Fluorene compound, method for producing the same, and use thereof

Abstract

To provide a fluorene compound exhibiting high heat resistance, and to provide a method for producing the same and use thereof.SOLUTION: A compound represented by formula (1) is prepared. (In the formula, R1 represents a substitution group, m1 represents an integer of 0 to 8, Z1a and Z1b independently represent an arene ring, A1a and A1b independently represent an alkylene group, n1a and n1b independently represent an integer of 0 or more, R2a and independently represent a saturated aliphatic group, and independently represent a substitution group, and and independently represent an integer of 0 or more.) R2b m3b R3a m3a R3b. ) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a fluorene compound having a 9,9-bisarylfluorene skeleton and an aliphatic carboxylic acid ester skeleton (aliphatic acyloxy skeleton), as well as a production method and uses thereof. [Background technology]

[0002] Compounds with a 9,9-bisarylfluorene skeleton, such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, have excellent optical properties and heat resistance, and are therefore often used not only as polymerization components for resins but also as various additives to modify resins (or improve their physical properties).

[0003] Japanese Patent Application Laid-Open No. 2005-162785 (Patent Document 1) discloses a resin composition composed of a specific compound having a 9,9-bisphenylfluorene skeleton and a thermoplastic resin, and describes that the excellent properties of the fluorene skeleton, such as a high refractive index, can be easily and efficiently imparted to the thermoplastic resin.

[0004] Japanese Patent Laid-Open Publication No. 2011-008017 (Patent Document 2) discloses an optical resin composition composed of a transparent resin and a compound having a 9,9-bisphenylfluorene skeleton in a predetermined proportion, a method of reducing birefringence by adding a compound having a 9,9-bisphenylfluorene skeleton in a predetermined proportion, etc. This document describes that birefringence can be reduced without impairing the inherent mechanical properties and heat resistance of the transparent resin.

[0005] Japanese Patent Laid-Open Publication No. 2014-205734 (Patent Document 3) discloses an Abbe number improver composed of a compound having a 9,9-bisphenylfluorene skeleton as an additive for increasing the Abbe number of a resin. This document also describes that the Abbe number improver can improve both the Abbe number and the refractive index, does not impair various resin properties, and can improve other resin properties (improving mechanical strength and heat resistance, and reducing birefringence).

[0006] Japanese Patent Laid-Open Publication No. 2014-218655 (Patent Document 4) discloses a heat resistance improver composed of a compound having a 9,9-bisphenylfluorene skeleton as an additive for improving the heat resistance of polyester resins having a number average molecular weight of 10,000 or less. This document describes that the heat resistance improver can achieve low viscosity and improved heat resistance, which are difficult to achieve simultaneously.

[0007] Japanese Patent Laid-Open Publication No. 2014-205733 (Patent Document 5) discloses a heat resistance improver composed of a compound having a 9,9-bisphenylfluorene skeleton as an additive for improving the heat resistance of aromatic polyester resins. This document also describes that the heat resistance improver can improve heat resistance, but also does not impair various resin properties and can improve other resin properties (improved mechanical strength, promoted crystallization, improved refractive index and Abbe number, reduced birefringence).

[0008] Japanese Patent Laid-Open Publication No. 2014-218656 (Patent Document 6) discloses a crystallization accelerator composed of a specific compound having a 9,9-bisphenylfluorene skeleton as an additive for promoting the crystallization of crystalline resins. This document also describes that the crystallization accelerator can promote crystallization, but also does not impair various resin properties and can improve other resin properties (improved mechanical strength and heat resistance, improved refractive index and Abbe number, reduced birefringence).

[0009] Japanese Patent Laid-Open Publication No. 2014-218659 (Patent Document 7) discloses a strength improver composed of a compound having a 9,9-bisphenylfluorene skeleton as an additive for improving the mechanical strength of resins. This document also describes that the strength improver can improve the mechanical strength of resins, as well as not impairing various resin properties and improving other resin properties (improving heat resistance, improving refractive index and Abbe number, and reducing birefringence).

[0010] Japanese Patent Laid-Open Publication No. 2014-218660 (Patent Document 8) discloses a resin composition containing a cyclic olefin copolymer and a compound having a 9,9-bisarylfluorene skeleton. This document describes that the compound having a 9,9-bisarylfluorene skeleton functions as an improver of mechanical properties and an improver of optical properties.

[0011] Japanese Patent Laid-Open Publication No. 2021-017578 (Patent Document 9) discloses a wear resistance improver containing a compound having a 9,9-bisphenylfluorene skeleton as an additive for improving the wear resistance of resins. This document describes that the wear resistance improver can improve the wear resistance without significantly impairing the properties of the resin, and can reduce the dynamic friction coefficient even when the resin contains a fibrous filler such as cellulose fiber.

[0012] Japanese Patent Laid-Open Publication No. 2011-144344 (Patent Document 10) discloses a plasticizer containing a specific compound having a 9,9-bisarylfluorene skeleton as a plasticizer for cellulose derivatives. This document describes that even cellulose derivatives with poor melting or solvent solubility can be effectively plasticized, and that a cellulose-based resin composition can be obtained that has excellent properties such as transparency, heat resistance, solvent resistance, water resistance, and surface hardness in addition to moldability.

[0013] WO 2016 / 139826 (Patent Document 11) discloses a flowability improver containing a compound having a 9,9-bisphenylfluorene skeleton as an additive for improving the melt flowability of polyamide resins. This document describes that the compound having a 9,9-bisphenylfluorene skeleton can improve the melt flowability and moldability of polyamide resins, and can improve the melt flowability without impairing the properties of the polyamide resin.

[0014] Japanese Patent Laid-Open Publication No. 2018-203975 (Patent Document 12) discloses a method for improving melt fluidity by adding a compound having a 9,9-bisphenylfluorene skeleton to a mixture containing an ester bond-containing thermoplastic resin and a fibrous reinforcing material. This document describes the formation of a fiber-reinforced resin composition that combines high mechanical properties with high melt fluidity (moldability).

[0015] International Publication No. 2020 / 022356 (Patent Document 13) discloses a method for improving melt fluidity by adding a compound having a 9,9-bisphenylfluorene skeleton to a thermoplastic elastomer. This document describes that a thermoplastic composition with excellent melt fluidity can be formed even when the composition contains a thermoplastic elastomer that tends to have extremely low melt fluidity, and that melt fluidity can be improved while suppressing deterioration of physical properties such as mechanical properties and thermal properties. [Prior art documents] [Patent documents]

[0016] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-162785 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-008017 [Patent Document 3] Japanese Patent Application Laid-Open No. 2014-205734 [Patent Document 4] Japanese Patent Application Laid-Open No. 2014-218655 [Patent Document 5] Japanese Patent Application Laid-Open No. 2014-205733 [Patent Document 6] Japanese Patent Application Laid-Open No. 2014-218656 [Patent Document 7] Japanese Patent Application Laid-Open No. 2014-218659 [Patent Document 8] Japanese Patent Application Laid-Open No. 2014-218660 [Patent Document 9] Patent Publication No. 2021-017578 [Patent Document 10] Japanese Patent Application Laid-Open No. 2011-144344 [Patent Document 11] International Publication No. 2016 / 139826 [Patent Document 12] Japanese Patent Application Publication No. 2018-203975 [Patent Document 13] International Publication No. 2020 / 022356 Summary of the Invention [Problem to be solved by the invention]

[0017] As such, compounds having a 9,9-bisarylfluorene skeleton are known to be usable as resin additives for improving various properties of resins, and in the examples of Patent Documents 1 to 13, fluorene compounds (diol compounds) such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (hereinafter also referred to as BPEF (registered trademark)) are commonly used as specific compounds having a 9,9-bisarylfluorene skeleton.

[0018] However, in cases where higher heat resistance is required during molding or use, the heat resistance of fluorene compounds such as BPEF itself may be insufficient and they may not function sufficiently as additives.

[0019] Therefore, an object of the present disclosure is to provide a fluorene compound that exhibits high heat resistance, as well as a method for producing the same and uses thereof. [Means for solving the problem]

[0020] As a result of intensive research to achieve the above object, the present inventors have found that a specific fluorene compound having a combination of a 9,9-bisarylfluorene skeleton and an aliphatic carboxylic acid ester skeleton (aliphatic acyloxy skeleton) unexpectedly exhibits high heat resistance despite having an aliphatic skeleton, and have completed the present invention (or the present disclosure). That is, the present disclosure may include the following aspects.

[0021] Aspect [1]: A compound (fluorene compound) represented by the following formula (1):

[0022] [ka]

[0023] (In the formula, R 1 represents a substituent, m1 represents an integer of 0 to 8, Z 1a and Z 1b each independently represents an arene ring, A 1a and A 1b each independently represents an alkylene group; n1a and n1b each independently represent an integer of 0 or more; R 2a and R 2b each independently represents a saturated aliphatic hydrocarbon group, R 3a and R 3b each independently represents a substituent, and m3a and m3b each independently represent an integer of 0 or more.

[0024] Aspect [2]: In the formula (1), R 1 represents a hydrocarbon group, m1 represents an integer of 0 to 4, Z 1a and Z 1b is independently C 6-14 represents an arene ring, A 1a and A 1b is independently C 2-6 represents an alkylene group, n1a and n1b independently represent an integer of 0 to 10, R 2a and R 2b each independently represents a saturated aliphatic hydrocarbon group having 40 or less carbon atoms, R 3a and R 3b each independently represents a hydrocarbon group; and m3a and m3b each independently represent an integer of 0 to 4.

[0025] Aspect [3]: In the formula (1), R 1 represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, m1 represents an integer of 0 to 2, Z 1a and Z 1b is independently C 6-12 represents an arene ring, A 1a and A 1b is independently C 2-4 an alkylene group, n1a and n1b independently represent an integer of 0 to 6; R 2a and R 2b each independently represents an alkyl group, a cycloalkyl group, or a group formed by combining two or more of these groups, R 3a and R 3b are independently an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group; and m3a and m3b are independently an integer of 0 to 2.

[0026] Aspect [4]: The compound according to any one of aspects [1] to [3], wherein the 5% weight loss temperature is 400 to 500°C or 355 to 420°C.

[0027] Aspect [5]: The compound according to any one of aspects [1] to [4], wherein the 10% weight loss temperature is 430 to 600°C or 375 to 440°C.

[0028] Aspect [6]: A diol component represented by the following formula (2) and R 2a and R 2b A method for producing the compound represented by formula (1) according to any one of aspects [1] to [5], comprising a step of reacting a corresponding saturated aliphatic carboxylic acid component with the compound represented by formula (1).

[0029] [ka]

[0030] (In the formula, R 1 , m1, Z 1a and Z 1b , A 1a and A 1b , n1a and n1b, R 3a and R 3b and m3a and m3b are the same as those in formula (1).

[0031] Aspect [7]: A resin composition comprising the compound according to any one of aspects [1] to [5] and a resin.

[0032] Aspect [8]: A molded article comprising the resin composition according to aspect [7].

[0033] In addition, the present disclosure may achieve the following secondary objectives (solve secondary problems).

[0034] That is, another object of the present disclosure is to provide a fluorene compound that is excellent in heat resistance and ease of handling, as well as a method for producing the same and uses thereof.

[0035] A further object of the present disclosure is to provide a method for easily and efficiently producing a fluorene compound having excellent heat resistance.

[0036] In this specification and claims, the number of carbon atoms in a substituent is represented by C1, C6, C 10 For example, an alkyl group with 1 carbon atom is called a "C1 alkyl group," and an aryl group with 6 to 10 carbon atoms is called a "C 6-10 It is sometimes referred to as an "aryl group".

[0037] In addition, in this specification and claims, the term "independently" means that multiple components are independent components, for example, Z 1a and Z 1b In this case, the arene rings may be the same or different from each other.

[0038] Furthermore, in this specification and claims, a numerical range indicated by "X to Y" may include the numerical values ​​X and Y. [Effects of the Invention]

[0039] According to the present disclosure, it is possible to provide a fluorene compound exhibiting high heat resistance, as well as a method for producing the same and uses thereof. DETAILED DESCRIPTION OF THE INVENTION

[0040] The fluorene compounds of the present disclosure exhibit high heat resistance (thermal decomposition resistance), and therefore can be effectively used as additives (resin additives) not only for general-purpose resins but also for resins used or molded in high-temperature environments (e.g., highly heat-resistant resins such as engineering plastics), to form resin compositions. Furthermore, the fluorene compounds of the present disclosure can provide fluorene compounds with excellent handleability in addition to high heat resistance, as well as methods for producing and using the same. Furthermore, the present disclosure also allows for the easy or efficient production of fluorene compounds with excellent heat resistance (e.g., with high productivity (high purity and / or high yield)).

[0041] [Fluorene compound represented by formula (1)] The fluorene compound of the present disclosure (hereinafter also referred to as fluorene compound (1)) is represented by the following formula (1): Fluorene compound (1) has an aliphatic carboxylic acid ester skeleton ([-OC(=O)-R 2a ] or [-OC(=O)-R 2b Despite the combination of these two structures, it appears to unexpectedly improve heat resistance.

[0042] [ka]

[0043] (In the formula, R 1represents a substituent, m1 represents an integer of 0 to 8, Z 1a and Z 1b each independently represents an arene ring, A 1a and A 1b each independently represents an alkylene group; n1a and n1b each independently represent an integer of 0 or more; R 2a and R 2b each independently represents a saturated aliphatic hydrocarbon group, R 3a and R 3b each independently represents a substituent, and m3a and m3b each independently represent an integer of 0 or more.

[0044] In the formula (1), R 1 The substituent represented by R may be a non-reactive group (or a non-polymerizable group) that is inert to the reaction. 1 Examples of the substituent represented by the formula include a halogen atom, a hydrocarbon group, a group [—OR h ](wherein, R h represents a hydrocarbon group), the group [-SR h ](wherein, R h represents a hydrocarbon group), an acyl group, a nitro group, a cyano group, a substituted amino group (mono- or di-substituted amino group), and the like.

[0045] In this specification and claims, R h The hydrocarbon groups represented by the following formula (I) each represent an independent hydrocarbon group, and may be the same or different from each other.

[0046] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0047] Hydrocarbon group (or R h ) may be a saturated or unsaturated hydrocarbon group, an aliphatic (including alicyclic) or aromatic hydrocarbon group, and may be a chain (straight or branched) or cyclic hydrocarbon group, or a hydrocarbon group having a structure combining a chain and a cyclic structure. hThe number of carbon atoms constituting the aryl group is not particularly limited, but may be, for example, about 20 or less, and preferably is 1 to 16, 1 to 12, 1 to 10, 1 to 8, and 1 to 6 in the following stepwise order.

[0048] Representative hydrocarbon groups (or R h ) includes, for example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and the like.

[0049] Examples of the alkyl group (linear or branched alkyl group) include C alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl group. 1-10 alkyl group, preferably C 1-6 alkyl group, more preferably C 1-4 It is an alkyl group.

[0050] Examples of the cycloalkyl group include C cyclopentyl and cyclohexyl groups. 5-10 Cycloalkyl groups are exemplified.

[0051] Examples of the aryl group include C phenyl, alkylphenyl, biphenylyl, and naphthyl groups. 6-12 Examples of the alkylphenyl group include mono- to tri-C alkylphenyl groups such as methylphenyl (or tolyl) and dimethylphenyl (or xylyl). 1-4 Examples include alkyl-phenyl groups.

[0052] Examples of the aralkyl group include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl-C 1-4 Examples of suitable alkyl groups include:

[0053] The group [-OR h ] and the group [-SR h ], R h The hydrocarbon group represented by R 1The hydrocarbon groups exemplified above, including preferred embodiments thereof, include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. h ] and the group [-SR h ] includes, for example, groups corresponding to the examples of the hydrocarbon group, and a representative group [—OR h ] includes, for example, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, etc.; a representative group [—SR h Examples of the arylthio group include an alkylthio group, a cycloalkylthio group, an arylthio group, and an aralkylthio group.

[0054] Examples of the alkoxy group (linear or branched alkoxy group) include C alkoxy groups such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, and t-butoxy group. 1-10 Examples of the cycloalkyloxy group include a C alkoxy group such as a cyclohexyloxy group. 5-10 Examples of the aryloxy group include a C aryloxy group such as a phenoxy group. 6-10 Examples of the aralkyloxy group include C aryloxy groups such as benzyloxy groups. 6-10 Aryl-C 1-4 Examples thereof include alkyloxy groups.

[0055] Examples of the alkylthio group include a C alkylthio group such as a methylthio group, an ethylthio group, a propylthio group, an n-butylthio group, and a t-butylthio group. 1-10 Examples of the cycloalkylthio group include a C alkylthio group such as a cyclohexylthio group. 5-10 Examples of the arylthio group include a C thiophenoxy group. 6-10 Examples of the aralkylthio group include a C arylthio group such as a benzylthio group. 6-10 Aryl-C 1-4 Examples include alkylthio groups.

[0056] The acyl group is C 1-12 acyl groups, for example, C such as acetyl group 1-6 Examples include alkyl-carbonyl groups.

[0057] Examples of the mono- or di-substituted amino group include a mono- or di-alkylamino group, a mono- or bis(alkylcarbonyl)amino group, etc. Examples of the mono- or di-alkylamino group include a mono- or di-C group such as a mono- or dimethylamino group. 1-4 Examples of the mono- or bis(alkylcarbonyl)amino group include mono- or bis(C alkylamino groups) such as mono- or diacetylamino groups. 1-4 alkyl-carbonyl)amino groups.

[0058] Representative R 1 Examples of the alkyl group include a halogen atom (such as a fluorine atom), a hydrocarbon group (such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group), a group [-OR h ] (such as an alkoxy group), an acyl group, etc., are preferred, and hydrocarbon groups such as alkyl groups and aryl groups are preferred. Examples of the alkyl group (linear or branched alkyl group) include C groups such as a methyl group, an ethyl group, and a t-butyl group. 1-6 alkyl groups, and C groups such as methyl groups. 1-4 The alkyl group is preferred. The aryl group is, for example, a C phenyl group. 6-10 Examples include an aryl group.

[0059] R 1 The number of substitutions m1 in the formula (I) is an integer of 0 to 8, for example, an integer of about 0 to 6, preferably an integer of 0 to 4, an integer of 0 to 2, more preferably 0 or 1, or 0 or 2, particularly 0. When m1 is 2 or more, 2 or more R 1 The types of R may be the same or different. In addition, when R is present in both of the two benzene rings forming the fluorene skeleton, 1 When R is substituted on one of the benzene rings, 1 The type of R on the other benzene ring1 The types of R may be the same or different. 1 The substitution position is not particularly limited, and may be, for example, the 2-position, the 3-position, the 2,7-position, etc.

[0060] Z 1a or Z 1b Examples of the arene ring (aromatic hydrocarbon ring) represented by the formula (I) include a monocyclic arene ring such as a benzene ring, a polycyclic arene ring, etc. Examples of the polycyclic arene ring include a fused polycyclic arene ring (fused polycyclic aromatic hydrocarbon ring), a ring-assembled arene ring (ring-assembled aromatic hydrocarbon ring), etc.

[0061] The fused polycyclic arene ring includes, for example, fused bicyclic arene rings, fused tricyclic arene rings, and other fused bicyclic to tetracyclic arene rings. The fused bicyclic arene ring includes, for example, fused bicyclic C rings such as naphthalene rings and indene rings. 9-16 Examples of the fused tricyclic arene ring include fused tricyclic C arenes such as an anthracene ring and a phenanthrene ring. 14-20 Preferred fused polycyclic arene rings include fused polycyclic C arene rings such as naphthalene rings. 10-14 It is an arene ring.

[0062] Examples of the ring-assembled arene ring include biarene rings such as biphenyl ring, phenylnaphthalene ring, and binaphthyl ring; and terarene rings such as terphenyl ring (e.g., m-terphenyl ring). Preferred ring-assembled arene rings are bi- or terarene rings (particularly terarene rings), and more preferably C 1 rings such as biphenyl ring and m-terphenyl ring. 12-18 A biarene ring, in particular a biphenyl ring.

[0063] In this specification and claims, the term "ring assembly arene ring" refers to two or more ring systems (arene ring systems) directly linked by single bonds or double bonds, and the number of bonds directly linking the rings is one less than the number of ring systems. For example, as described above, phenylnaphthalene rings and binaphthyl rings are classified as ring assembly arene rings even though they have a fused polycyclic arene ring skeleton, and are clearly distinguished from "fused polycyclic arene rings" such as naphthalene rings (non-ring assembly arene rings).

[0064] Z 1a ,Z 1b As the arene ring represented by the formula (I), preferably C 6-14 arene rings, and more preferably C rings such as benzene rings, naphthalene rings, and biphenyl rings. 6-12 Arene rings (e.g., C rings such as benzene rings and naphthalene rings) 6-10 arene rings), and from the viewpoint of high refractive index, polycyclic arene rings (e.g., C 10-14 C arene ring, preferably naphthalene ring, biphenyl ring, etc. 10-12 In terms of heat resistance, a benzene ring or a biphenyl ring (particularly a benzene ring) is more preferred, and a benzene ring is particularly preferred in terms of an excellent balance between heat resistance, a high refractive index, and productivity (high purity and / or high yield). 1a ,Z 1b When Z is a ring assembly arene ring such as a benzene ring or a biphenyl ring (especially when it is a benzene ring), it appears that the heat resistance can be improved more effectively than when it is a condensed polycyclic arene ring such as a naphthalene ring. 1a and Z 1b The types may be the same or different from each other, and are preferably the same from each other.

[0065] In addition, Z bonded to the 9-position of the fluorene ring 1a and Z 1b The substitution position of is not particularly limited, and for example, Z 1a ,Z 1b When Z is a benzene ring, it may be at any position. 1a ,Z 1bWhen is a naphthalene ring, it is either the 1-position (1-naphthyl) or the 2-position (2-naphthyl), preferably the 2-position, and Z 1a ,Z 1b When is a biphenyl ring, it is at the 2-position, 3-position or 4-position, preferably the 3-position.

[0066] A 1a or A 1b Examples of the alkylene group (linear or branched alkylene group) represented by the formula (I) include C alkylene groups such as an ethylene group, a propylene group (1,2-propanediyl group), a trimethylene group, a 1,2-butanediyl group, and a tetramethylene group. 2-6 alkylene groups, and preferably C 2-4 C alkylene group, more preferably ethylene group, propylene group, etc. 2-3 An alkylene group, particularly an ethylene group, is preferred. 1a and A 1b The types may be the same or different from each other, but are preferably the same from each other.

[0067] [-(A 1a O)-] or [-(A 1b The repeat numbers (number of moles added) n1a and n1b of the alkyleneoxy group represented by (O)-) may each be 0 or greater, and may be selected from, for example, an integer of about 0 to 15, preferably in the following stepwise order: 0 to 10, 0 to 8, 0 to 6, 0 to 4, or 0 to 2, and more preferably 0 or 1, and particularly 1. In this specification and claims, the "repeated number (number of moles added)" may be an average value (arithmetic mean value, additive mean value) or the average number of moles added. Therefore, n1a and n1b may each be selected from the range of about 0 to 15, and preferably in the following stepwise order: 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, or 0 to 1. When n1a and / or n1b are in a moderate range that is not too large, a decrease in heat resistance and refractive index tends to be easily suppressed.

[0068] In addition, n1a and n1b may be the same or different. When n1a is 2 or more, two or more alkyleneoxy groups [-(A 1a The types of alkyleneoxy groups [-(A 1b O)-] may be different from each other, but are preferably the same.

[0069] The total number of n1a and n1b (total number of added moles), n1a+n1b, may be 0 or more, and may be selected from the range of, for example, about 0 to 30, preferably in the following stepwise order: 0 to 20, 0 to 16, 0 to 12, 0 to 8, 0 to 4, 0 to 2, and 1 to 2. When n1a+n1b is in an appropriate range that is not too large, it tends to be easier to suppress a decrease in heat resistance and refractive index. n1a+n1b may be an integer or an average value (arithmetic mean value, additive mean value, or average number of added moles).

[0070] R 2a or R 2b The saturated aliphatic hydrocarbon group (including a saturated alicyclic hydrocarbon group) represented by the formula (I) may be a chain (straight-chain or branched-chain), a cyclic (monocyclic or polycyclic), or a structure combining a chain and a cyclic structure (preferably a chain, more preferably a straight-chain).

[0071] R 2a ,R 2bThe number of carbon atoms constituting the saturated aliphatic hydrocarbon group (particularly, an alkyl group) represented by the formula (I) is not particularly limited, and may be, for example, an integer of about 50 or less, preferably an integer of 40 or less (e.g., 1 to 38), an integer of 35 or less (e.g., 2 to 33), an integer of 30 or less (e.g., 3 to 28), or an integer of 25 or less (e.g., 4 to 23); in terms of easier improvement of heat resistance, it may be an integer of 4 to 28, an integer of 5 to 25, an integer of 6 to 22, an integer of 7 to 18, an integer of 8 to 16, an integer of 9 to 14, or an integer of 10 to 12, and particularly preferably an integer of 9 to 26, an integer of 11 to 25, an integer of 14 to 24, an integer of 15 to 23, an integer of 16 to 22, or an integer of 17 to 21. In terms of ease of improving the refractive index, the number of carbon atoms constituting the saturated aliphatic hydrocarbon group (particularly, an alkyl group) may be, for example, an integer of about 25 or less (e.g., 1 to 20), preferably in a stepwise manner thereafter, such as an integer of 15 or less (e.g., 2 to 12), an integer of 10 or less (e.g., 3 to 8), or an integer of 6 or less (e.g., 4 to 6). In terms of excellent handleability, the number of carbon atoms constituting the saturated aliphatic hydrocarbon group (particularly, an alkyl group) may be, for example, an integer of about 14 or more (e.g., 14 to 40), preferably in a stepwise manner thereafter, such as an integer of 15 or more (e.g., 15 to 30), an integer of 16 or more (e.g., 16 to 25), or an integer of 17 or more (e.g., 17 to 21). Furthermore, from the viewpoint of ease and efficiency of production, the number of carbon atoms constituting the saturated aliphatic hydrocarbon group (particularly, the alkyl group) may be, for example, an integer of about 5 or more (e.g., 6 to 30), preferably an integer of 7 to 25 (e.g., 8 to 21), more preferably an integer of 9 to 20 (e.g., 10 to 18), and especially an integer of 10 to 16 (e.g., 10 to 14, and especially 11 to 12). When the number of carbon atoms constituting the saturated aliphatic hydrocarbon group (particularly, the alkyl group) is within an appropriate range, not too small, heat resistance, handleability, and productivity tend to be easily improved, and when it is within an appropriate range, not too large, heat resistance, refractive index, and productivity tend to be easily improved.

[0072] R 2a ,R 2bRepresentative saturated aliphatic hydrocarbon groups represented by the formula (I) include, for example, alkyl groups (straight-chain or branched-chain alkyl groups), cycloalkyl groups, polycyclic aliphatic hydrocarbon groups (polycyclic alkyl groups), and groups in which two or more of these are combined.

[0073] Examples of alkyl groups (linear or branched alkyl groups) include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, hexyl, 1-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, heptyl, 1-methylhexyl, 1-ethylpentyl, 1,1-dimethylpentyl, octyl, 3-methylheptyl, 2,4,4-trimethylpentyl, nonyl, 3-methyloctyl, 6,6-dimethylhex ... Butyl, decyl, undecyl, dodecyl, tridecyl, 11-methyl-dodecyl, tetradecyl, 11-methyl-tridecyl, pentadecyl, 13-methyl-tetradecyl, 1-hexyl-nonyl, hexadecyl, 1-methyl-pentadecyl, 13-methyl-pentadecyl, heptadecyl, 15-methyl-hexadecyl, 1-(1 ,3,3-trimethylbutyl)-4,6,6-trimethyl-heptyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, hentriacontyl group, tritriacontyl group, 1-hexadecyl-heptadecyl group, etc. 1-50 The number of carbon atoms in the alkyl group is determined by the above-mentioned R 2a ,R 2b The same applies to the number of carbon atoms constituting the saturated aliphatic hydrocarbon group represented by the following formula (1), including preferred embodiments. The alkyl group is preferably a linear alkyl group.

[0074] Examples of the cycloalkyl group include a C cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. 3-12 cycloalkyl groups, and preferably C 4-10 Cycloalkyl groups, more preferably C 5-8 It is a cycloalkyl group.

[0075] The polycyclic aliphatic hydrocarbon group (polycyclic alkyl group) may be a bridged cyclic or spirocyclic group, and examples of the bridged cyclic aliphatic hydrocarbon group (bridged cyclic alkyl group) include a bicyclo[1.1.1]pentan-1-yl group, a tricyclo[3.3.1.0]pentan-1-yl group, and a cyclo[1.1.1]pentan-1-yl group. 3,7 ]nonan-3-yl group (noradamantan-1-yl group), tricyclo[3.3.1.1 3,7 ]Decan-1-yl group (adamantan-1-yl group), pentacyclo[4.2.0.0 2,5 .0 3,8 .0 4,7 ] octan-1-yl group (cuban-1-yl group) and other bi- or pentacycloalkyl groups.

[0076] Examples of groups formed by combining two or more selected from alkyl groups, cycloalkyl groups, and polycyclic (e.g., bridged cyclic) alkyl groups include alkyl-cycloalkyl groups, alkyl-polycyclic (e.g., bridged cyclic) alkyl groups, cycloalkyl-alkyl groups, polycyclic (e.g., bridged cyclic) alkyl-alkyl groups, and alkyl-cycloalkyl-alkyl groups.

[0077] Examples of alkyl-cycloalkyl groups include mono- to tetra-C alkyl groups such as 1-methylcyclopropyl group, 2,2,3,3-tetramethylcyclopropyl group, 1-methyl-1-cyclohexyl group, 4-methyl-1-cyclohexyl group, 4-ethyl-1-cyclohexyl group, 4-propyl-1-cyclohexyl group, 4-isopropyl-1-cyclohexyl group, 4-butyl-1-cyclohexyl group, 4-isobutyl-1-cyclohexyl group, 4-t-butyl-1-cyclohexyl group, and 4-pentyl-1-cyclohexyl group. 1-6 Alkyl-C3-10 cycloalkyl groups, preferably mono- or di-C 1-5 Alkyl-C 5-8 Cycloalkyl groups are exemplified.

[0078] Examples of alkyl-polycyclic (e.g., bridged cyclic) alkyl groups include mono- to tetra-C alkyl groups such as 3-methyl-bicyclo[1.1.1]pentan-1-yl group. 1-6 Alkyl-bi- or pentacycloalkyl groups, preferably mono- or di-C 1-4 Examples include alkyl-bi- to tricycloalkyl groups.

[0079] Examples of the cycloalkyl-alkyl group include a C methyl group, a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a 2-cyclopentyl-ethyl group, a cyclohexylmethyl group, a 2-cyclohexyl-ethyl group, and a 3-cyclohexyl-propyl group. 3-10 Cycloalkyl-C 1-6 alkyl groups, preferably C 5-8 Cycloalkyl-C 1-4 Examples of suitable alkyl groups include:

[0080] Examples of polycyclic (e.g., bridged) alkyl-alkyl groups include tricyclo[3.3.1.1 3,7 ] Bi- or tricycloalkyl-C such as decan-1-yl-methyl (1-adamantyl-methyl) 1-4 Examples include alkyl groups.

[0081] Examples of alkyl-cycloalkyl-alkyl groups include C 2-(3-ethylcyclopentyl)ethyl groups. 1-4 Alkyl-C 5-10 Cycloalkyl-C 1-4 Examples include alkyl groups.

[0082] Of these saturated aliphatic hydrocarbon groups, alkyl groups (straight-chain or branched-chain alkyl groups), cycloalkyl groups, cross-linked cyclic alkyl groups, and groups combining two or more of these are preferred, and alkyl groups, cycloalkyl groups, and groups combining two or more of these are more preferred, with alkyl groups (particularly straight-chain alkyl groups) being particularly preferred.

[0083] R 2a and R 2b The types may be different from each other, but are preferably the same.

[0084] The group [-O-(A 1a O) n1a -C(=O)-R 2a ],[-O-(A 1b O) n1b -C(=O)-R 2b ](Hereinafter, R 2a ,R 2b Z of the containing group 1a ,Z 1b The substitution position for Z is not particularly limited. 1a ,Z 1b All you have to do is substitute the appropriate positions in R. 2a ,R 2b Z of the containing group 1a ,Z 1b The substitution position for Z 1a ,Z 1b When Z is a benzene ring, it is preferably at the 2-, 3- or 4-position of the phenyl group bonded to the 9-position of the fluorene ring, more preferably at the 3- or 4-position, and even more preferably at the 4-position. 1a ,Z 1b When Z is a naphthalene ring, it is often substituted at any one of the 5- to 8-positions of the naphthyl group bonded to the 9-position of the fluorene ring. For example, the 1- or 2-position of the naphthalene ring is substituted with respect to the 9-position of the fluorene ring (substitution in a 1-naphthyl or 2-naphthyl relationship), and it is preferred that Z be substituted with respect to this substitution position in a 1,5- or 2,6-position relationship, particularly in a 2,6-position relationship. 1a ,Z 1b If is a ring set arene ring, then R 2a,R 2b The substitution position of the containing group is not particularly limited, and for example, it may be substituted on the arene ring bonded to the 9-position of the fluorene or on the arene ring adjacent to this arene ring. For example, Z 1a ,Z 1b is a biphenyl ring (or Z 1a ,Z 1b is a benzene ring, m3a and m3b are 1, R 3a ,R 3b is a phenyl group), it is preferable that the 3-position of the biphenyl ring is bonded to the 9-position of the fluorene, and the 6-position of the biphenyl ring is bonded to R 2a ,R 2b It is preferred to bond to the containing group.

[0085] R 3a or R 3b The substituent represented by R may be a non-reactive group (or a non-polymerizable group) that is inert to the reaction. 3a or R 3b Examples of the substituent represented by R 1 (or R h ) and the like. 3a or R 3b Representative substituents represented by the formula are halogen atoms (fluorine atoms, etc.), hydrocarbon groups (e.g., alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, etc.), groups [-OR h Examples of the alkyl group (linear or branched chain alkyl group) include C groups such as methyl, ethyl, and t-butyl groups. 1-6 alkyl groups, and C groups such as methyl groups. 1-4 An alkyl group is preferred. Examples of the aryl group include C aryl groups such as phenyl groups. 6-10 Examples include aryl groups. R 3a and R 3b The types of R may be different from each other, but are preferably the same. 3a ,R 3b When is an aryl group, R 3a ,R 3b are Z1a ,Z 1b may form a ring assembly arena ring together with

[0086] R 3a or R 3b The substitution numbers m3a and m3b of Z can be integers equal to or greater than 0. 1a ,Z 1b The number of m3a and m3b can be appropriately selected depending on the type of R, and may be, for example, an integer of about 0 to 6, preferably an integer of 0 to 4, more preferably an integer of 0 to 2, even more preferably 0 or 1, and particularly preferably 0. m3a and m3b may be different from each other, but are preferably the same. When m3a is 2 or more, two or more R 3a may be the same or different from each other; when m3b is 2 or more, two or more R 3b The types may be the same or different from each other.

[0087] R 3a ,R 3b The substitution position of Z is not particularly limited. 1a ,Z 1b In the formula (I), the bonding position to the 9-position of the fluorene ring and the R 2a ,R 2b Any position other than the bonding position with the containing group may be used. For example, Z 1a ,Z 1b In the above R 2a ,R 2b Ortho position (R 2a ,R 2b It may be substituted or bonded to the carbon atom adjacent to the carbon atom to which the containing group is bonded.

[0088] Representative fluorene compounds (1) include those represented by the formula (1): R 1 represents a hydrocarbon group (for example, a hydrocarbon group having 20 or less carbon atoms), m1 represents an integer of 0 to 4, Z 1a and Z 1b is independently C 6-14 Showing the arene ring, A 1a and A1b is independently C 2-6 an alkylene group, n1a and n1b independently represent an integer of 0 to 10; R 2a and R 2b each independently represents a saturated aliphatic hydrocarbon group having 40 or less carbon atoms (e.g., an alkyl group, a cycloalkyl group, a bridged cyclic alkyl group, or a group formed by combining two or more of these groups), R 3a and R 3b each independently represents a hydrocarbon group (for example, a hydrocarbon group having 20 or less carbon atoms), and m3a and m3b each independently represent an integer of 0 to 4;

[0089] Preferably, R 1 represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, m1 represents an integer of 0 to 2, Z 1a and Z 1b are independently C groups such as benzene ring, naphthalene ring, and biphenyl ring. 6-12 Showing the arene ring, A 1a and A 1b is independently C 2-4 an alkylene group, n1a and n1b independently represent an integer of 0 to 6; R 2a and R 2b each independently represents an alkyl group, a cycloalkyl group, or a group formed by combining two or more of these groups, R 3a and R 3b each independently represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and m3a and m3b each independently represent an integer of 0 to 2;

[0090] More preferably, R 1 is C 1-6 Alkyl group or C 6-10 represents an aryl group, m1 represents an integer of 0 to 2, Z 1a and Z 1bare independently C such as benzene ring, naphthalene ring, etc. 6-10 Indicates an arene ring (especially a benzene ring), A 1a and A 1b are independently ethylene groups, propylene groups, etc. 2-3 represents an alkylene group (preferably an ethylene group), n1a and n1b independently represent an integer of 0 to 3 (preferably an integer of 0 to 2), R 2a and R 2b are independently alkyl groups (e.g., C 1-30 Alkyl groups, preferably C 4-26 Alkyl groups, more preferably C 8-23 alkyl group, more preferably C 10-12 It may be an alkyl group, and particularly preferably, C 5-27 Alkyl group, C 9-26 Alkyl group, C 11-25 Alkyl group, C 14-24 Alkyl group, C 15-23 Alkyl group, C 16-22 Alkyl group, C 17-21 alkyl group), R 3a and R 3b is independently C 1-6 Alkyl group or C 6-10 represents an aryl group, and m3a and m3b each independently represent an integer of 0 to 2.

[0091] Specific examples of the fluorene compound (1) include 9,9-bis[C fluorene] such as 9,9-bis[4-(2-(caproyloxy)ethoxy)phenyl]fluorene, 9,9-bis[4-(2-(lauroyloxy)ethoxy)phenyl]fluorene, 9,9-bis[4-(2-(stearoyloxy)ethoxy)phenyl]fluorene, 9,9-bis[4-(2-(behenoyloxy)ethoxy)phenyl]fluorene, 9,9-bis[6-(2-(stearoyloxy)ethoxy)-2-naphthyl]fluorene, and 9,9-bis[4-(2-(stearoyloxy)ethoxy)-3-phenylphenyl]fluorene. 1-40 Alkanoyloxy (mono or tri) C 2-4Alkoxy)C 6-12 aryl]fluorene and the like.

[0092] [Method for producing a fluorene compound represented by formula (1)] The method for producing the fluorene compound (1) is not particularly limited. For example, the method may be a method for producing the fluorene compound (1) by reacting a diol component represented by the following formula (2) [hereinafter also referred to as the fluorene compound (2)] with R 2a and R 2b The method may also include an esterification step of reacting (esterification reaction or transesterification reaction) the above with a corresponding saturated aliphatic carboxylic acid component.

[0093] [ka]

[0094] [In the formula, R 1 , m1, Z 1a and Z 1b , A 1a and A 1b , n1a and n1b, R 3a and R 3b and m3a and m3b are the same as those in formula (1) above, including preferred embodiments.

[0095] Examples of the fluorene compound (2) include 9,9-bis(hydroxyaryl)fluorenes in which n1a and n1b are 0 in the formula (2); and 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes in which n1a and n1b are 1 or more, for example, about 1 to 10.

[0096] In this specification and claims, unless otherwise specified, the term "(poly)alkoxy" is used to mean both an alkoxy group and a polyalkoxy group.

[0097] Examples of 9,9-bis(hydroxyaryl)fluorenes include 9,9-bis(hydroxyphenyl)fluorene, 9,9-bis(alkyl-hydroxyphenyl)fluorene, 9,9-bis(aryl-hydroxyphenyl)fluorene, and 9,9-bis(hydroxynaphthyl)fluorene.

[0098] Examples of 9,9-bis(hydroxyphenyl)fluorene include 9,9-bis(4-hydroxyphenyl)fluorene.

[0099] Examples of the 9,9-bis(alkyl-hydroxyphenyl)fluorene include 9,9-bis[(mono- or di-)C]fluorene such as 9,9-bis(4-hydroxy-3-methylphenyl)fluorene and 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene. 1-4 alkyl-hydroxyphenyl]fluorene and the like.

[0100] Examples of 9,9-bis(aryl-hydroxyphenyl)fluorene include 9,9-bis[(mono- or di-)C]fluorene such as 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene and 9,9-bis(4-hydroxy-3,5-diphenylphenyl)fluorene. 6-10 aryl-hydroxyphenyl]fluorene and the like.

[0101] Examples of 9,9-bis(hydroxynaphthyl)fluorene include 9,9-bis(6-hydroxy-2-naphthyl)fluorene and 9,9-bis(5-hydroxy-1-naphthyl)fluorene.

[0102] Examples of 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes include 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorene, 9,9-bis[alkyl-hydroxy(poly)alkoxyphenyl]fluorene, 9,9-bis[aryl-hydroxy(poly)alkoxyphenyl]fluorene, and 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorene.

[0103] Examples of the 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[hydroxy(mono- to deca)C such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene and 9,9-bis[4-(2-hydroxypropoxy)phenyl]fluorene. 2-4 alkoxy-phenyl]fluorene and the like.

[0104] Examples of the 9,9-bis[alkyl-hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[(mono- or di-)C such as 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene, and 9,9-bis[4-(2-hydroxypropoxy)-3-methylphenyl]fluorene. 1-4 Alkyl-hydroxy (mono or deca)C 2-4 alkoxy-phenyl]fluorene and the like.

[0105] Examples of the 9,9-bis[aryl-hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[(mono- or di)C such as 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, 9,9-bis[4-(2-hydroxypropoxy)-3-phenylphenyl]fluorene, and 9,9-bis[4-(2-hydroxyethoxy)-3,5-diphenylphenyl]fluorene. 6-10 Aryl-hydroxy(mono or deca)C 2-4 alkoxy-phenyl]fluorene and the like.

[0106] Examples of the 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorene include 9,9-bis[hydroxy(mono- to deca)C such as 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, 9,9-bis[5-(2-hydroxyethoxy)-1-naphthyl]fluorene, and 9,9-bis[6-(2-hydroxypropoxy)-2-naphthyl]fluorene. 2-4 Alkoxy-naphthyl]fluorene and the like.

[0107] R 2a or R 2b The saturated aliphatic carboxylic acid component corresponding to R 2a or R 2b The saturated aliphatic carboxylic acid may be a saturated aliphatic carboxylic acid in which a carboxyl group is bonded to a saturated aliphatic hydrocarbon group (monovalent group) represented by the formula (I), or an ester-forming derivative thereof. Examples of the ester-forming derivative of a saturated aliphatic carboxylic acid include esters such as alkyl esters (saturated aliphatic carboxylic acid esters), acid halides such as acid chlorides and acid bromides (saturated aliphatic carboxylic acid halides), and acid anhydrides (saturated aliphatic carboxylic acid anhydrides). Examples of the saturated aliphatic carboxylic acid esters include lower alkyl esters, specifically C esters such as methyl esters, ethyl esters, and t-butyl esters. 1-4 Alkyl esters and the like.

[0108] In addition, R 2a and a saturated aliphatic carboxylic acid component corresponding to R 2b The saturated aliphatic carboxylic acid components corresponding to the above may be different from each other, but are preferably the same compound.

[0109] As the saturated aliphatic carboxylic acid component, saturated aliphatic carboxylic acid, saturated aliphatic carboxylic acid halide, saturated aliphatic carboxylic acid anhydride are preferred, and saturated aliphatic carboxylic acid is more preferred.

[0110] R 2a ,R 2bSpecific saturated aliphatic carboxylic acids corresponding to the above include, for example, alkanoic acids (alkanecarboxylic acids), cycloalkanecarboxylic acids, bridged cyclic alkanecarboxylic acids, alkyl-cycloalkanecarboxylic acids, alkyl-bridged cyclic alkanecarboxylic acids, cycloalkyl-alkanoic acids, bridged cyclic alkyl-alkanoic acids, and alkyl-cycloalkyl-alkanecarboxylic acids.

[0111] Examples of alkanoic acids (linear or branched alkanoic acids) include acetic acid, propionic acid, butyric acid (butanoic acid), isobutyric acid (2-methylpropionic acid), valeric acid (pentanoic acid), isovaleric acid (3-methylbutanoic acid), 2-methylbutanoic acid, pivalic acid (2,2-dimethylpropionic acid), caproic acid (hexanoic acid), 2-methylpentanoic acid, 3-methylpentanoic acid, 4-methylpentanoic acid, 2-ethylbutanoic acid, 2,2-dimethylbutanoic acid, 3,3-dimethylbutanoic acid, 4-methylpentanoic acid, 4-methylpentanoic acid, 4-methylpentanoic acid, 4-methylbut ... Methylbutanoic acid, Enanthic acid (Heptanoic acid), 2-Methylhexanoic acid, 4-Methylhexanoic acid, 5-Methylhexanoic acid, 2,2-Dimethylpentanoic acid, Caprylic acid (Octanoic acid), 2-Methylheptanoic acid, 2-Ethylhexanoic acid, 2,2-Dimethylhexanoic acid, Pelargonic acid (Nonanoic acid), 4-Methyloctanoic acid, 3,5,5-Trimethylhexanoic acid, Decanoic acid, 4-Methylnonanoic acid, 7,7-Dimethyloctanoic acid, Undecanoic acid, Lauric acid (Dodecanoic acid) Decanoic acid), tridecanoic acid, myristic acid (tetradecanoic acid), 12-methyltridecanoic acid, pentadecanoic acid, 12-methyltetradecanoic acid, palmitic acid (hexadecanoic acid), 14-methylpentadecanoic acid, 2-hexyldecanoic acid, margaric acid (heptadecanoic acid), 2-methylhexadecanoic acid, 14-methylhexadecanoic acid, stearic acid (octadecanoic acid), 16-methylheptadecanoic acid, 2-(1,3,3-trimethylbutyl)-5,7, C-trimethyloctanoic acid, nonadecanoic acid, arachidic acid (icosanoic acid), henicosanoic acid, behenic acid (docosanoic acid), tricosanoic acid, lignoceric acid (tetracosanoic acid), pentacosanoic acid, cerotic acid (hexacosanoic acid), heptacosanoic acid, montanic acid (octacosanoic acid), nonacosanoic acid, melissic acid (triacontanoic acid), laxeronic acid (dotriacontanoic acid), gedaic acid (tetratriacontanoic acid), 2-hexadecyloctadecanoic acid, etc. 1-50 Alkane-carboxylic acids and the like.

[0112] Examples of cycloalkanecarboxylic acids include C carboxylic acids such as cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, and cycloheptanecarboxylic acid. 3-12 Examples include cycloalkane-carboxylic acids.

[0113] Examples of the bridged cyclic alkanecarboxylic acid include bicyclo[1.1.1]pentane-1-carboxylic acid, tricyclo[3.3.1.0]pentane-1-carboxylic acid, and the like. 3,7 ]nonane-3-carboxylic acid (noradamantane-3-carboxylic acid), tricyclo[3.3.1.1 3,7 ]Decane-1-carboxylic acid (adamantane-1-carboxylic acid), pentacyclo[4.2.0.0 2,5 .0 3,8 .0 4,7 ]octane-1-carboxylic acid (cubane-1-carboxylic acid), and other bi- or pentacycloalkanecarboxylic acids.

[0114] Examples of alkyl-cycloalkanecarboxylic acids include mono- to tetra-C alkyl-cycloalkanecarboxylic acids such as 1-methylcyclopropane-1-carboxylic acid, 2,2,3,3-tetramethylcyclopropanecarboxylic acid, 1-methyl-1-cyclohexanecarboxylic acid, 4-methyl-1-cyclohexanecarboxylic acid, 4-ethyl-1-cyclohexanecarboxylic acid, 4-propyl-1-cyclohexanecarboxylic acid, 4-isopropyl-1-cyclohexanecarboxylic acid, 4-butyl-1-cyclohexanecarboxylic acid, 4-isobutyl-1-cyclohexanecarboxylic acid, 4-t-butyl-1-cyclohexanecarboxylic acid, and 4-pentyl-1-cyclohexanecarboxylic acid. 1-6 Alkyl-C 3-10 Examples include cycloalkane-carboxylic acids.

[0115] Examples of alkyl-bridged cyclic alkanecarboxylic acids include mono- to tetra-C alkyl alkanecarboxylic acids such as 3-methyl-bicyclo[1.1.1]pentane-1-carboxylic acid. 1-6 Examples thereof include alkyl-bi- or pentacycloalkanecarboxylic acids.

[0116] Examples of cycloalkyl-alkanoic acids include C alkanoic acids such as cyclopropyl acetic acid, cyclobutyl acetic acid, cyclopentyl acetic acid, 3-cyclopentylpropionic acid, cyclohexyl acetic acid, 3-cyclohexylpropionic acid, and 4-cyclohexylbutanoic acid. 3-10Cycloalkyl-C 1-6 Alkane-carboxylic acids and the like.

[0117] Examples of bridged cyclic alkyl-alkanoic acids include bicycloalkyl-C such as 1-adamantylacetic acid, tricycloalkyl-C 1-4 Alkane-carboxylic acids and the like.

[0118] Examples of alkyl-cycloalkyl-alkanecarboxylic acids include C 3-(3-ethylcyclopentyl)propionic acid. 1-4 Alkyl-C 5-10 Cycloalkyl-C 1-4 Alkane-carboxylic acids and the like.

[0119] Preferred saturated aliphatic carboxylic acid components include R 2a and R 2b The same applies to the preferred embodiments of the above.

[0120] R 2a and R 2b The total amount of the saturated aliphatic carboxylic acid components corresponding to the above is, for example, 1 to 10 mol, preferably 1.05 to 5 mol, more preferably 1.1 to 2 mol, and even more preferably 1.2 to 1.4 mol, relative to 1 mol of the hydroxyl group of the fluorene compound (2).

[0121] When the saturated aliphatic carboxylic acid component is a saturated aliphatic carboxylic acid or an ester thereof, the reaction may be carried out in the presence of a conventional esterification catalyst, such as an acid catalyst, a base catalyst, or a metal catalyst, with an acid catalyst being preferred.

[0122] Examples of the acid catalyst include inorganic acids, organic acids, Lewis acids such as boron trifluoride etherate and tin tetrachloride, and solid acid catalysts such as cation exchange resins. These acid catalysts may be used alone or in combination. These acid catalysts may also be hydrates.

[0123] Examples of the inorganic acid include strong acids, specifically sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, etc.; and homo- or heteropoly acids, specifically tungstophosphoric acid, molybdophosphoric acid, tungstosilicic acid, molybdosilicic acid, etc.

[0124] Examples of the organic acid include sulfonic acids, specifically, alkanesulfonic acids such as methanesulfonic acid and ethanesulfonic acid, fluorinated alkanesulfonic acids such as trifluoromethanesulfonic acid, and arenesulfonic acids such as p-toluenesulfonic acid. Of these, arenesulfonic acids such as p-toluenesulfonic acid monohydrate are preferred.

[0125] The proportion of the catalyst is, for example, 0.001 to 1 mol, preferably 0.01 to 0.5 mol, more preferably 0.05 to 0.2 mol, and particularly preferably 0.1 to 0.15 mol, per 1 mol of the fluorene compound (2).

[0126] When the saturated aliphatic carboxylic acid component is a saturated aliphatic carboxylic acid halide or a saturated aliphatic carboxylic acid anhydride, the reaction may be carried out in the presence of a base to capture (trap) acids such as hydrogen halide produced in the reaction. The base can be broadly classified into, for example, inorganic bases and organic bases. The base may be used alone or in combination of two or more types.

[0127] Examples of inorganic bases include metal hydroxides, specifically alkali metal or alkaline earth metal hydroxides such as sodium hydroxide and calcium hydroxide; metal carbonates, specifically alkali metal or alkaline earth metal carbonates such as sodium carbonate and calcium carbonate; and metal hydrogen carbonates, specifically alkali metal or alkaline earth metal hydrogen carbonates such as sodium hydrogen carbonate.

[0128] Examples of organic bases include amines, specifically trialkylamines such as triethylamine, aromatic tertiary amines such as benzyldimethylamine, and heterocyclic amines such as pyridine and N-methylmorpholine.

[0129] Among these bases, amines, for example, trialkylamines such as triethylamine, are often used. The amount of base used is not particularly limited, but for example, 2a and R 2b The amount is 1 to 2 moles, preferably 1.05 to 1.5 moles, and more preferably 1.1 to 1.2 moles, relative to 1 mole of the total amount of the saturated aliphatic carboxylic acid components corresponding to the above.

[0130] The reaction may be carried out in the presence of a solvent. Examples of the solvent include hydrocarbons, specifically aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons, specifically methylene chloride, chloroform, 1,2-dichloroethane, and chlorobenzene; ethers, specifically dialkyl ethers such as diethyl ether, and cyclic ethers such as tetrahydrofuran (THF) and 1,4-dioxane; ketones, specifically acetone and methyl ethyl ketone; sulfoxides, specifically dimethyl sulfoxide; amides, specifically N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; and nitriles such as acetonitrile. The solvent may be used alone or in combination. Among these solvents, aromatic hydrocarbons such as toluene are preferred. The ratio of the solvents is determined based on the ratio of the fluorene compound (2) and R 2a and R 2b For example, it may be about 10 to 1000 parts by mass, preferably 30 to 500 parts by mass, and more preferably 50 to 150 parts by mass, relative to 100 parts by mass of the total amount of the saturated aliphatic carboxylic acid components corresponding to the above.

[0131] The reaction temperature and reaction time can be appropriately selected depending on the type of raw material used. When the saturated aliphatic carboxylic acid component is a saturated aliphatic carboxylic acid or its ester, the reaction temperature is, for example, 50 to 150°C, preferably 100 to 130°C, and more preferably 110 to 120°C. When the saturated aliphatic carboxylic acid component is a saturated aliphatic carboxylic acid halide or a saturated aliphatic carboxylic acid anhydride, the reaction temperature is, for example, -10 to 50°C, preferably 0 to 30°C, and more preferably 5 to 20°C. The reaction may be carried out at reflux temperature. The reaction time is not particularly limited and may be, for example, about 1 to 24 hours.

[0132] The reaction may be carried out in air or in an inert gas atmosphere such as nitrogen gas or a rare gas, under normal pressure, elevated pressure or reduced pressure, and may be carried out with stirring.

[0133] After the reaction is completed, the produced fluorene compound (1) may be separated and purified by a conventional method, such as neutralization, washing, dehydration, filtration, adsorption, concentration, extraction, crystallization, recrystallization, reprecipitation, centrifugation, column chromatography, or a combination thereof.

[0134] [Characteristics and uses of the fluorene compound represented by formula (1)] (characteristic) The fluorene compound (1) has excellent heat resistance, and therefore, the 5% weight loss temperature Td5 of the fluorene compound (1) may be, for example, 350°C or higher (for example, about 400 to 500°C), preferably 410 to 490°C, 420 to 480°C, 425 to 470°C, 430 to 460°C, or 435 to 450°C in the following stepwise manner, and more preferably 350 to 430°C, 355 to 420°C, 360 to 410°C, 365 to 408°C, 370 to 405°C, 375 to 402°C, 380 to 400°C, or 385 to 395°C in the following stepwise manner. The 10% weight loss temperature Td10 of the fluorene compound (1) may be, for example, 380°C or higher (for example, about 400 to 600°C), preferably 420°C or higher (for example, 430 to 550°C), 450°C or higher (for example, 455 to 550°C), 460°C or higher (for example, 470 to 530°C), 480°C or higher (for example, 490 to 520°C), or 500°C or higher (for example, 500 to 510°C), more preferably 370 to 450°C, 375 to 440°C, 380 to 430°C, 385 to 425°C, 390 to 420°C, 395 to 415°C, or 400 to 410°C.

[0135] In this specification and claims, the 5% weight loss temperature Td5 and the 10% weight loss temperature Td10 can be measured by the method described in the examples below.

[0136] The refractive index nD of the fluorene compound (1) may be selected from the range of, for example, about 1.5 or more (for example, about 1.5 to 1.6) at a temperature of 25°C and a wavelength of 589 nm, and is preferably 1.51 to 1.59, more preferably 1.52 to 1.585 (for example, 1.53 to 1.57), and particularly preferably 1.54 to 1.58 (for example, 1.545 to 1.56).

[0137] In this specification and claims, the refractive index nD can be measured by a method described in the examples below, in which a solution capable of dissolving the fluorene compound (1) is prepared using a refractometer, the refractive index of the obtained solution is measured, and a calibration curve (approximate straight line) is prepared, and the refractive index nD can be determined by extrapolating the concentration to 100 mass %.

[0138] The fluorene compound (1) may be crystalline or amorphous, and is preferably amorphous.

[0139] (Resin composition and molded article thereof) The resin composition of the present disclosure may contain at least a resin and the fluorene compound (1) of the present disclosure. The resin may be a curable resin (thermo- or photo-curable resin), a thermoplastic resin, or the like.

[0140] Examples of curable resins (thermo- or photo-curable resins) include phenolic resins (resole type, novolac type, etc.); amino resins (urea resin, melamine resin, guanamine resin, etc.); furan resins; unsaturated polyester resins; diallyl phthalate resins; vinyl ester resins [or epoxy (meth)acrylate resins]; polyfunctional (meth)acrylate resins; epoxy resins; urethane resins; polyimide resins; and silicone resins.

[0141] Examples of thermoplastic resins include polyolefin resins (such as linear or cyclic olefin resins); styrene resins (such as polystyrene (PS) or styrene copolymers (including rubber-containing styrene resins (or rubber-grafted styrene copolymers) such as high impact polystyrene (HIPS) and ABS resin)); (meth)acrylic resins (such as homopolymers or copolymers of (meth)acrylic monomers); vinyl acetate resins (including polyvinyl alcohol (PVA) and polyvinyl acetal); vinyl chloride resins (such as homopolymers or copolymers of vinyl chloride and / or vinylidene chloride); fluororesins; polyester resins (such as polyalkylene arylate resins, polyarylate resins, and liquid crystalline polyesters); polycarbonate resins (PC), specifically, bisphenol A Examples include bisphenol-type polycarbonate resins such as polyamide resins (PA) [aliphatic polyamide resins, aromatic polyamide resins (aramid resins)], polyacetal resins (POM), polyphenylene ether resins (PPE), polyphenylene sulfide resins (PPS), polysulfone resins [polysulfone resins (PSF), polyethersulfone (PES)], polyetherketone resins [polyetherketone resins (PEK), polyetheretherketone resins (PEEK), polyetherketoneetherketoneketone (PEKEKK)], phenoxy resins, polyketone resins, cellulose derivatives (cellulose esters, cellulose ethers), thermoplastic polyimide resins, polyethernitrile resins, and thermoplastic elastomers (TPE).

[0142] These resins may be contained alone or in combination of two or more.

[0143] The proportion of the fluorene compound (1) in the resin composition may be appropriately selected depending on the application, etc., and may be, for example, about 50% by mass or less, preferably 30% by mass or less, 15% by mass or less, 10% by mass or less (e.g., 0.1 to 5% by mass) in stages relative to the total amount of the resin and the fluorene compound (1), or may be, for example, about 50% by mass or more, preferably 70% by mass or more, 80% by mass or more, 90% by mass or more in stages.

[0144] The resin composition may contain, as necessary, various conventional additives, for example, fillers or reinforcing agents, colorants such as dyes and pigments, conductive agents, flame retardants, flame retardant assistants, plasticizers, lubricants, stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), release agents, antistatic agents, dispersants, compatibilizers, flow control agents, leveling agents, antifoaming agents, surface modifiers, stress reducing agents, carbon materials, etc. These additives may be used alone or in combination of two or more.

[0145] The total proportion of these additives may be, for example, 50 parts by mass or less, preferably 30 parts by mass or less, 0 to 10 parts by mass, or about 0.1 to 5 parts by mass, stepwise, relative to 100 parts by mass of the resin in the resin composition.

[0146] The resin composition may be prepared by mixing a resin, a fluorene compound (1), and, if necessary, other components, for example, by a conventional method such as dry mixing or melt kneading, and the resin composition may be in the form of pellets or the like.

[0147] The present disclosure encompasses a molded article containing at least the resin composition of the present disclosure. The shape of the molded article is not particularly limited and may be selected depending on the application. For example, the molded article may be in the form of a pellet, a linear (fiber or thread) or rod-like one-dimensional structure, a film, sheet, or plate-like two-dimensional structure, a block, a concave or convex lens-like lens, or a hollow (tubular or tubular) three-dimensional structure, or a composite or complex shape combining these shapes.

[0148] The molded body can be molded using a conventional molding method depending on the type of resin, the shape and application of the molded body, etc., and can be manufactured using, for example, injection molding, compression molding, transfer molding, laminate molding, FRP molding, casting, powder molding, extrusion molding, blow molding, lamination, casting molding, calendar processing, foam molding, 3D printer method, etc.

[0149] The molded article may also be a composite molded article including the resin composition of the present disclosure and other constituent members. The proportion of the resin composition of the present disclosure in the molded article is not particularly limited and may be, for example, about 10 to 100 mass %, or about 20 to 80 mass %. [Example]

[0150] The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples. Details of evaluation items and raw materials are shown below.

[0151] [Evaluation method] (HPLC) The sample was dissolved in acetonitrile and measured using an HPLC (high performance or high performance liquid chromatograph) device "LC-2030" or "LC-2010A HT" manufactured by Shimadzu Corporation and an "ODS-80™" manufactured by Tosoh Corporation as the column, and the HPLC purity (LC purity) [area %] was calculated.

[0152] ( 1 H-NMR) The sample was dissolved in a heavy solvent containing tetramethylsilane as an internal standard, and the NMR spectra were analyzed using a nuclear magnetic resonance spectrometer (JEOL "JNM-ECZ400S" in Examples 1 to 4; BRUKER "AVANCE III HD" in Examples 5 and 6). 1 H-NMR spectrum was measured.

[0153] (weight loss temperature) Using a thermogravimetry-differential thermal analyzer (TG-DTA) (Rigaku Corporation, "TG-DTA8122"), the temperature at which the sample lost 5% mass (5% weight loss temperature, Td5) and the temperature at which the sample lost 10% mass (10% weight loss temperature, Td10) were measured under conditions of a nitrogen atmosphere, a heating rate of 10°C / min, and a temperature range of 30 to 500°C.

[0154] (Refractive index nD) The refractive index nD was measured using a refractometer (ATAGO Co., Ltd., "RX-7000i") at a temperature of 25°C and a wavelength of 589 nm (D line). For solid samples, the sample was dissolved in cyclohexanone to prepare solutions with concentrations of 10 mass%, 15 mass%, and 20 mass%, and the refractive index of the resulting solution and a concentration of 0 mass% (cyclohexanone only) was measured to create a calibration curve (approximate straight line). The refractive index was calculated by extrapolating the concentration to 100 mass%. For liquid samples, the refractive index was calculated directly without preparing a solution.

[0155] [Raw materials] (Diol component) BPEF (registered trademark): 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, manufactured by Osaka Gas Chemicals Co., Ltd. BNEF (registered trademark): 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, manufactured by Osaka Gas Chemicals Co., Ltd. BOPPEF (registered trademark): 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, manufactured by Osaka Gas Chemicals Co., Ltd. (carboxylic acid component) Caproic acid: CH3-(CH2)4-COOH, manufactured by Tokyo Chemical Industry Co., Ltd. Lauric acid: CH3-(CH2) 10 -COOH, manufactured by Kishida Chemical Co., Ltd. Stearic acid: CH3-(CH2) 16 -COOH, manufactured by Tokyo Chemical Industry Co., Ltd. Behenic acid: CH3-(CH2) 20 -COOH, manufactured by Combi-Blocks 3-Hydroxybenzoic acid: HO-C6H4-COOH

[0156] [Example 1] 230 g (0.52 mol) of BPEF, 158.4 g (1.36 mol) of caproic acid, and 512 g of toluene were added to a reaction vessel and dissolved with stirring. 12.5 g (0.066 mol) of p-toluenesulfonic acid monohydrate was added to the resulting solution and stirred at an internal temperature of 115°C for 4 hours. After the reaction was completed, the mixture was allowed to cool, and then 1825 g of toluene and 194 g of 20% by weight saline solution were added. The mixture was transferred to a separatory funnel and heated to 60-70°C. The aqueous layer was removed to obtain an organic layer. 187 g of 10% by weight aqueous sodium hydroxide solution was then added to the organic layer and stirred to neutralize it. The organic layer obtained after removing the aqueous layer was washed once with 186 g of 20% by weight saline solution. The aqueous layer was then removed, and the resulting organic layer was washed with 190 g of ion-exchanged water. This procedure was repeated four times. The aqueous layer was then removed, and insoluble matter was removed from the resulting organic layer by filtration. The obtained organic layer (filtrate) was concentrated under reduced pressure to remove the solvent, and then dried to obtain 220 g (yield 66%, LC purity 96.9%, refractive index 1.5794) of the target product (9,9-bis[4-(2-(caproyloxy)ethoxy)phenyl]fluorene) represented by the following formula as a brown viscous liquid.

[0157] [ka]

[0158] 1 H NMR(400MHz,CD2Cl2):δ(ppm)0.86(6H,t), 1.24-1.34(8H,m), 1.55-1.63(4H,m), 2.30(4H,t), 4.09-4.11(4H, m), 4.34-4.36(4H,m), 6.75-6.78(4H,m), 7.07-7.11(4H,m), 7.25-7.29(2H,m), 7.34-7.38(4H,m), 7.78(2H,d)

[0159] [Example 2] 220 g (0.50 mol) of BPEF, 261.3 g (1.30 mol) of lauric acid, and 490 g of toluene were added to a reaction vessel and stirred to dissolve. 11.9 g (0.063 mol) of p-toluenesulfonic acid monohydrate was added to the resulting solution and stirred at an internal temperature of 115°C for 4 hours. After the reaction was completed, the mixture was allowed to cool, and then 1745 g of toluene and 186 g of 20% by weight saline solution were added. The mixture was transferred to a separatory funnel and heated to 60-70°C. The aqueous layer was removed to obtain an organic layer. 179 g of 10% by weight aqueous sodium hydroxide solution and 178 g of 20% by weight saline solution were then added to the organic layer for neutralization. The aqueous layer was removed, and the precipitate generated by neutralization was removed from the resulting organic layer by filtration. 178 g of 20% by weight saline solution was added to the resulting organic layer (filtrate) for washing. The aqueous layer was then removed, and the resulting organic layer was washed with 182 g of ion-exchanged water. This procedure was repeated four times. The aqueous layer was removed, and insoluble matter was removed from the resulting organic layer by filtration. The resulting organic layer (filtrate) was concentrated under reduced pressure to remove the solvent, and then dried to obtain 359 g (yield 89%, LC purity 97.4%, refractive index 1.5499) of the target product (9,9-bis[4-(2-(lauroyloxy)ethoxy)phenyl]fluorene) represented by the following formula as a pale brown viscous liquid.

[0160] [ka]

[0161] 1 H NMR(400MHz,CD2Cl2):δ(ppm)0.87(6H,t), 1.25(32H,s), 1.54-1.60(4H,m), 2.29(4H,t), 4.09-4.11(4H,m) , 4.34-4.36(4H,m), 6.74-6.79(4H,m), 7.07-7.11(4H,m), 7.25-7.29(2H,m), 7.34-7.38(4H,m), 7.77(2H,d)

[0162] [Example 3] 212 g (0.48 mol) of BPEF, 358 g (1.26 mol) of stearic acid, and 472 g of toluene were added to a reaction vessel and dissolved with stirring. 11.5 g (0.06 mol) of p-toluenesulfonic acid monohydrate was added to the resulting solution and stirred at an internal temperature of 115°C for 4 hours. After the reaction was completed, the mixture was allowed to cool, and then 1682 g of toluene and 179 g of 20% by weight saline solution were added. The mixture was transferred to a separatory funnel and heated to 60-70°C. The aqueous layer was removed to obtain an organic layer. 172 g of 10% by weight aqueous sodium hydroxide solution and 171 g of 20% by weight saline solution were then added to the organic layer and stirred to neutralize it. The organic layer obtained after removing the aqueous layer was washed once with 171 g of 20% by weight saline solution. The organic layer obtained after removing the aqueous layer was then washed with 171 g of ion-exchanged water, and this process was repeated five times. The insoluble matter was removed from the organic layer obtained after removing the aqueous layer by filtration. The obtained organic layer (filtrate) was concentrated under reduced pressure to remove the solvent, and then dried to obtain 402 g (yield 86%, LC purity 97.4%, refractive index 1.5282) of the target product (9,9-bis[4-(2-(stearoyloxy)ethoxy)phenyl]fluorene) represented by the following formula as a light brown solid.

[0163] [ka]

[0164] 1 H NMR(400MHz,CD2Cl2):δ(ppm)0.88(6H,t), 1.25-1.30(56H,m), 1.54-1.60(4H,m), 2.29(4H,t), 4.09-4.11(4H, m), 4.34-4.36(4H,m), 6.74-6.78(4H,m), 7.07-7.11(4H,m), 7.25-7.29(2H,m), 7.34-7.38(4H,m), 7.77(2H,d)

[0165] [Example 4] A reaction vessel was charged with 185 g (0.42 mol) of BPEF, 373.6 g (1.1 mol) of behenic acid, and 752 g of toluene, and the mixture was stirred and dissolved. 10.0 g (0.053 mol) of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at an internal temperature of 115°C for 4 hours. After the reaction was completed, the mixture was allowed to cool, and then 1128 g of toluene and 156 g of 20% by weight saline solution were added. The mixture was transferred to a separatory funnel and heated to 60-70°C. The aqueous layer was removed to obtain an organic layer. The organic layer was then neutralized with 150 g of 10% by weight sodium hydroxide aqueous solution and 150 g of 20% by weight saline solution, followed by washing once with 150 g of 20% by weight saline solution. The aqueous layer was removed, and the resulting organic layer was washed with 153 g of toluene and 153 g of ion-exchanged water. This process was repeated twice. The aqueous layer was then removed, and the resulting organic layer was washed with 153 g of ion-exchanged water. This process was repeated five times. The aqueous layer was removed, and insoluble matter was removed from the resulting organic layer by filtration. The resulting organic layer (filtrate) was concentrated under reduced pressure to remove the solvent, and then dried to obtain 333 g (yield 73%, LC purity 85.1%, refractive index 1.5182) of the target product (9,9-bis[4-(2-(behenoyloxy)ethoxy)phenyl]fluorene) represented by the following formula as a light brown solid.

[0166] [ka]

[0167] 1 H NMR(400MHz,CD2Cl2):δ(ppm)0.88(6H,t), 1.25-1.30(72H,m), 1.57-1.60(4H,m), 2.29(4H,t), 4.09-4.11(4H, m), 4.33-4.36(4H,m), 6.74-6.78(4H,m), 7.07-7.11(4H,m), 7.25-7.29(2H,m), 7.34-7.38(4H,m), 7.77(2H,d)

[0168] [Example 5] 32.34 g (0.06 mol) of BNEF, 44.4 g (0.156 mol) of stearic acid, and 59.14 g of toluene were added to a reaction vessel, heated, and stirred. At 62 ° C, 1.45 g (0.0076 mol) of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at an internal temperature of 120 ° C for 4 hours. After the reaction was completed, the mixture was allowed to cool, 100.1 g of toluene was added, and the mixture was completely dissolved at 70 ° C. After that, the mixture was transferred to a separatory funnel and 23.54 g of 20% by weight saline was added. The aqueous layer was removed to obtain an organic layer. 22.2 g of 20% by weight saline and 21.8 g of 10% by weight aqueous sodium hydroxide solution were added to the organic layer, and the precipitated solid was filtered. The filtrate was then transferred to a separatory funnel again and washed once with 23.7 g of 20% by weight saline. The water bath was then removed, and 21 g of ion-exchanged water was added to wash the mixture. This operation was repeated five times. The resulting organic layer was concentrated under reduced pressure to remove the solvent, and then dried to obtain 57.55 g (yield 83.5%, refractive index 1.5483) of the target product (9,9-bis[6-(2-(stearoyloxy)ethoxy)-2-naphthyl]fluorene) represented by the following formula as a light brown solid.

[0169] [ka]

[0170] 1 H NMR (300MHz, CDCl3): δ(ppm)0.87(6H,t), 1.19-1.32(56H,m), 1.57-1.65(4H,m), 2.34(4H,t), 4.23(4H,t), 4.46( 4H,t), 7.07-7.10(4H,m), 7.24-7.30(2H,m), 7.35-7.41(4H,m), 7.49-7.74(6H,m), 7.59-7.62(2H,m), 7.81(2H,d)

[0171] [Example 6] 35.92 g (0.06 mol) of BOPPEF, 44.4 g (0.156 mol) of stearic acid, and 109.48 g of toluene were added to a reaction vessel, heated, and stirred. At 60°C, 1.45 g (0.0076 mol) of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at an internal temperature of 114°C for 9 hours. After the reaction was completed, the mixture was allowed to cool, 143.6 g of toluene was added, and the mixture was completely dissolved at 70°C. The mixture was then transferred to a separatory funnel and 23.36 g of 20% by weight saline was added, and the aqueous layer was removed to obtain an organic layer. 22.4 g of 20% by weight saline and 22.7 g of 10% by weight aqueous sodium hydroxide solution were then added to the organic layer, and the precipitated solid was filtered. The filtrate was then transferred to a separatory funnel again and washed once with 23.6 g of 20% by weight saline. This process of adding 21 g of ion-exchanged water and washing with water was repeated five times. The resulting organic layer was concentrated under reduced pressure to remove the solvent, and then dried to obtain 39.14 g (yield 54.4%, refractive index 1.5482) of the target product (9,9-bis[4-(2-(stearoyloxy)ethoxy)-3-phenylphenyl]fluorene) represented by the following formula as a light brown solid.

[0172] [ka]

[0173] 1 H NMR (300MHz, CDCl3): δ(ppm)0.88(6H,t), 1.24-1.25(56H,m), 1.53-1.58(4H,m), 2.24(4H,t), 4.08 (4H,t), 4.29(4H,t), 6.78(2H,d), 7.09(2H,dd), 7.22-7.36(12H,m), 7.41-7.45(6H,m), 7.74(2H,d)

[0174] [Reference example 1] 300 g (685 mmol) of BPEF, 246 g (1.78 mol) of 3-hydroxybenzoic acid, 699 g of toluene, and 1.5 g (12.2 mmol) of methoquinone were added to a reaction vessel and stirred to dissolve. 16.3 g (85.5 mmol) of p-toluenesulfonic acid monohydrate was added and stirred at an internal temperature of 110°C for 24 hours. After the reaction was completed, the mixture was allowed to cool, and 1.25 L of ethyl acetate and 510 g of ion-exchanged water were added. The mixture was transferred to a separatory funnel and heated to 60-70°C. The aqueous layer was removed to obtain an organic layer. The resulting organic layer was washed twice with water. The aqueous layer was removed, and the resulting organic layer was concentrated under reduced pressure to remove the solvent. The residue was then dried to obtain 387.7 g (yield 83%, LC purity 84.0%) of the target compound (9,9-bis[4-(2-(3-hydroxybenzoyloxy)ethoxy)phenyl]fluorene) represented by the following formula as pale brown crystals.

[0175] [ka]

[0176] [Comparative Examples 1 to 6] The weight loss temperatures of the diol components or carboxylic acid components shown in Table 1 below were measured.

[0177] The results are shown in Table 1 below.

[0178] [Table 1]

[0179] As is clear from the results in Table 1, the Examples all exhibited higher heat resistance than the Comparative Examples, which contained only a diol component or a carboxylic acid component. In particular, it was an unexpected result that heat resistance was improved despite the introduction of an aliphatic skeleton derived from a carboxylic acid component, which has a low weight loss temperature, into the diol component, rather than an aromatic skeleton, which is more likely to improve heat resistance. Among Examples 1 to 4, in which a carboxylic acid component was added, Examples 2 to 4 (particularly Examples 3 and 4) had better heat resistance, and among Examples 3, 5, and 6, in which a diol component was added, Examples 3 and 6 (particularly Example 3) had better heat resistance. Note that as the number of carbon atoms in the introduced aliphatic skeleton increased, heat resistance improved, while the refractive index decreased.

[0180] Moreover, from the viewpoint of handling, Examples 3 to 6, which were obtained as solids, were superior.

[0181] Furthermore, in terms of productivity (high yield, high purity), Examples 2 and 3 were superior.

[0182] Example 3 was preferable in that it had an excellent balance of heat resistance, ease of handling, and productivity (high yield, high purity). [Industrial Applicability]

[0183] The fluorene compounds of the present disclosure have a 9,9-bisarylfluorene skeleton and can therefore be used as additives (resin additives) such as refractive index modifiers (e.g., refractive index improvers), Abbe number modifiers (e.g., Abbe number improvers), birefringence modifiers, heat resistance improvers, strength improvers, abrasion resistance improvers, crystallization promoters, plasticizers, and flowability improvers.

Claims

1. A compound represented by the following formula (1): 【Chemistry 1】 (In the formula, R １ represents a substituent, m1 represents an integer of 0 to 8, Z １ａ and Z １ｂ are independently arene rings, A １ａ and A １ｂ each independently represents an alkylene group; n1a and n1b each independently represents an integer of 0 or more; R ２ａ and R ２ｂ each independently represents a saturated aliphatic hydrocarbon group, R ３ａ and R ３ｂ each independently represents a substituent, and m3a and m3b each independently represent an integer of 0 or more.

2. In the formula (1), R １ represents a hydrocarbon group, m1 represents an integer of 0 to 4, Z １ａ and Z １ｂ is independently C ６－１４ Showing an arene ring, A １ａ and A １ｂ is independently C ２－６ represents an alkylene group, n1a and n1b independently represent an integer of 0 to 10, R ２ａ and R ２ｂ each independently represents a saturated aliphatic hydrocarbon group having 40 or less carbon atoms, R ３ａ and R ３ｂ The compound according to claim 1, wherein m3a and m3b independently represent an integer of 0 to 4.

3. In the formula (1), R １ represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group; m1 represents an integer of 0 to 2; Z １ａ and Z １ｂ is independently C ６－１２ Showing an arene ring, A １ａ and A １ｂ is independently C ２－４ represents an alkylene group, n1a and n1b independently represent an integer of 0 to 6, R ２ａ and R ２ｂ each independently represents an alkyl group, a cycloalkyl group, or a group formed by combining two or more of these groups, R ３ａ and R ３ｂ The compound according to claim 1 or 2, wherein m3a and m3b independently represent an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group; and m3a and m3b independently represent an integer of 0 to 2.

4. 3. The compound according to claim 1, wherein the 5% weight loss temperature is 355 to 420°C.

5. 3. The compound according to claim 1, wherein the 10% weight loss temperature is 375 to 440°C.

6. A diol component represented by the following formula (2) and R ２ａ and R ２ｂ A method for producing a compound represented by formula (1) according to claim 1 or 2, comprising the step of reacting a corresponding saturated aliphatic carboxylic acid component with a compound represented by formula (1). 【Chemistry 2】 (In the formula, R １ , m1, Z １ａ and Z １ｂ , A １ａ and A １ｂ , n1a and n1b, R ３ａ and R ３ｂ , and m3a and m3b are the same as those in formula (1).

7. A resin composition comprising the compound according to claim 1 or 2 and a resin.

8. A molded article comprising the resin composition according to claim 7.

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