 5% mass loss temperature is 443°C. 1 Results of H-NMR The following is shown.

[0254] 1 H-NMR (CDCl3, 300MHz): δ(ppm)4.9(s,2H), 7. 0(d,2H), 7.1(s,2H), 7.4-7.7(m,14H), 7.8-8.1 (m,14H)

[0255] [Example 1B] Synthesis of DNBNF DBrBNF 21.3g (0.035mol), 2-naphthylboronic acid 1 3.2g (0.077mol), 130mL of toluene, and 8.1M potassium carbonate aqueous solution 30 mL (0.245 mol) of the solution was added and dissolved under a nitrogen atmosphere at 70-80°C. in tetrakis(triphenylphosphine)palladium(0) [or Pd(PPh3)] 4) 20.2 mg (0.018 mmol) was added and the mixture was reacted at an internal temperature of 80°C for 1 hour. 30 mL of deionized water was added to the reaction mixture and stirred, then liquid-liquid extraction was performed. After repeating the washing procedure with water three times, the organic layer is diluted twice with toluene, and 350 ml of heptane is added. Dropwise addition yielded pale reddish-orange crude crystals. After drying under reduced pressure, 20.5 g of DNBNF (pale reddish-orange solid) was obtained. A yield of 83.3% and HPLC purity of 88.6% were obtained. The refractive index of the obtained DNBNF was also noted. nD, 5% mass loss temperature; 1 The 1H-NMR results were the same as in Example 1A. The melting (dissolution) start temperature was 176.4°C, and the melting (dissolution) end temperature was 224.1°C. Oh, X-ray diffraction (XRD) shows a halo peak, indicating that it is an amorphous material. This was confirmed.

[0256] [Example 1C] Synthesis of DNBNF DBrBNF 21.3g (0.035mol), 2-naphthylboronic acid 1 3.8g (0.081mol), triphenylphosphine 36.7mg (0.140mg) ol), 80 mL of methyl isobutyl ketone (MIBK), and 4M potassium carbonate aqueous solution. 60 mL (0.245 mol) was added and dissolved at 70°C under a nitrogen atmosphere. Furthermore, acetic acid was added. Add 7.9 mg (0.035 mmol) of palladium and react at an internal temperature of 75°C for 7 hours. The water in the reaction solution was drained, 30 mL of deionized water was added, and then the solution was neutralized with 10% hydrochloric acid by mass. Subsequently, the rinsing process with deionized water was repeated three times. The reaction solution was concentrated to a concentration of approximately 4. Adjust to 0-45% by mass, and allow to cool from 60°C to room temperature while stirring at 250 rpm. Crystallization occurred by lowering the temperature. Precipitation began at approximately 45°C. After vacuum drying, DNBNF 18.7 g (white solid, yield 76.0%, HPLC purity 99.0%) was obtained. Example 1A Compared to the DNBNF obtained in 1B, the coloration is significantly reduced, and the yield and purity are also higher. The refractive index nD of the obtained DNBNF, the 5% mass loss temperature, 1 H-NMR The results were the same as in Example 1A. The melting start temperature was 188.5°C, and the melting end temperature was The temperature was 218.8°C. Note that in X-ray diffraction (XRD), a predetermined number of peaks were observed, rather than a halo peak. A folding pattern was observed, confirming that it was crystalline, unlike Example 1B.

[0257] [Example 2] 9,9-bis(6-hydroxy-2-naphthyl)-2,7-diphenyl Synthesis of ruolene (hereinafter also called DPBNF)

[0258] [ka]

[0259] 21.3g (0.035mol) of DBrBNF and 9.9g of phenylboronic acid were added to the reactor. g (0.081 mol), triphenylphosphine 36.7 mg (0.140 mmol) , MIBK 80 mL, and 4M potassium carbonate aqueous solution 60 mL (0.245 mol) The preparation was carried out under a nitrogen atmosphere at 70°C. Furthermore, 7.9 mg (0.03) of palladium acetate was added. 5 mmol) was added and the reaction was carried out at an internal temperature of 75°C for 5 hours. The water in the reaction solution was drained, and After adding 30 mL of ion-exchanged water, the pH was adjusted to 7 with 10% hydrochloric acid by mass. Then, ion exchange was performed. The rinsing procedure with water was repeated three times. The reaction solution was concentrated to remove MIBK, and toluene was added. 21 g (0.230 mmol) of heptane was added to the toluene solution. By adding it dropwise to (mol), 17.7g of DPBNF (pale yellow solid, yield 84.0%, HP) was produced. An LC purity of 87.9% was obtained. The refractive index nD of the obtained DPBNF was 1.75, and 5% The mass reduction temperature is 360°C. 1 The 1H-NMR results are shown below. Also, the melting onset temperature. The temperature was 180.7°C, and the melting termination temperature was 227.4°C.

[0260] 1 H-NMR (CDCl3, 300MHz): δ(ppm)5.49(s,2H), 7 0.0 (m, 4H), 7.2-8.0 (m, 24H)

[0261] [Comparative Example 1] 9,9-Bis(6-hydroxy-2-naphthyl)fluorene (Osaka Gas Chemical Co., Ltd.) The refractive index nD of the manufactured "BNF" is 1.74, and the 5% mass loss temperature is 369°C. The melting start temperature was 259°C, and the melting end temperature was 263°C.

[0262] [Comparative Example 2] 9,9-Bis(4-hydroxyphenyl)fluorene (manufactured by Osaka Gas Chemical Co., Ltd.) PF (melting point 223-224°C) has a refractive index nD of 1.68 and a 5% mass loss temperature of 3 The temperature was 0.1°C.

[0263] [Comparative Example 3] 9,9-Bis(4-hydroxy-3-methylphenyl)fluorene (Osaka Gas Chemical) The refractive index nD of "BCF" manufactured by (Co., Ltd., melting point 218-219°C) is 1.68, and the 5% mass is 1.68. The temperature decrease was 313°C.

[0264] [Comparative Example 4] 9,9-Bis[4-(2-hydroxyethoxy)phenyl]fluorene (Osaka Gas Chemical Co., Ltd.) The refractive index nD of "BPEF" manufactured by CAL Corporation (melting point 161-163°C) is 1.65, and 5 The % mass loss temperature was 342°C.

[0265] Table 1 below shows the physical properties (refractive index, 5% concentration) of the fluorene compounds obtained in the examples and comparative examples. The table shows the temperature at which the amount of liquid decreases and the melting temperature. (The numbers in parentheses next to the melting temperature in Table 1 indicate the melting point of commercially available products.) vinegar).

[0266] [Table 1]

[0267] As is clear from the results in Table 1, the refractive index is significantly higher compared to the examples and comparative examples. In addition, a benzene ring was introduced at the 2,7 positions of the fluorene skeleton in Comparative Example 1 (BNF). In Example 2 (DPBNF), a 5% decrease in the mass loss temperature was observed, while naphthalate In Example 1 (DNBNF), in which a ring was introduced, the 5% mass loss temperature was significantly improved, resulting in greater heat resistance. It has excellent properties. Furthermore, Examples 1 (DNBNF) and 2 (DPBNF) have high performance. While it exhibits a 5% mass loss temperature, surprisingly, the melting initiation temperature is low, particularly in Example 1 (DNBN In F), a naphthalene ring with more benzene ring skeletons than in Example 2 (DPBNF) is introduced. Nevertheless, it was found that the melting termination temperature was low, indicating that it could be easily melted.

[0268] Table 2 below shows the concentrations of the fluorene compounds obtained in Example 1C, Example 2, and Comparative Example 1. The results of the solubility evaluation when dissolved in each solvent at 30% by mass are shown. Note that in the table, PGMEA is Propylene glycol monomethyl ether acetate, PGME is propylene glycol Monomethyl ether, n-PrOH is n-propanol, NMP is N-methyl-2-pyro Lidone and DMF are N,N-dimethylformamide, and DMSO is dimethyl sulfoxide. These are shown below (the same applies hereafter). [Table 2]

[0269] As is clear from the results in Table 2, Example 1 (DNBNF) and Example 2 (DPBNF) ) contains many benzene ring skeletons, so it was expected that the solubility would decrease significantly, It also showed high solubility in other solvents. In particular, in Example 1 (DNBNF), all measured solvent species showed high solubility. It was soluble in [the specified area].

[0270] Table 3 below shows the concentrations of the fluorene compounds obtained in Example 1C, Example 2, and Comparative Example 1. Storage stability of the solution dissolved in PGMEA at 30% by mass (solution prepared using the solubility test in Table 2) The results of the gender evaluation are shown. [Table 3]

[0271] As is clear from the results in Table 3, in all examples, precipitation occurred under high concentration and low temperature conditions. In this state, it remained stable in solution without precipitation.

[0272] [Example 3A] 9,9-bis(6-glycidyloxy-2-naphthyl)-2,7-di( Synthesis of 2-naphthyl)fluorene (hereinafter also referred to as DNBNFG)

[0273] [ka]

[0274] 105.43 g (0.15 mol) of DNBNF obtained in Example 1C was placed in the reactor. Loromethyloxirane 303.6g (3.3mol), Dimethyl sulfoxide 83.2g The mixture was added and heated and dissolved at 40°C for 30 minutes under a nitrogen stream. Then, the flake-shaped sodium hydroxide was added. 13.2g (0.33mol) of sodium hydroxide was added. 4 hours after the addition of sodium hydroxide. After heating and stirring while maintaining the temperature at 40°C, the raw material DNBNF was found to be dissolved by HPLC. The loss was confirmed. Subsequently, chloromethyloxirane was concentrated and removed using an evaporator, MI After adding 550g of BK, the washing procedure with 200mL of deionized water was repeated 5 times. Prepare the IBK solution by adjusting the solid content to 20% by mass, and add 1635g of isopropyl alcohol (IPA). By adding it dropwise over 1 hour, 107g of DNBNFG (white solid, yield 88%) was obtained. HPLC purity of 95% was obtained. The refractive index nD of the obtained DNBNFG was 1.76, and 5 The % mass loss temperature was 405°C, and it exhibited very high refractive index and heat resistance. The obtained D The melting onset temperature (temperature at which it begins to melt) of NBNFG is 149°C, and its epoxy equivalent is 432. It is 0.4g / eq, 1 The results of the 1H-NMR spectrum are shown below.

[0275] 1 H-NMR (CDCl3, 300MHz): δ(ppm)2.8(t,2H), 2. 9(t,2H), 3.4(m,2H), 4.0(dd,2H), 4.3(dd,2H), 7.1 (m, 4H), 7.4-7.9 (m, 28H)

[0276] [Example 3B] Synthesis of DNBNFG In a 200 mL four-necked round-bottom flask, add 35.1 g (0) of the DNBNF obtained in Example 1B. Add 0.05 mol) and 101 g (1.1 mol, 22 eq.) of epichlorohydrin, and The inside of the apparatus was purged with nitrogen. 6.6 g (0.17 mol, 3.3 eq) of sodium hydroxide (granules) was added. Add .) and heat under reflux at 118°C, then use Deans The mixture was returned to the system using Turk. After stirring for 3 hours, the epichlorohydrin was concentrated and removed. After dissolving in 199g (2.0mol, 40eq.) of butyl ketone (MIBK), add 1 oz of distilled water. 17g and 2g of Celite were added and stirred at 70°C. Celite was filtered out, and after draining, the organic layer was removed. The process of washing with 80 mL of distilled water was repeated four times. The organic layer was reprecipitation with 205 g of methanol. The obtained solid was then dried at 70°C to obtain a pale yellow solid. Furthermore, silica gel was used. By purifying using chromatography (dichloromethane / hexane = 6 / 4 (volume ratio)), 5.64 g of DNBNFG (slightly yellowish solid, yield 16.1%, HPLC purity 94%) was obtained. The refractive index nD of the obtained DNBNFG, the 5% mass loss temperature, and the melting onset temperature are as follows: It was the same as 3A. Furthermore, DNBNFG 1 The results of the 1H-NMR spectrum are shown below.

[0277] 1 H-NMR (CDCl3,300MHz): δ(ppm)2.8(t,2H), 2. 9(t,2H), 3.4(m,2H), 4.0(dd,2H), 4.4(dd,2H), 7.1(m,4H), 7.4-7.7(m,14H), 7.8-8.0(m,14H)

[0278] [Example 4] 9,9-bis(6-glycidyloxy-2-naphthyl)-2,7-dife Synthesis of Nylfluorene (hereinafter also known as DPBNFG) [ka]

[0279] The procedure was carried out except that 90.4g (0.15mol) of DPBNF was used instead of DNBNF. Using the same method as in Example 3A, 93g of DPBNFG (pale yellow solid, yield 87%, HPLC) was obtained. A purity of 87% was obtained. The refractive index nD of the obtained DPBNFG was 1.72, and the mass was reduced by 5%. The minimum temperature is 380°C, the melting start temperature is 195°C, and the epoxy equivalent is 384.4g. / eq, 1 The results of the 1H-NMR spectrum are shown below.

[0280] 1 H-NMR (CDCl3, 300MHz): δ(ppm)2.8(t,2H), 2. 9(t,2H), 3.4(m,2H), 4.0(dd,2H), 4.3(dd,2H), 7 0.1 (m, 4H), 7.3-7.9 (m, 24H)

[0281] [Comparative Example 5] 9,9-Bis(6-glycidyloxy-2-naphthyl)fluorene (Osaka Gas Chemical) The refractive index nD of "BNFG" manufactured by (Co., Ltd.) is 1.70, and the 5% mass loss temperature is 391°C. Yes, the melting onset temperature was 113°C, and the epoxy equivalent was 292.0 g / eq.

[0282] [Comparative Example 6] Refractive index nD of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation's "jER828") The coefficient is 1.58, the 5% mass loss temperature is 380°C, and the epoxy equivalent is 187 g / eq That was the case.

[0283] Table 4 below shows the physical properties of the fluorene compounds (epoxy resins) obtained in the examples and comparative examples. This indicates.

[0284] [Table 4]

[0285] As is clear from the results in Table 4, the refractive index is significantly higher compared to the examples and comparative examples. In addition, the benzene ring is attached to the 2,7 position of the fluorene skeleton in Comparative Example 5 (BNFG). In the introduced Example 4 (DPBNFG), a 5% decrease in the mass loss temperature was observed, while naph In Example 3 (DNBNFG), in which a talene ring was introduced, the 5% mass loss temperature was greatly improved, and resistance It has excellent heat resistance. The example shows excellent heat resistance, while the melting start temperature is relatively low, and the curing agent It was found that it can be easily or efficiently mixed with other components such as the naphthalene ring. Example 3, which introduced [the element], had a lower melting onset temperature than Example 4, which introduced a benzene ring. That was unexpected.

[0286] Table 5 below shows the fluorene compounds (epo) obtained in Example 3A, Example 4, and Comparative Example 5. The results of the solubility evaluation when xylyl resin is dissolved in each solvent at a concentration of 30% by mass are shown. [Table 5]

[0287] As is clear from the results in Table 5, Example 3A (DNBNFG) has many benzene ring skeletons. Because it contains [a certain substance], a significant decrease in solubility was expected, but for all the solvents measured, It was soluble and surprisingly showed high solubility. In particular, the example in which a naphthalene ring was introduced. It was surprising that example 3 showed superior solubility compared to example 4, which incorporated a benzene ring.

[0288] Note that even at a concentration of 50% by mass, Example 3A (DNBNFG) contains ethyl acetate and acetate. Ton, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, DMF and D Dissolve each in MSO at room temperature (25°C): cyclohexanone, PGMEA, P GME, benzyl alcohol, 1,4-dioxane, methyl lactate, ethyl lactate, butyrate Toxyl 3-ethyl ethoxypropionate, γ-butyrolactone, NMP, and toluene They were then dissolved by heating to a temperature of 80°C or lower.

[0289] In contrast, Example 4 (DPBNFG) at a concentration of 50 wt% was found to be NMP at room temperature (25 It only dissolved at °C.

[0290] <Preparation of curable compositions and cured products> The epoxy resins of Example 3A and Comparative Examples 5-6, and phenol novolat as a curing agent The resin (PSM-4261 manufactured by Gun-ei Chemical Industry Co., Ltd., hydroxyl group equivalent 105g / eq) The mixture was prepared in an equivalent ratio of 1:1 and kneaded at 190°C using two rollers. After the kneaded mixture has cooled to room temperature, TPP (triphenylphosphine) is used as a catalyst. Add (manufactured by Chemical Co., Ltd.) to 100 parts by mass of the total amount of epoxy resin and phenol novolac resin. One part by mass was added to the mixture and kneaded at 120°C using a roller. The resulting mixture was then heated at 175°C. After pressing and molding for 30 minutes, bake in an oven at 175°C for 5 hours (post-curing). A hardened product was obtained.

[0291] Table 6 below shows the fluorene compounds (epoxy resins) obtained in the examples and comparative examples, and The physical properties of the cured product obtained using this epoxy resin are shown.

[0292] [Table 6]

[0293] As is clear from Table 6, Example 3A exhibited higher heat resistance compared to Comparative Examples 5 and 6. Furthermore, the DNBNFG used in Example 3A had a higher concentration of [number missing] in its chemical structure compared to Comparative Examples 5-6. Although a decrease in solubility (miscibility) is expected due to the presence of a benzene ring skeleton, Surprisingly, it exhibits good compatibility with curing agents and other materials, and can produce a uniform curable composition and cured product. It was made. [Industrial applicability]

[0294] The fluorene compound represented by formula (1) of the present invention exhibits a high refractive index and excellent heat resistance. Therefore, resin raw materials, such as polyester resins like polyarylate resin, and polycarbonate resins, are used. Polynate resins, polyether resins, polyether ketone resins, polyether ether Monomer components of thermoplastic resins such as ketone resins and polyether ketone resins, and ( T) Acrylic resin, vinyl ester resin (or epoxy (meth)acrylate resin), It can be effectively used as a raw material for curable resins such as vinyl ether resin and epoxy resin. In particular, the fluorene compound represented by formula (1) has a high 5% mass loss temperature and high resistance Despite exhibiting thermal properties, it surprisingly has a low melting temperature. Furthermore, it also has excellent solubility. Therefore, it may be used as a monomer for melt polymerization or solution polymerization.

[0295] Furthermore, the fluorene compound represented by formula (1) is a refractive index improver, a heat resistance improver, and a hardener. It can be effectively used as an additive (or resin additive) such as a curing agent. Examples include epoxy resin curing agents. Fluorene formation represented by formula (1) above. Compounds not only have a low melting temperature, but also excellent solubility (mismatch), so molten mixtures A uniform composition may be easily or efficiently prepared by kneading or other methods.

[0296] A resin or fluorene made from the fluorene compound represented by formula (1) of the present invention. Compositions containing this as an additive can be suitably used in optical components (optical materials or transparent materials), etc. The optical components include, for example, a reflow lens, a pickup lens, and a micro Optical lenses such as lenses, polarizing films, anti-reflective films, touch panel films, flexible Optical films such as films for sible substrates and display films, films for fuel cells, and light Examples include fibers, optical waveguides, and holograms.

[0297] Furthermore, the epoxy resin represented by formula (1E) and the curable compound containing this epoxy resin The resulting product (or its cured product) has excellent properties such as high refractive index and high heat resistance, for example Resins such as insulating materials between layers of electronic components, solder resists for printed circuit boards, and coverlays. Materials such as inks, color filters, printing inks, electronic components, or semiconductor encapsulants. Which sealants, paints, coatings, adhesives, underfills, antistatic agents, fillers Fillers, conductive members or conductive materials, laminated materials, thermal materials such as thermal paper materials, carbon materials all materials such as insulating materials, foams, pressure-sensitive materials, and the aforementioned optical materials (or transparent materials) It is useful. Surprisingly, the epoxy resin represented by formula (1E) melts (melts). Not only is the starting temperature relatively low, but it also has excellent solubility (miscibility), so it can be used at relatively low temperatures. It is also possible to easily or efficiently prepare a uniform curable composition.

Claims

1. The following formula (1E) 【Chemistry 1】 [In the formula, Y １ａ and Y １ｂ Each of these independently corresponds to the following equation (Y1) 【Chemistry 2】 (In the formula, Z １ This represents a benzene ring or a naphthalene ring. R １ (where represents a substituent, and m1 represents 0.) This represents a monovalent group represented by , where k1a and k1b represent 1. R 2a and R ２ｂ Each of these independently represents a substituent, and m2a and m2b represent 0. Y 3a and Y ３ｂ Each of these independently corresponds to the following equation (Y3) 【Transformation 3】 (In the formula, Z ２ It exhibits a polycyclic C 10-14 arene ring, R ３ represents a substituent, and m3 represents 0. A １ represents a linear or branched C2-3 alkylene group, n1 represents 0 or 1, R ４ (This represents a hydrogen atom or a methyl group.) This represents a monovalent group. A raw material for curable resins, consisting of a fluorene compound represented by [formula].

2. In the above formula (1E), Y 3a and Y ３ｂ In the equation (Y3) that represents Z ２ The raw material for a curable resin according to claim 1, wherein is a naphthalene ring or a biphenyl ring.

3. In the above formula (1E), Y １ａ and Y １ｂ In the equation (Y1) that represents Z １ A raw material for a curable resin according to claim 1 or 2, wherein the ring is a naphthalene ring.

4. The following formula (1) 【Chemistry 4】 [In the formula, Y ２ａ and Y ２ｂ Each of these independently corresponds to the following equation (Y2) 【Transformation 5】 (In the formula, Z ２ , R ３ , m3, A １ (And n1 are the same as formula (Y3) described in claim 1, respectively.) This represents a monovalent group, Y １ａ and Y １ｂ This is the same as formula (Y1) described in claim 1, k1a and k1b, R ２ａ and R ２ｂ m2a and m2b are each independently the same as formula (1E) described in claim 1. A method for producing a raw material for a curable resin comprising a compound represented by formula (1E) according to any one of claims 1 to 3, by reacting a fluorene compound represented by with an epihalohydrin component.

5. A curable composition comprising a compound represented by formula (1E) as described in any one of claims 1 to 3.

6. A cured product obtained by curing the curable composition according to claim 5.

7. An optical component comprising the cured product according to claim 6.

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