Fluorene compound, production method therefor, and use thereof

Abstract

Provided is a fluorene compound represented by formula (1) (wherein Z1 and Z2 each independently represent an aromatic hydrocarbon ring, A1 and A2 each independently represent an alkylene group, n1 and n2 each independently indicate an integer of 0 or larger, R1 and R2 each independently represent a hydrocarbon group, R3 and R4 each independently represent a substituent, m1 and m2 each independently indicate an integer of 0 or larger, R5 represents a substituent, and k indicates an integer of 0-8). Use of the fluorene compound as an additive for a resin component can improve the fluidity of the resin component.

Description

Fluorene compounds, their production methods and uses

[0001] The present disclosure relates to a fluorene compound having a 9,9-bis(acyloxyaryl)fluorene skeleton, a method for producing the same, and uses thereof.

[0002] Compounds having a fluorene skeleton have excellent heat resistance and optical properties, and are therefore used primarily in the optical field as raw materials for resins, or as resin additives such as refractive index improvers and heat resistance improvers. In particular, in the optical field in recent years, technological innovation has been remarkable, and advanced functions are required in terms of optical properties and heat resistance, so fluorene compounds with further improved functions by introducing substituents into the fluorene skeleton have been proposed.

[0003] Japanese Patent Laid-Open Publication No. 2020-169144 (Patent Document 1) discloses a biphenyl derivative having a 9,9-bisarylfluorene skeleton and an oxyalkylene group as a fluorene compound having high heat resistance and useful as a raw material for polyester resins.

[0004] Japanese Patent Laid-Open No. 2021-187768 (Patent Document 2) discloses 9,9-bis(4-benzoyloxyphenyl)fluorenes as raw materials from which high-purity polyester resins having excellent heat resistance and the like can be obtained.

[0005] Japanese Patent Laid-Open Publication No. 2022-143442 (Patent Document 3) discloses a dicarboxylic acid or a derivative thereof having a structure in which fused tetracyclic to hexacyclic aryl groups are linked to positions 1 to 8 of a fluorene skeleton, as a fluorene compound having a high refractive index and heat resistance and useful as a resin raw material or a resin additive.

[0006] JP 2020-169144 A JP 2021-187768 A JP 2022-143442 A

[0007] On the other hand, when a fluorene compound is used as an additive for a resin component, it is necessary to improve the function of the resin component without impairing the moldability of the resin component, and it is also required to ensure fluidity during molding. Furthermore, for resin components that require molding at high temperatures, it is also required to exhibit their functions without deterioration due to thermal decomposition, etc.

[0008] In contrast, Patent Documents 1 and 2 do not describe the use of a fluorene compound as an additive to a resin. On the other hand, Patent Document 3 describes the use of a fluorene compound as an additive to a resin, but does not describe the improvement of the fluidity of the resin.

[0009] Therefore, an object of the present disclosure is to provide a fluorene compound capable of improving the fluidity of a resin component, a method for producing the same, and uses thereof.

[0010] As a result of intensive research to achieve the above object, the present inventors have found that a fluorene compound having a 9,9-bis(acyloxyaryl)fluorene skeleton that can improve the fluidity of a resin can be provided by reacting a dihydroxy compound having a 9,9-bisarylfluorene skeleton with a carboxylic acid or an ester-forming derivative thereof, and have completed the present invention (or the present disclosure).

[0011] That is, the present disclosure includes the following aspects.

[0012] Aspect [1]: Formula (1) below

[0013]

[0014] (In the formula, Z １ and Z ２ each independently represents an arene ring; １ and A ２ each independently represents an alkylene group, n1 and n2 independently represent an integer of 0 or more, R １ and R ２ each independently represents a hydrocarbon group; R ３ and R ４ each independently represents a substituent, m1 and m2 independently represent an integer of 0 or more, R ５ represents a substituent, and k represents an integer of 0 to 8.

[0015] Aspect [2]: In the formula (1), Z １ and Z ２ wherein each independently represents a fused polycyclic arene ring or a ring-assembled arene ring.

[0016] Aspect [3]: In the formula (1), Z １ and Z ２ wherein each independently represents a naphthalene ring or a biphenyl ring.

[0017] Aspect [4]: ​​In the formula (1), R １ and R ２

[0023] The resin additive according to any one of the above aspects [1] to [3], wherein each independently represents an optionally substituted aryl group.

[0018] Aspect [5]: In the formula (1), R １ and R ２ The resin additive according to any one of the above aspects [1] to [4], wherein independently represent a naphthyl group.

[0019] Aspect [6]: The resin additive according to any one of aspects [1] to [5], wherein n1 and n2 represent 0 in formula (1).

[0020] Aspect [7]: The resin additive according to any one of Aspects [1] to [6], wherein the 5% weight loss temperature of the fluorene compound is 350°C or higher.

[0021] Aspect [8]: The resin additive according to any one of aspects [1] to [7], wherein the melting point of the fluorene compound is 350° C. or less.

[0022] Aspect [9]: The resin additive according to any one of aspects [1] to [8], which is a flowability improver for a resin component.

[0023] Aspect

[10] : Formula (2) below

[0024]

[0025] (In the formula, Z １ , Z ２ , A １ , A ２ , n1, n2, R ３ , R ４ , m1, m2, R ５ , k is the same as in formula (1) above), and a compound represented by the following formulas (3) and (4):

[0026]

[0027] (In the formula, X １ and X ２ each independently represents a halogen atom, a hydroxyl group, or an alkoxy group; R １ and R ２ is the same as the formula (1) above) to obtain the fluorene compound represented by the formula (1).

[0028] Aspect

[11] : A resin composition comprising a resin component and the resin additive according to any one of aspects [1] to [9].

[0029] Aspect

[12] : The resin composition according to aspect

[11] , wherein the resin component is a thermoplastic resin.

[0030] Aspect

[13] : The resin composition according to aspect

[12] , wherein the thermoplastic resin comprises an engineering plastic.

[0031] Aspect

[14] : The resin composition according to aspect

[13] , wherein the engineering plastic comprises a polyarylene sulfide-based resin and / or a polyether ketone-based resin.

[0032] Aspect

[15] : The resin composition according to any one of aspects

[11] to

[14] , wherein the proportion of the resin additive is 0.1 to 100 parts by mass per 100 parts by mass of the resin component.

[0033] Aspect

[16] : A method for improving the fluidity of a resin component by adding the resin additive according to any one of aspects [1] to [8] to the resin component.

[0034] Aspect

[17] : In the formula (1) according to the aspect [1], Z １ and Z ２ represents a benzene ring, and R １ and R ２ are independently fused polycyclic arene rings or ring-assembled arene rings.

[0035] Aspect

[18] : In the formula (1) according to the aspect [1], Z １ and Z ２A fluorene compound in which:

[0036] In addition, the present disclosure may achieve the following secondary objectives (solve the problems).

[0037] Another object of the present disclosure is to provide a fluorene compound that can improve the fluidity (particularly, melt fluidity) of a resin component without excessively reducing the mechanical properties of the resin component, as well as a production method and uses thereof.

[0038] Yet another object of the present disclosure is to provide a fluorene compound that has high heat resistance, is resistant to deterioration even when melted at high temperatures, and is easily melted to effectively exhibit its function (particularly, its fluidity improving function) in a resin composition, as well as a production method and use thereof.

[0039] Another object of the present disclosure is to provide a novel fluorene compound that can be used as an additive or a resin raw material, and a method for producing the same.

[0040] In this specification and claims, the number of carbon atoms in a substituent or the like is represented by C １ , C ６ , C １０ For example, "C １ "Alkyl group" means an alkyl group having one carbon atom, ６－１０ The term "aryl group" refers to an aryl group having 6 to 10 carbon atoms.

[0041] In the present specification and claims, the term "independently" means that two components are independent components, for example, an alkylene group A １ and A ２ In this case, A １ and A ２ and do not necessarily have to be the same alkylene group, but may be different alkylene groups.

[0042] Furthermore, in the present specification and claims, when a numerical range is indicated using "X to Y," the endpoints X and Y may be included.

[0043] According to the present disclosure, it is possible to provide a fluorene compound having a 9,9-bis(acyloxyaryl)fluorene skeleton that can improve the fluidity of resins.

[0044] [Fluorene Compound Represented by Formula (1)] The fluorene compound represented by formula (1) of the present disclosure (hereinafter also referred to as "fluorene compound (1)") can improve the fluidity of resins and can therefore be used as a resin additive (resin additive) such as a flowability improver. Furthermore, the fluorene compound (1) of the present disclosure can achieve high heat resistance by selecting a specific structure, and can be used, for example, as an additive for engineering plastics. In particular, the fluorene compound (1) of the present disclosure has high heat resistance, but its melting point can be kept low. Therefore, when melt-kneaded with a resin component, it can be easily melted and uniformly kneaded or dispersed in the resin component, thereby exhibiting its functions and also having excellent handleability.

[0045] In the formula (1), Z １ and Z ２ Examples of the aromatic hydrocarbon ring (arene ring) represented by the formula (I) include monocyclic arene rings such as a benzene ring, polycyclic arene rings, etc. Examples of the polycyclic arene ring include fused polycyclic arene rings (fused polycyclic aromatic hydrocarbon rings), and ring-assembled arene rings (ring-assembled aromatic hydrocarbon rings).

[0046] The fused polycyclic arene ring includes fused bicyclic arene rings, fused tricyclic arene rings, and other fused bicyclic to tetracyclic arene rings. The fused bicyclic arene ring includes fused bicyclic C rings such as naphthalene ring and indene ring. ８－２０ Examples of the fused tricyclic arene ring include fused tricyclic C arenes such as an acenaphthylene ring, a fluorene ring, a phenalene ring, an anthracene ring, and a phenanthrene ring. １２－２０ Examples of the fused tetracyclic aromatic hydrocarbon ring include a fused tetracyclic C ring such as a pyrene ring and a naphthacene ring. １６－２２ arene rings.

[0047] Examples of the ring-assembled arene ring include biarene rings such as a biphenyl ring, a phenylnaphthalene ring, and a binaphthyl ring; and terarene rings such as a terphenyl ring.

[0048] 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).

[0049] Ring Z １ is Ring Z ２ Among the arene rings, ring Z may be different from ring Z, but is preferably the same. １ and ring Z ２ As the ring, a benzene ring, a fused polycyclic arene ring, or a ring assembly arene ring is preferred, and a fused polycyclic arene ring or a ring assembly are more preferred from the viewpoint of improving the heat resistance and refractive index, and a fused polycyclic C ring such as a naphthalene ring is preferred. １０－１４ C such as arene ring, biphenyl ring １２－１８ A biarene ring is more preferred, and a naphthalene ring is most preferred.

[0050] In addition, Z bonded to the 9-position of the fluorene ring １ and Z ２ The substitution position of is not particularly limited, and for example, Z １ and Z ２ When is a benzene ring, it may be at any position, and Z １ and Z ２ is a naphthalene ring, it is either the 1-position (1-naphthyl) or the 2-position (2-naphthyl), preferably the 2-position; Z １ and Z ２ When is a biphenyl ring, it is at the 2-, 3- or 4-position, preferably the 3-position.

[0051] A １ and A ２Examples 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, a trimethylene group, a 1,2-butanediyl group, and a tetramethylene group. ２－６ alkylene groups, etc. ２－６ An alkylene group is preferred, and C ２－４ Alkylene groups are more preferred, and C groups such as ethylene groups and propylene groups are preferred. ２－３ An alkylene group is more preferred, and an ethylene group is most preferred. １ is an alkylene group A ２ may be different from, but are preferably the same.

[0052] The repeat numbers n1 and n2 are each 0 or more and can be selected, for example, from the range of integers from 0 to 15, preferably in the following stepwise order: 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, 0 to 1, with 0 being the most preferred from the viewpoint of improving heat resistance. When n1 and n2 are equal to or less than the upper limit values, the heat resistance and refractive index tend to improve. Furthermore, the repeat number n1 may be the same as or different from the repeat number n2. When n1 and n2 are each an integer of 2 or more, two or more alkylene groups A １ and A ２ The types may be the same or different.

[0053] In this specification and claims, the "number of repetitions (number of moles added)" may be an average value (arithmetic mean value, additive mean value) or an average number of moles added, and the preferred range may be the same as the preferred range of integers described above.

[0054] Ring Z １ and ring Z ２ The group [—O—(A １ O) ｎ１ -] and the group [-O-(A ２ O) ｎ２ The substitution position of the ether bond-containing group is not particularly limited.

[0055] Ring Z １ and ring Z ２ The group [—O—(A １ O)ｎ１ -] and the group [-O-(A ２ O) ｎ２ -] is substituted at the ring Z １ and ring Z ２ When is a benzene ring, the 2-, 3- or 4-position of the phenyl group bonded to the 9-position of the fluorene ring is preferred, among which the 3- or 4-position, and particularly the 4-position.

[0056] Ring Z １ and ring Z ２ The group [—O—(A １ O) ｎ１ -] and the group [-O-(A ２ O) ｎ２ -] is substituted at the ring Z １ and ring Z ２ is a naphthalene ring, it is often 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 the 9-position of the fluorene ring (substitution in a 1-naphthyl or 2-naphthyl relationship), and it is preferred that the 1,5-position or 2,6-position, particularly 2,6-position, be substituted with respect to this substitution position.

[0057] Ring Z １ and ring Z ２ is a ring-assembled arene ring, the group [—O—(A １ O) ｎ１ -] and the group [-O-(A ２ O) ｎ２ The substitution position of [-] is not particularly limited, and may be substituted, for example, on the arene ring bonded to the 9-position of the fluorene ring or on the arene ring adjacent to this arene ring. １ and ring Z ２ When is a biphenyl ring, the 3- or 4-position of the biphenyl ring, preferably the 3-position, may be bonded to the 9-position of the fluorene ring, and when the 3-position of the biphenyl ring is bonded to the 9-position of the fluorene ring, the group [—O—(A １ O) ｎ１ -] and the group [-O-(A ２ O) ｎ２The substitution position of [-] may be, for example, any of the 2-, 4-, 5-, 6-, 2'-, 3'-, and 4'-positions of the biphenyl ring, preferably the 6- or 4'-position, and particularly preferably the 6-position.

[0058] R １ and R ２ Examples of the hydrocarbon group represented by the formula include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

[0059] Examples of the alkyl group (linear or branched alkyl group) include C groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, hexyl group, 2-ethylhexyl group, octyl group, and decyl group. １－１２ Examples include alkyl groups.

[0060] Examples of the cycloalkyl group include a C cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a bicycloheptyl group, a decahydronaphthyl group, and an adamantyl group. ５－１４ Examples include a cycloalkyl group.

[0061] The aryl group is R ３ and R ４ The aryl group may have one or more of the substituents exemplified as: ６－１２ Aryl group or C １－６ Alkyl C ６－１２ The alkylphenyl group includes mono- to tri-C groups such as a methylphenyl group (or tolyl group) and a dimethylphenyl group (or xylyl group). １－４ Examples of the alkylbiphenylyl group include mono- to tetra-C alkyl groups such as methylbiphenylyl and dimethylbiphenylyl. １－４ Examples of the alkylnaphthyl group include mono- to tetra-C alkyl groups such as methylnaphthyl and dimethylnaphthyl groups. １－４ Examples include alkyl-naphthyl groups.

[0062] 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:

[0063] Of these, R １ and R ２ As the alkyl group, an aryl group which may have a substituent is preferable, from the viewpoint of facilitating improvement in fluidity, heat resistance, and refractive index, a biphenylyl group, an alkylbiphenylyl group, a naphthyl group, or an alkylnaphthyl group is more preferable, a naphthyl group or an alkylnaphthyl group is even more preferable, a naphthyl group is still more preferable, and a 2-naphthyl group is most preferable.

[0064] R ３ and R ４ Examples of the substituent represented by the formula (I) include a halogen atom, a hydrocarbon group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, a mono- or di-substituted amino group, a nitro group, and a cyano group.

[0065] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0066] The hydrocarbon group is R １ and R ２ Examples of the hydrocarbon groups include those exemplified as:

[0067] 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, and t-butoxy group. １－１０ Examples thereof include an alkoxy group.

[0068] Examples of the cycloalkyloxy group include a C cyclohexyloxy group. ５－１０ Examples include cycloalkyloxy groups.

[0069] The aryloxy group includes C aryloxy groups such as phenoxy groups. ６－１０ Examples thereof include an aryloxy group.

[0070] Examples of the aralkyloxy group include C aryloxy groups such as benzyloxy groups. ６－１０Aryl-C １－４ Examples thereof include an alkyloxy group.

[0071] 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 include an alkylthio group.

[0072] Examples of the cycloalkylthio group include a C cyclohexylthio group. ５－１０ Examples include a cycloalkylthio group.

[0073] The arylthio group includes C thiophenoxy group (phenylthio group) and the like. ６－１０ An example is an arylthio group.

[0074] Examples of the aralkylthio group include C arylthio groups such as benzylthio groups. ６－１０ Aryl-C １－４ Examples include an alkylthio group.

[0075] Examples of the acyl group include C groups such as an acetyl group. １－６ C such as alkyl-carbonyl group, benzoyl group ６－１０ Examples include an aryl-carbonyl group.

[0076] Examples of the mono- or di-substituted amino group include a dialkylamino group and a bis(alkylcarbonyl)amino group. Examples of the dialkylamino group include a diC group such as a dimethylamino group. １－４ Examples of the bis(alkylcarbonyl)amino group include bis(C １－４ alkyl-carbonyl)amino group.

[0077] These substituents may be contained alone or in combination of two or more. Among these, hydrocarbon groups are preferred, alkyl groups and aryl groups are particularly preferred, and C １－４ Alkyl group, C ６－１２ An aryl group is more preferred, and a C １－２ C such as alkyl group and phenyl group ６－１０ An aryl group is more preferred, and C １－２Alkyl groups are even more preferred, with methyl groups being most preferred.

[0078] The numbers of substitutions m1 and m2 are each an integer of 0 or more, and the number of substitutions m1 and m2 is an integer of 0 or more. １ or ring Z ２ The number of substitutions m1 and m2 can be selected depending on the type of group, and may be, for example, an integer of 0 to 8, preferably an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, an integer of 0 to 1, and most preferably 0. When the number of substitutions m1 and m2 is an integer of 2 or more, two or more groups R ３ and R ４ The types may be the same or different.

[0079] Substituent R ３ and R ４ The substitution position of is not particularly limited, and is usually １ and Z ２ In these compounds, the substituent is often at least at the ortho position (the carbon atom adjacent to the bonding position of the ether bond-containing group) relative to the ether bond-containing group.

[0080] R ５ Examples of the substituent represented by R ３ and R ４ The substituents may be contained alone or in combination of two or more. Among the substituents, the substituent R ５ As the alkyl group, a hydrocarbon group is preferred, and an alkyl group (especially a C group such as a methyl group) is preferred. １－２ Among these, alkyl groups and aryl groups are more preferred, and aryl groups are more preferred from the viewpoint of facilitating improvement in heat resistance, with phenyl, biphenylyl and naphthyl groups being most preferred.

[0081] The number of substitutions k may be an integer of 0 to 8, but is preferably an integer of 0 to 6, an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, more preferably 0 or 2, and most preferably 0. In addition, in the two benzene rings constituting the fluorene ring, the group R ５ The number of substitutions in each of the above may be different from each other, but is preferably the same.

[0082] In addition, the group R ５When the number of substitutions k is 2 or more, two or more groups R ５ The types of groups may be the same or different, and two or more groups R ５ The types of groups R may be the same or different. ５ The bonding positions (substitution positions) of are not particularly limited as long as they are the 1st to 8th positions of the fluorene ring, and examples thereof include the 2nd, 7th, and 2,7th positions of the fluorene ring, with the 2,7th positions being preferred.

[0083] A preferred fluorene compound (1) is a compound represented by the formula (1) in which the ring Z １ and ring Z ２ represents a benzene ring, and R １ and R ２ In the fluorene compound (1A), A in the formula (1) may be a fluorene compound (1A) in which A independently represents a fused polycyclic arene ring or a ring assembly arene ring. １ , A ２ , n1, n2, R ３ , R ４ , m1, m2, R ５ and k are the same as those in the fluorene compound (1), including preferred embodiments.

[0084] This fluorene compound (1A) is a novel compound, and in particular, in the formula (1), １ and ring Z ２ represents a benzene ring, and A １ and A ２ became independent and became C ２－６ represents an alkylene group, n1 and n2 independently represent integers of 0 to 10, R １ and R ２ each independently represents a biphenylyl group, an alkylbiphenylyl group, a naphthyl group, or an alkylnaphthyl group; R ３ and R ４ each independently represents a hydrocarbon group; m1 and m2 each independently represent an integer of 0 to 8; R ５ represents a hydrocarbon group, and k represents an integer of 0 to 6, １ and ring Z ２ represents a benzene ring, and A１ and A ２ became independent and became C ２－４ represents an alkylene group, n1 and n2 independently represent integers of 0 to 4, R １ and R ２ each independently represents a naphthyl group or an alkylnaphthyl group, and R ３ and R ４ each independently represents an alkyl group or an aryl group, m1 and m2 each independently represents an integer of 0 to 4, and R ５ represents an alkyl group or an aryl group, and k represents an integer of 0 to 4, １ and ring Z ２ represents a benzene ring, and A １ and A ２ became independent and became C ２－３ represents an alkylene group, n1 and n2 independently represent an integer of 0 to 2, R １ and R ２ each independently represents a naphthyl group; R ３ and R ４ each independently represents an alkyl group; m1 and m2 each independently represents an integer of 0 to 2; R ５ represents an aryl group, and k represents an integer of 0 to 2, and １ and ring Z ２ represents a benzene ring, and A １ and A ２ represents an ethylene group, n1 and n2 independently represent an integer of 0 to 1, and R １ and R ２ each independently represents a naphthyl group; R ３ and R ４ became independent and became C １－４ m1 and m2 each independently represent an integer of 0 to 2; R ５ are independently a phenyl group, a biphenylyl group or a naphthyl group, and k is an integer of 0 to 2, and １ and ring Z ２ represents a benzene ring, n1 and n2 represent 0, R １ and R ２ represents a 2-naphthyl group, and R ３ and R ４ became independent and became C１－２ It is most preferred that the compound is an alkyl group, m1 and m2 are independently an integer of 0 to 1, and k is 0.

[0085] A preferred fluorene compound (1) is a compound represented by the formula (1) in which the ring Z １ and ring Z ２ In the fluorene compound (1B), Z in the formula (1) may be a fluorene compound (1B) in which each independently represents a fused polycyclic arene ring. １ , Z ２ , A １ , A ２ , n1, n2, R １ , R ２ , R ３ , R ４ , m1, m2, R ５ and k are the same as those in the fluorene compound (1), including preferred embodiments.

[0086] This fluorene compound (1B) is a novel compound, and in particular, in the formula (1), １ and ring Z ２ each independently represents a fused polycyclic arene ring; １ and A ２ became independent and became C ２－６ represents an alkylene group, n1 and n2 independently represent integers of 0 to 10, R １ and R ２ each independently represents an aryl group; R ３ and R ４ each independently represents a hydrocarbon group; m1 and m2 each independently represent an integer of 0 to 8; R ５ represents a hydrocarbon group, and k represents an integer of 0 to 6, １ and ring Z ２ are independently fused polycyclic C １０－１４ represents an arene ring, and A １ and A ２ became independent and became C ２－４ represents an alkylene group, n1 and n2 independently represent integers of 0 to 4, R １ and R ２ each independently represents an aryl group; R ３ and R ４each independently represents an alkyl group or an aryl group, m1 and m2 each independently represents an integer of 0 to 4, and R ５ represents an alkyl group or an aryl group, and k represents an integer of 0 to 4, １ and ring Z ２ represents a naphthalene ring, and A １ and A ２ became independent and became C ２－３ represents an alkylene group, n1 and n2 independently represent an integer of 0 to 2, R １ and R ２ each independently represents a biphenylyl group, an alkylbiphenylyl group, a naphthyl group, or an alkylnaphthyl group; R ３ and R ４ each independently represents an alkyl group; m1 and m2 each independently represents an integer of 0 to 2; R ５ represents an aryl group, and k represents an integer of 0 to 2, and １ and ring Z ２ represents a naphthalene ring, and A １ and A ２ represents an ethylene group, n1 and n2 independently represent an integer of 0 to 1, and R １ and R ２ each independently represents a naphthyl group or an alkylnaphthyl group, and R ３ and R ４ became independent and became C １－４ m1 and m2 each independently represent an integer of 0 to 2; R ５ are independently a phenyl group, a biphenylyl group or a naphthyl group, and k is an integer of 0 to 2, and １ and ring Z ２ represents a naphthalene ring, n1 and n2 represent 0, and R １ and R ２ represents a naphthyl group, and R ３ and R ４ became independent and became C １－２ It is most preferred that the compound is an alkyl group, m1 and m2 are independently an integer of 0 to 1, and k is 0.

[0087] A preferred fluorene compound (1) is a compound represented by the formula (1) in which the ring Z １and ring Z ２ In the fluorene compound (1C), Z in the formula (1) may be independently a ring assembly arene ring. １ , Z ２ , A １ , A ２ , n1, n2, R １ , R ２ , R ３ , R ４ , m1, m2, R ５ and k are the same as those in the fluorene compound (1), including preferred embodiments.

[0088] This fluorene compound (1C) is a novel compound, and in particular, in the formula (1), １ and ring Z ２ each independently represents a ring-assembled arene ring, and A １ and A ２ became independent and became C ２－６ represents an alkylene group, n1 and n2 independently represent integers of 0 to 10, R １ and R ２ each independently represents an aryl group; R ３ and R ４ each independently represents a hydrocarbon group; m1 and m2 each independently represent an integer of 0 to 8; R ５ represents a hydrocarbon group, and k represents an integer of 0 to 6, １ and ring Z ２ represents a biphenyl ring, and A １ and A ２ became independent and became C ２－４ represents an alkylene group, n1 and n2 independently represent integers of 0 to 4, R １ and R ２ each independently represents an aryl group; R ３ and R ４ each independently represents an alkyl group or an aryl group, m1 and m2 each independently represents an integer of 0 to 4, and R ５ represents an alkyl group or an aryl group, and k represents an integer of 0 to 4, １ and ring Z ２ represents a biphenyl ring, and A １ and A２ became independent and became C ２－３ represents an alkylene group, n1 and n2 independently represent an integer of 0 to 2, R １ and R ２ each independently represents a biphenylyl group, an alkylbiphenylyl group, a naphthyl group, or an alkylnaphthyl group; R ３ and R ４ each independently represents an alkyl group; m1 and m2 each independently represents an integer of 0 to 2; R ５ represents an aryl group, and k represents an integer of 0 to 2, and １ and ring Z ２ represents a biphenyl ring, and A １ and A ２ represents an ethylene group, n1 and n2 independently represent an integer of 0 to 1, and R １ and R ２ each independently represents a naphthyl group or an alkylnaphthyl group, and R ３ and R ４ became independent and became C １－４ m1 and m2 each independently represent an integer of 0 to 2; R ５ are independently a phenyl group, a biphenylyl group or a naphthyl group, and k is an integer of 0 to 2, and １ and ring Z ２ each independently represents a biphenyl ring, n1 and n2 represent 0, and R １ and R ２ represents a naphthyl group, and R ３ and R ４ became independent and became C １－２ It is most preferred that the compound is an alkyl group, m1 and m2 are independently an integer of 0 to 1, and k is 0.

[0089] Specifically, preferred fluorene compounds (1A) include those having the ring Z in the formula (1). １ and ring Z ２ is a benzene ring, and the substituent R １ and R ２is a naphthyl group, for example, 9,9-bis(naphthoyloxy-phenyl)fluorenes such as 9,9-bis[4-(2-naphthoyloxy)-phenyl]fluorene and 9,9-bis[4-(1-naphthoyloxy)-phenyl]fluorene; 9,9-bis(naphthoyloxy-phenyl)fluorene such as 9,9-bis[4-(2-naphthoyloxy)-3-methylphenyl]fluorene and 9,9-bis[4-(1-naphthoyloxy)-3-methylphenyl]fluorene; 9,9-bis(naphthoyloxy(poly)alkoxy-phenyl)fluorenes such as 9,9-bis{4-[2-(2-naphthoyloxy)ethoxy]-phenyl}fluorene; and 9,9-bis(naphthoyloxy(poly)alkoxy-alkylphenyl)fluorenes such as 9,9-bis{4-[2-(2-naphthoyloxy)ethoxy]-3-methylphenyl}fluorene.

[0090] Specifically, preferred fluorene compounds (1B) include those having the ring Z in the formula (1). １ and ring Z ２ is a naphthalene ring, and the substituent R １ and R ２ is a naphthyl group, for example, 9,9-bis(naphthyloxy-naphthyl)fluorenes such as 9,9-bis[6-(2-naphthoyloxy)-2-naphthyl]fluorene, 9,9-bis[6-(1-naphthoyloxy)-2-naphthyl]fluorene, and 9,9-bis[5-(2-naphthoyloxy)-1-naphthyl]fluorene; and 9,9-bis(naphthoyloxy(poly)alkoxy-naphthyl)fluorenes such as 9,9-bis{6-[2-(2-naphthoyloxy)ethoxy]-2-naphthyl}fluorene and 9,9-bis{5-[2-(2-naphthoyloxy)ethoxy]-1-naphthyl}fluorene.

[0091] Specifically, preferred fluorene compounds (1C) include those having the formula (1) in which the ring Z １ and ring Z ２ is a biphenyl ring, and the substituent R １ and R ２is a naphthyl group, for example, 9,9-bis(naphthoyloxy-phenylphenyl)fluorenes such as 9,9-bis[4-(2-naphthoyloxy)-3-phenylphenyl]fluorene and 9,9-bis[4-(1-naphthoyloxy)-3-phenylphenyl]fluorene; and 9,9-bis(naphthoyloxy(poly)alkoxy-phenylphenyl)fluorenes such as 9,9-bis{4-[2-(2-naphthoyloxy)ethoxy]-3-phenylphenyl}fluorene.

[0092] Among these fluorene compounds, fluorene compound (1B) and fluorene compound (1C) are preferred from the viewpoint of excellent heat resistance, fluorene compound (1B) is particularly preferred from the viewpoint of highly excellent heat resistance, and fluorene compound (1C) is particularly preferred from the viewpoint of an excellent balance between heat resistance and fluidity.

[0093] More preferably, the fluorene compound (1) may be a fluorene compound represented by the following formula (1a) [fluorene compound (1a)], a fluorene compound represented by the following formula (1b) [fluorene compound (1b)], or a fluorene compound represented by the following formula (1c) [fluorene compound (1c)]:

[0094]

[0095] (In the formula, R ６ and R ７ each independently represents a substituent, p1 and p2 independently represent an integer of 0 to 7, and A １ , A ２ , n1, n2, R ３ , R ４ , m1, m2, R ５ , k is the same as in the above formula (1)

[0096]

[0097] (In the formula, R ６ and R ７ each independently represents a substituent, p1 and p2 independently represent an integer of 0 to 7, and A １ , A ２ , n1, n2, R ３ , R ４ , m1, m2, R５ , k is the same as in the above formula (1)

[0098]

[0099] (In the formula, R ６ and R ７ each independently represents a substituent, p1 and p2 independently represent an integer of 0 to 7, and A １ , A ２ , n1, n2, R ３ , R ４ , m1, m2, R ５ , k is the same as in the above formula (1)

[0100] In the formulas (1a) to (1c), R ６ and R ７ Examples of the substituent represented by R ３ and R ４ The substituents may be contained alone or in combination of two or more. Among these, alkyl groups are preferred, and C １－４ Alkyl groups are more preferred, and C １－２ Alkyl groups are more preferred.

[0101] The numbers of substitutions p1 and p2 are each an integer of 0 or more, and may be an integer of 0 to 7, preferably an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, an integer of 0 to 1, and most preferably 0. When the numbers of substitutions p1 and p2 are an integer of 2 or more, two or more groups R ６ and R ７ The types may be the same or different.

[0102] Among the fluorene compound (1a), the fluorene compound (1b), and the fluorene compound (1c), the fluorene compound (1b) and the fluorene compound (1c) are preferred because of their excellent heat resistance, the fluorene compound (1b) is particularly preferred because of its high heat resistance, and the fluorene compound (1c) is particularly preferred because of its excellent balance between heat resistance and fluidity.

[0103] The molecular weight of the fluorene compound (1) is, for example, 500 to 2000, preferably 600 to 1500, more preferably 700 to 1300, and even more preferably 750 to 1000. When the molecular weight is equal to or higher than the lower limit, the heat resistance tends to be easily improved, and when it is equal to or lower than the upper limit, the flowability tends to be easily improved.

[0104] The fluorene compound (1) has excellent heat resistance, and the 5% weight loss temperature may be 250°C or higher, preferably 350°C or higher, further preferably 400°C or higher, and even more preferably 450°C or higher, specifically about 250 to 550°C, and preferably the following stepwise temperatures: 270 to 550°C, 300 to 530°C, 350 to 520°C, 400 to 510°C, 450 to 500°C, 455 to 490°C, and 460 to 480°C.

[0105] The fluorene compound (1) may be amorphous or crystalline (crystal form), but is preferably crystalline.

[0106] The melting point of the fluorene compound (1) may be 350°C or lower, preferably 320°C or lower, more preferably 310°C or lower, and more preferably 300°C or lower; specifically, it is about 50 to 330°C, and preferably the following stepwise: 60 to 320°C, 70 to 310°C, 80 to 300°C, 100 to 290°C, 120 to 280°C, and 150 to 270°C. The fluorene compound (1) of the present disclosure has a high 5% weight loss temperature and excellent heat resistance, yet has a low melting point, making it a rare fluorene compound with excellent handleability. In particular, when used as an additive to prepare a resin composition, it not only melts during molding to easily improve flowability, but also has the advantage of not thermally decomposing even at molding temperatures.

[0107] In this specification and claims, the 5% weight loss temperature and melting point of the fluorene compound (1) can be measured by the method described in the examples below.

[0108] The fluorene compound (1) may have a 5% weight loss temperature of 250°C or higher and a melting point of 350°C or lower (the 5% weight loss temperature may be 250°C or higher and the melting point may be 350°C or lower), preferably a 5% weight loss temperature of 350°C or higher and a melting point of 320°C or lower, more preferably a 5% weight loss temperature of 400°C or higher and a melting point of 300°C or lower, and even more preferably a 5% weight loss temperature of 450°C or higher and a melting point of 280°C or lower.

[0109] The fluorene compound (1A) [particularly, the fluorene compound (1a)] may have a 5% weight loss temperature of 300 to 550°C and a melting point of 100 to 350°C, preferably a 5% weight loss temperature of 350 to 500°C and a melting point of 150 to 300°C, and more preferably a 5% weight loss temperature of 370 to 450°C and a melting point of 230 to 270°C.

[0110] The fluorene compound (1B) [particularly, the fluorene compound (1b)] may have a 5% weight loss temperature of 350 to 550°C and a melting point of 80 to 350°C, preferably a 5% weight loss temperature of 400 to 520°C and a melting point of 100 to 300°C, more preferably a 5% weight loss temperature of 430 to 500°C and a melting point of 130 to 250°C, and even more preferably a 5% weight loss temperature of 460 to 480°C and a melting point of 150 to 210°C.

[0111] The fluorene compound (1C) [particularly, the fluorene compound (1c)] may have a 5% weight loss temperature of 300 to 550°C and a melting point of 150 to 350°C, preferably a 5% weight loss temperature of 350 to 520°C and a melting point of 200 to 350°C, more preferably a 5% weight loss temperature of 400 to 500°C and a melting point of 230 to 300°C, and even more preferably a 5% weight loss temperature of 450 to 480°C and a melting point of 250 to 280°C.

[0112] [Method for producing fluorene compound (1) or resin additive] The method for producing fluorene compound (1) (or resin additive) is not particularly limited, but may be a method of esterifying the compound represented by formula (2) with the compound represented by formulas (3) and (4) or their ester-forming derivatives (such as acid anhydrides) to obtain fluorene compound (1).As the method for esterification, a conventional ester synthesis method or transesterification method can be used depending on the type of compound represented by formulas (3) and (4).

[0113] In the formulas (3) and (4), X １ and X ２ Examples of the halogen atom represented by the formula (I) include a chlorine atom, a bromine atom, an iodine atom, etc. Among these, a chlorine atom and a bromine atom are preferred, and a chlorine atom is particularly preferred.

[0114] X １ and X ２ Examples of the alkoxy group (linear or branched alkoxy group) represented by the formula (I) include C alkoxy groups such as methoxy group, ethoxy group, propoxy group, n-butoxy group, and t-butoxy group. １－４ Among these, C alkoxy groups such as methyl and ethyl groups are preferred. １－３ An alkoxy group is preferred, and C １－２ Alkoxy groups are particularly preferred.

[0115] In this specification and claims, X １ and X ２ is a hydroxyl group, the compounds represented by the formulas (3) and (4) may be acid anhydrides.

[0116] Preferred X １ and X ２ As the halogen atom, a halogen atom is preferred, and chlorine is particularly preferred, in view of the ease of improving reactivity.

[0117] The compound represented by the formula (3) may be different from the compound represented by the formula (4), but it is preferable that they are the same.

[0118] Preferable compounds represented by the formulas (3) and (4) include naphthalenecarboxylic acids such as 2-naphthalenecarboxylic acid (2-naphthoic acid), 1-naphthalenecarboxylic acid, and 2-naphthoyl chloride, or ester-forming derivatives thereof.

[0119] The total amount of the compounds represented by the formulas (3) and (4) is, for example, 2 to 10 mol, preferably 2 to 5 mol, further preferably 2 to 3 mol, even more preferably 2 to 2.5 mol, and most preferably 2.05 to 2.3 mol, relative to 1 mol of the compound represented by the formula (2).

[0120] The esterification reaction may be carried out in the presence of a conventional esterification catalyst or may be carried out without using an esterification catalyst.

[0121] In particular, in the formulas (3) and (4), X １ and X ２ In the production method using compounds in which R is a halogen atom (hereinafter referred to as "acid halides (3) and (4)"), the reaction may be carried out in the presence of a base to trap the hydrogen halide produced in the reaction and also to act as a catalyst. Bases can be broadly classified into inorganic bases and organic bases.

[0122] 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.

[0123] Examples of organic bases include amines, specifically trialkylamines such as triethylamine; alkanolamines such as triethanolamine and dimethylaminoethanol; aromatic tertiary amines such as benzyldimethylamine; and heterocyclic amines such as pyridine and N-methylmorpholine.

[0124] The base may be contained alone or in combination of two or more kinds. Among these bases, amines, for example, trialkylamines such as triethylamine, and heterocyclic amines such as pyridine, are often used.

[0125] The amount of the base used is, for example, 1 to 5 mol, preferably 1 to 4 mol, further preferably 1.5 to 3.5 mol, even more preferably 1.5 to 3 mol, and most preferably 2 to 3 mol, relative to 1 mol of the total amount of the compounds represented by the formulas (3) and (4).

[0126] The esterification reaction can be carried out in the presence or absence of a solvent inert to the reaction. Any organic solvent inert to the reaction may be used. Examples of organic solvents include hydrocarbons such as hexane, cyclohexane, toluene, and xylene; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone (MIBK); ethers such as dioxane, tetrahydrofuran (THF), and diisopropyl ether; halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, and dibromoethane; nitriles such as acetonitrile; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; and sulfoxides such as dimethyl sulfoxide. These solvents may be used alone or in combination. Among these, ketones such as MIBK and ethers such as THF are preferred. The organic base may also be used as a solvent.

[0127] The esterification reaction may be carried out at a temperature of 0 to 100° C., preferably 15 to 65° C. The reaction time is, for example, 0.5 to 24 hours, preferably 1 to 12 hours.

[0128] The esterification reaction may be carried out in air or in an inert atmosphere such as nitrogen gas or rare gas, among which an inert atmosphere is preferred from the standpoint of reactivity.

[0129] The esterification reaction can be carried out with stirring, and may be carried out under normal pressure, elevated pressure, or reduced pressure.

[0130] After completion of the reaction, the reaction mixture may be separated and purified, if necessary, by a conventional separation and purification method, such as neutralization, washing, extraction, filtration, dehydration, concentration, decantation, drying, crystallization, reprecipitation, column chromatography, adsorption, or a combination thereof.

[0131] [Resin Additive] The resin additive of the present disclosure may contain a fluorene compound (1). In the resin additive of the present disclosure, the proportion of the fluorene compound (1) may be 10% by mass or more, preferably 30% by mass or more, 50% by mass or more, 70% by mass or more, 90% by mass or more, and most preferably 100% by mass. The resin additive may be used as a masterbatch containing a resin component of the same type (particularly the same) as the resin component described below and a high concentration of the fluorene compound (1). In the masterbatch, the concentration of the fluorene compound (1) is, for example, 10 to 90% by mass, preferably 20 to 80% by mass, and more preferably 30 to 60% by mass.

[0132] The resin additives of the present disclosure may be used as flow improvers or flow modifiers, refractive index improvers, heat resistance improvers, strength improvers, and the like.

[0133] [Resin Composition] The resin composition of the present disclosure includes a resin component and the resin additive. The resin component may be a curable resin (thermo- or photo-curable resin) or a thermoplastic resin.

[0134] Examples of the curable resin include phenolic resins such as resol-type phenolic resins and novolac-type phenolic resins; amino resins such as urea resins, melamine resins and guanamine resins; 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 such as bismaleimide resins; and silicone resins.

[0135] Examples of thermoplastic resins include polyolefin resins such as linear olefin resins and cyclic olefin resins; styrene resins such as polystyrene, styrene-methyl methacrylate copolymer (MS resin), styrene-acrylonitrile copolymer (AS resin), high impact polystyrene (HIPS), acrylonitrile-butadiene-styrene copolymer (ABS resin), and methyl methacrylate-butadiene-styrene copolymer (MBS resin); and (meth)acrylic acid copolymers such as polymethyl methacrylate (PMMA) and (meth)acrylic acid-(meth)acrylic acid ester copolymers. ) acrylic resins; vinyl acetate resins such as polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), and polyvinyl acetal (polyvinyl formal (PVF), polyvinyl butyral (PVB), etc.); vinyl chloride homopolymers (PVC); vinyl chloride resins such as vinyl chloride-vinyl acetate copolymers; vinylidene chloride resins such as vinylidene chloride-vinyl chloride copolymers and vinylidene chloride-acrylonitrile copolymers; fluororesins such as polytetrafluoroethylene (PTFE); polyalkylene arylate resins, polyarylate resins polyester-based resins such as bisphenol A polycarbonate-based resins; polyamide-based resins such as aliphatic polyamide resins, aromatic polyamide resins, and aramid resins; polyacetal-based resins such as polyacetal resin (POM); polyphenylene ether-based resins such as polyphenylene ether (PPE); polyether ketone-based resins such as polyether ketone (PEK), polyether ether ketone (PEEK), and polyether ketone ether ketone ketone (PEKEKK); cellulose ethers such as ethyl cellulose and carboxymethyl cellulose; thermoplastic polyimide resins such as polyetherimide (PEI) and polyamideimide; polyethernitrile resins;Examples of thermoplastic elastomers include polystyrene-based thermoplastic elastomers (polystyrene-based TPEs), polyolefin-based TPEs (TPOs), polydiene-based TPEs, chlorine-based TPEs, fluorine-based TPEs, polyurethane-based TPEs (TPUs), polyester-based TPEs (TPEEs), and polyamide-based TPEs (TPAs).

[0136] These resin components can be used alone or in combination of two or more. Among them, thermoplastic resins are preferred because they can easily improve fluidity (melt fluidity), engineering plastics are more preferred because they can easily exhibit the effect of the resin additive of the present invention, which can be used at high temperatures, polyester resins, polyacetal resins, polyphenylene ether resins, polyarylene sulfide resins, polyether ketone resins, polysulfone resins, and thermoplastic polyimide resins are more preferred, and polyarylene sulfide resins and polyether ketone resins are most preferred.

[0137] The proportion of the thermoplastic resin in the resin component may be, for example, about 10% by mass or more, and is preferably 30% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, and 100% by mass in the following stepwise manner.

[0138] The proportion of the engineering plastic (particularly, the polyarylene sulfide-based resin and / or the polyether ketone-based resin) in the resin component may be, for example, about 10% by mass or more, and is preferably 30% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, and 100% by mass in the following stepwise manner.

[0139] (Polyarylene sulfide resin) The polyarylene sulfide resin may be a resin having a repeating unit represented by the following formula (5).

[0140]

[0141] (In the formula, Z ３ represents an arene ring, and R ８ represents a substituent, and s represents an integer of 0 or more.

[0142] In the formula (5), ring Z ３ As the arene ring (or aromatic hydrocarbon ring) represented by the formula: １ and ring Z ２ Examples of the arene ring include the arene rings exemplified below.

[0143] The arene rings can be used alone or in combination of two or more. Among these arene rings, a benzene ring and a biphenyl ring are preferred, and a benzene ring is particularly preferred. Ring Z ３ The phenylene group in which R is a benzene ring may be any of a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group, but preferably contains at least a 1,4-phenylene group, and is particularly preferably a 1,4-phenylene group from the viewpoint of forming a linear polyphenylene sulfide resin and improving the mechanical properties.

[0144] Ring Z ３ is a benzene ring, the substituent R ８ The proportion of the 1,4-phenylene sulfide units (p-phenylene sulfide units) which may have the formula (5) may be 50 mol % or more, preferably 70 mol % or more, more preferably 90 mol % or more, and most preferably 100 mol %.

[0145] R ８ Examples of the substituent represented by R ３ and R ４ The substituents may be used alone or in combination of two or more. Among the substituents, alkyl groups are preferred. Examples of the alkyl groups include linear or branched C alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl groups. １－６ These alkyl groups can be used alone or in combination of two or more. Among these, C １－４ Alkyl groups are preferred.

[0146] R ８ The number of substitutions s in the ring Z may be an integer of 0 or more. ３The number can be appropriately selected depending on the type of , for example, an integer of 0 to 8, preferably an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, more preferably 0 or 1, and most preferably 0.

[0147] In the polyarylene sulfide resin, the proportion of the repeating unit represented by the formula (5) may be 50 mol% or more of all the structural units, preferably 80 mol% or more, more preferably 90 mol% or more, and even more preferably 100 mol%.

[0148] Other units include units containing an arene ring, such as a phenylene ether unit, a phenylene carbonyl unit, a phenylene sulfonyl unit, and a phenylene sulfone unit.

[0149] From the viewpoint of mechanical properties, etc., the polyarylene sulfide-based resin is preferably a polyphenylene sulfide-based resin (polyphenylene sulfide-based resin or polyphenylene thioether-based resin). Examples of polyphenylene sulfide-based resins include polyphenylene sulfide (PPS), polyphenylene sulfide ketone (PPSK), polyphenylene sulfide sulfone (PPSS), and polybiphenylene sulfide (PBPS). Of these, PPS is preferred, and linear PPS is particularly preferred.

[0150] The weight-average molecular weight (Mw) of the polyarylene sulfide resin may be 1,000 or more, for example, 1,000 to 500,000, preferably 5,000 to 300,000, further preferably 10,000 to 100,000, more preferably 15,000 to 80,000, and most preferably 20,000 to 60,000. When the molecular weight is equal to or greater than the lower limit, the mechanical properties of the resin composition tend to be improved. The weight-average molecular weight range may be the range of the weight-average molecular weight of the polyphenylene sulfide resin.

[0151] In this specification and claims, the weight average molecular weight of the polyarylene sulfide resin can be measured by gel permeation chromatography (standard resin: polystyrene).

[0152] The melt flow rate (MFR) of the polyarylene sulfide-based resin (particularly, the polyphenylene sulfide-based resin) is, for example, 1 to 100 g / 10 min, preferably 5 to 70 g / 10 min, further preferably 10 to 50 g / 10 min, further preferably 20 to 40 g / 10 min, and most preferably 30 to 40 g / 10 min.

[0153] In this specification and claims, the MFR of the polyarylene sulfide resin or resin composition can be measured by the method described in the examples below.

[0154] The melting point of the polyarylene sulfide-based resin (particularly, the polyphenylene sulfide-based resin) is, for example, 200 to 350° C., preferably 230 to 320° C., further preferably 250 to 300° C., further preferably 260 to 290° C., and most preferably 270 to 280° C. The melting point range may be the melting point range of the polyphenylene sulfide-based resin.

[0155] The glass transition temperature of the polyarylene sulfide-based resin (particularly, the polyphenylene sulfide-based resin) is, for example, 50 to 150° C., preferably 60 to 130° C., further preferably 70 to 120° C., further preferably 80 to 110° C., and most preferably 90 to 100° C. The glass transition temperature range may be the glass transition temperature range of the polyphenylene sulfide-based resin.

[0156] In this specification and claims, the melting point and glass transition temperature of the polyarylene sulfide resin can be measured using a differential scanning calorimeter (DSC).

[0157] The proportion of the polyarylene sulfide-based resin (particularly, the polyphenylene sulfide-based resin) in the resin components may be, for example, about 10% by mass or more, and is preferably 30% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, and 100% by mass in the following stepwise manner.

[0158] The proportion of the polyarylene sulfide-based resin (particularly, the polyphenylene sulfide-based resin) in the resin composition may be, for example, 10% by mass or more, and is, for example, 10 to 99.9% by mass, preferably 30 to 99% by mass, further preferably 50 to 98% by mass, more preferably 60 to 97% by mass, and most preferably 65 to 96% by mass.

[0159] (Polyetherketone-based resin) The polyetherketone-based resin may be a resin containing a repeating unit composed of an arylene group which may have a substituent, and an ether group and a carbonyl group interposed between a plurality of the arylene groups.

[0160] Examples of the arylene group include C phenylene groups and naphthylene groups. ６－１０ arylene group; biphenylene group or the like ６－１０ Examples of the phenylene group include a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group. Examples of the biphenylene group include a 2,2'-biphenylene group, a 3,3'-biphenylene group, and a 4,4'-biphenylene group. These arylene groups can be used alone or in combination of two or more. Of these arylene groups, phenylene groups such as a 1,4-phenylene group and biphenylene groups such as a 4,4'-biphenylene group are preferred, with a 1,4-phenylene group being particularly preferred.

[0161] Examples of the substituent of the arylene group include a halogen atom, a haloalkyl group, an alkyl group, a hydroxyl group, an alkoxy group, a mercapto group, an alkylthio group, a carboxyl group, a sulfo group, an amino group, an N-substituted amino group, and a cyano group. These substituents can be used alone or in combination of two or more. Among these substituents, C groups such as a methyl group and an ethyl group are preferred. １―６ Alkyl groups are preferred, and C １－４ Alkyl groups are more preferred, and C １－２ Alkyl groups are more preferred.

[0162] Examples of polyetherketone resins include polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone, polyetherketoneetherketoneketone (PEKEKK), polyetheretherketoneketone (PEEKK), and polyether-diphenyl-ether-phenyl-ketone-phenyl. The polyetherketone resin may be a conventional polyetherketone resin (or polyetherketone resin) such as polyetherketone (PEK) or polyetheretherketone (PEEK). These polyetherketone resins can be used alone or in combination of two or more. Of these, polyetherketone and polyetheretherketone are preferred, with polyetheretherketone being particularly preferred.

[0163] The polyether ether ketone may be a resin having a repeating unit represented by the formula [-Ph-C(=O)-Ph-O-Ph-O-] (wherein Ph represents a phenylene group) obtained by polycondensation of a dihalogenobenzophenone and hydroquinone.

[0164] The weight average molecular weight of the polyether ketone resin (particularly polyether ether ketone) is, for example, 5,000 to 1,000,000, preferably 10,000 to 800,000, and more preferably 15,000 to 500,000. When the molecular weight is equal to or higher than the lower limit, the mechanical properties of the resin composition tend to be easily improved.

[0165] In this specification and claims, the weight average molecular weight of the polyether ketone resin can be measured using gel permeation chromatography (standard resin: polystyrene).

[0166] The melt flow rate (MFR) of the polyether ketone resin (particularly polyether ether ketone) is, for example, 1 to 100 g / 10 min, preferably 5 to 50 g / 10 min, further preferably 10 to 40 g / 10 min, further preferably 14 to 30 g / 10 min, and most preferably 15 to 20 g / 10 min.

[0167] In this specification and claims, the MFR of the polyether ketone resin or resin composition can be measured by the method described in the examples below.

[0168] The proportion of the polyether ketone resin (particularly polyether ether ketone) in the resin components may be, for example, about 10% by mass or more, and is preferably 30% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, and 100% by mass in the following stepwise manner.

[0169] The proportion of the polyether ketone resin (particularly polyether ether ketone) in the resin composition may be, for example, 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, more preferably 80% by mass or more, and most preferably 90% by mass or more, and may be 90 to 99% by mass. When the resin composition contains a filler, the proportion of the polyether ketone resin in the resin composition is, for example, 10 to 99% by mass, preferably 30 to 98% by mass, more preferably 50 to 95% by mass, more preferably 70 to 93% by mass, and most preferably 80 to 90% by mass.

[0170] (Combination of Polyarylene Sulfide Resin and Polyether Ketone Resin) The polyarylene sulfide resin and the polyether ketone resin may be combined in a mass ratio of the polyarylene sulfide resin to the polyether ketone resin (former / latter) of 99 / 1 to 1 / 99, preferably 90 / 10 to 10 / 90, more preferably 80 / 20 to 20 / 80, and even more preferably 70 / 30 to 30 / 70.

[0171] The total amount of the polyarylene sulfide-based resin and the polyether ketone-based resin in the resin component may be, for example, about 10% by mass or more, and is preferably 30% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, and 100% by mass in the following stepwise manner.

[0172] (Fluorene Compound (1)) The resin composition of the present disclosure contains the fluorene compound (1) as a resin additive, and therefore can improve at least one property (particularly, fluidity) selected from the group consisting of fluidity, refractive index, and strength. In particular, in a resin composition containing a polyarylene sulfide-based resin, Z １ and Z ２ By using a fluorene compound in which represents a benzene ring or a biphenyl ring (particularly a biphenyl ring), the fluidity can be highly improved.

[0173] The proportion of the fluorene compound (1) can be selected from a range of about 0.01 to 1000 parts by mass relative to 100 parts by mass of the resin component, preferably in the following stepwise manner: 0.05 to 500 parts by mass, 0.1 to 100 parts by mass, 0.3 to 50 parts by mass, 0.5 to 30 parts by mass, 1 to 10 parts by mass, 3 to 8 parts by mass, and 4 to 7 parts by mass. When the proportion of the fluorene compound (1) is equal to or greater than the lower limit, the fluidity and heat resistance of the resin composition tend to be improved, and when it is equal to or less than the upper limit, the mechanical properties of the resin composition tend to be improved. These proportions may be the proportion relative to 100 parts by mass of a thermoplastic resin such as a polyarylene sulfide resin (particularly, a polyphenylene sulfide resin) or a polyether ketone resin (particularly, a polyether ether ketone). The ratio may also be a ratio of at least one compound selected from the group consisting of fluorene compound (1A) [particularly, fluorene (1a)], fluorene compound (1B) [particularly, fluorene (1b)], and fluorene compound (1C) [particularly, fluorene (1c)].

[0174] The proportion of the resin additive of the present disclosure can be selected from a range of about 0.01 to 1000 parts by mass relative to 100 parts by mass of the resin component, and is preferably 0.05 to 500 parts by mass, 0.1 to 100 parts by mass, 0.3 to 50 parts by mass, 0.5 to 30 parts by mass, 1 to 10 parts by mass, 3 to 8 parts by mass, and 4 to 7 parts by mass in the following stepwise manner. When the proportion of the resin additive is equal to or greater than the lower limit, the fluidity and heat resistance of the resin composition tend to improve, and when it is equal to or less than the upper limit, the mechanical properties of the resin composition tend to improve.

[0175] (Other Components) The resin composition of the present disclosure may further contain, as necessary, at least one selected from the group consisting of other resin components, fillers, and commonly used additives.

[0176] When the resin component is a polyarylene sulfide resin or a polyether ketone resin, examples of the other resin component include other thermoplastic resins. Examples of the other thermoplastic resin include the above-mentioned thermoplastic resins other than the polyarylene sulfide resin or the polyether ketone resin. The proportion of the other thermoplastic resin in the resin component is 50% by mass or less, preferably 30% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0177] Examples of fillers include fibrous reinforcing agents such as carbon fiber and glass fiber, and granular reinforcing agents such as carbon black and silica. The filler content is, for example, 1 to 200 parts by mass, preferably 3 to 150 parts by mass, 5 to 100 parts by mass, 10 to 80 parts by mass, and 15 to 50 parts by mass, relative to 100 parts by mass of the resin component. These content ratios may be based on 100 parts by mass of a thermoplastic resin such as a polyarylene sulfide resin (particularly, a polyphenylene sulfide resin) or a polyether ketone resin (particularly, a polyether ether ketone).

[0178] Examples of conventional additives that may be included include colorants such as dyes and pigments, conductive agents, flame retardants, plasticizers, lubricants, stabilizers, release agents, antistatic agents, dispersants, leveling agents, antifoaming agents, surface modifiers, stress reducing agents, etc. The total proportion of these additives in the resin composition may be 30% by mass or less, preferably 10% by mass or less, for example, 0.1 to 10% by mass.

[0179] [Resin Composition and Molded Article] The resin composition of the present disclosure can be prepared by mixing a resin component, a fluorene compound (1) as a resin additive, and, if necessary, other components 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.

[0180] The resin composition of the present disclosure has high melt fluidity, and the MFR (melt flow rate) may be 10 g / 10 min or more, preferably 10 to 200 g / 10 min, more preferably 15 to 150 g / 10 min, and even more preferably 20 to 110 g / 10 min. When the MFR is equal to or higher than the lower limit, moldability tends to be improved.

[0181] When the resin component contains a polyarylene sulfide resin (particularly a polyphenylene sulfide resin) as a main component, the MFR of the resin composition is, for example, 10 to 200 g / 10 min, preferably 30 to 180 g / 10 min, more preferably 45 to 170 g / 10 min, more preferably 50 to 150 g / 10 min, even more preferably 60 to 130 g / 10 min, and most preferably 80 to 120 g / 10 min. These MFR ranges may be the MFR ranges of the resin composition that does not contain a fibrous reinforcing agent.

[0182] When the resin component contains a polyether ketone resin (particularly polyether ether ketone) as a main component, the MFR of the resin composition is, for example, 10 to 150 g / 10 min, preferably 12 to 100 g / 10 min, more preferably 15 to 70 g / 10 min, more preferably 17 to 60 g / 10 min, even more preferably 18 to 50 g / 10 min, and most preferably 20 to 30 g / 10 min. These MFR ranges may also be the MFR ranges of the resin composition that does not contain a fibrous reinforcing agent.

[0183] A preferred resin composition may be a polyarylene sulfide-based resin composition in which the resin component contains a polyarylene sulfide-based resin, and among these, in terms of excellent heat resistance and flowability, a polyarylene sulfide-based resin composition in which the resin component contains a polyarylene sulfide-based resin, the fluorene compound (1) contains fluorene compound (1A), fluorene compound (1B) or fluorene compound (1C), the proportion of the fluorene compound (1) is 0.1 to 100 parts by mass per 100 parts by mass of the resin component, and the MFR of the resin composition is 45 to 200 g / 10 min is preferred; More preferred is a polyarylene sulfide-based resin composition in which the resin component is a polyarylene sulfide-based resin, the fluorene compound (1) is fluorene compound (1A) or fluorene compound (1C), the proportion of the fluorene compound (1) is 0.3 to 50 parts by mass relative to 100 parts by mass of the resin component, and the MFR of the resin composition is 50 to 180 g / 10 min; More preferred is a polyarylene sulfide-based resin composition in which the resin component is a polyphenylene sulfide-based resin, the fluorene compound (1) is fluorene compound (1a) or fluorene compound (1c), the proportion of the fluorene compound (1) is 1 to 10 parts by mass relative to 100 parts by mass of the resin component, and the MFR of the resin composition is 60 to 150 g / 10 min; The most preferred polyarylene sulfide-based resin composition is one in which the resin component is a polyphenylene sulfide-based resin, the fluorene compound (1) is fluorene compound (1c), the proportion of the fluorene compound (1) is 3 to 8 parts by mass per 100 parts by mass of the resin component, and the MFR of the resin composition is 80 to 120 g / 10 min.

[0184] A preferred resin composition may be a polyetherketone-based resin composition in which the resin component contains a polyetherketone-based resin, and among these, a polyetherketone-based resin composition in which the resin component contains a polyetherketone-based resin, the fluorene compound (1) contains fluorene compound (1A), fluorene compound (1B) or fluorene compound (1C), the proportion of fluorene compound (1) is 0.1 to 100 parts by mass per 100 parts by mass of the resin component, and the MFR of the resin composition is 10 to 150 g / 10 min is preferred.

[0185] In particular, as the polyetherketone-based resin composition, from the viewpoint of excellent heat resistance, more preferred are polyetherketone-based resin compositions in which the resin component is a polyetherketone-based resin, the fluorene compound (1) is fluorene compound (1B) or fluorene compound (1C), the proportion of the fluorene compound (1) is 0.3 to 50 parts by mass relative to 100 parts by mass of the resin component, and the MFR of the resin composition is 12 to 100 g / 10 min; and even more preferred are polyetherketone-based resin compositions in which the resin component is polyetheretherketone, the fluorene compound (1) is fluorene compound (1b) or fluorene compound (1c), the proportion of the fluorene compound (1) is 1 to 10 parts by mass relative to 100 parts by mass of the resin component, and the MFR of the resin composition is 15 to 50 g / 10 min. A polyether ketone-based resin composition in which the resin component is a polyether ether ketone resin, the fluorene compound (1) is the fluorene compound (1b), the proportion of the fluorene compound (1) is 3 to 8 parts by mass per 100 parts by mass of the resin component, and the MFR of the resin composition is 20 to 30 g / 10 min is most preferred.

[0186] Further, as the polyetherketone-based resin composition, in view of an excellent balance between heat resistance and fluidity, a polyetherketone-based resin composition in which the resin component is a polyetherketone-based resin, the fluorene compound (1) is fluorene compound (1B) or fluorene compound (1C), the proportion of the fluorene compound (1) is 0.3 to 50 parts by mass relative to 100 parts by mass of the resin component, and the MFR of the resin composition is 12 to 100 g / 10 min is more preferred; a polyetherketone-based resin composition in which the resin component is polyetheretherketone, the fluorene compound (1) is fluorene compound (1b) or fluorene compound (1c), the proportion of the fluorene compound (1) is 1 to 10 parts by mass relative to 100 parts by mass of the resin component, and the MFR of the resin composition is 15 to 50 g / 10 min is even more preferred; A polyether ketone-based resin composition in which the resin component is a polyether ether ketone resin, the fluorene compound (1) is the fluorene compound (1c), the proportion of the fluorene compound (1) is 3 to 8 parts by mass per 100 parts by mass of the resin component, and the MFR of the resin composition is 20 to 30 g / 10 min is most preferred.

[0187] Furthermore, as the polyetherketone-based resin composition, from the viewpoint of excellent fluidity, a polyetherketone-based resin composition in which the resin component is a polyetherketone-based resin, the fluorene compound (1) is fluorene compound (1A) or fluorene compound (1C), the proportion of the fluorene compound (1) is 0.3 to 50 parts by mass relative to 100 parts by mass of the resin component, and the MFR of the resin composition is 12 to 100 g / 10 min is more preferred; a polyetherketone-based resin composition in which the resin component is polyetheretherketone, the fluorene compound (1) is fluorene compound (1a) or fluorene compound (1c), the proportion of the fluorene compound (1) is 1 to 10 parts by mass relative to 100 parts by mass of the resin component, and the MFR of the resin composition is 15 to 50 g / 10 min is even more preferred; Most preferred is a polyether ketone-based resin composition in which the resin component is a polyether ether ketone resin, the fluorene compound (1) is fluorene compound (1a), the proportion of the fluorene compound (1) is 3 to 8 parts by mass per 100 parts by mass of the resin component, and the MFR of the resin composition is 25 to 30 g / 10 min.

[0188] The resin composition of the present disclosure has good mechanical properties despite containing the fluorene compound (1) having a relatively low molecular weight. The flexural modulus of the resin composition of the present disclosure may be 1 GPa or more, for example, 1,000 to 100,000 MPa, preferably 2,000 to 10,000 MPa, and more preferably 3,000 to 5,000 MPa. These flexural modulus ranges may be the flexural modulus range of a resin composition that does not contain a fibrous reinforcing agent.

[0189] The flexural strength of the resin composition of the present disclosure is, for example, 50 to 1000 MPa, preferably 100 to 500 MPa, and more preferably 130 to 300 MPa. These flexural strength ranges may be the flexural strength range of a resin composition that does not contain a fibrous reinforcing agent.

[0190] In this specification and claims, the flexural modulus and flexural strength of the resin composition can be measured by the method described in the examples below.

[0191] The molded article of the present disclosure can be produced by molding the resin composition using a conventional molding method. Conventional molding methods include compression molding, injection molding, injection-compression molding, extrusion molding, transfer molding, blow molding, pressure molding, and casting molding. In these molding methods, the heating temperature (molding temperature) for molding, such as the melt-kneading temperature, may be a temperature equal to or higher than the melting point or melting temperature of the resin component. A temperature 5 to 80°C higher than the melting point or melting temperature is preferred, a temperature 10 to 60°C higher than the melting point or melting temperature is more preferred, and a temperature 20 to 50°C higher than the melting point or melting temperature is most preferred.

[0192] The shape of the molded article of the present disclosure is not particularly limited and can be selected depending on the application. Examples include one-dimensional structures such as linear, fibrous, or thread-like structures; two-dimensional structures such as film-like, sheet-like, or plate-like structures; and three-dimensional structures such as block-like, rod-like, tubular, hollow, and lens-like structures (e.g., concave or convex lens-like structures).

[0193] 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.

[0194] [LC Purity (HPLC Purity)] Using an HPLC (high performance or high performance liquid chromatograph) apparatus "LC-20AD" manufactured by Shimadzu Corporation and a column "Kinetex XB-C18" manufactured by Phenomenex, a sample was dissolved in THF, diluted with acetonitrile, and measured, and the HPLC purity [area %] was calculated.

[0195] [5% Weight Loss Temperature] Using a thermogravimetry-differential thermal analyzer (TG-DTA) ("Discovery TGA550" manufactured by TA Instruments), the temperature at which the mass of the sample decreased by 5% by mass was measured under conditions of a nitrogen atmosphere and a heating rate of 10°C / min.

[0196] [Melting Point] Using a melting point measuring device ("Melting Point M-565" manufactured by BUCHI), measurements were performed under the conditions of the measurement start temperature shown in Table 1, the heating rate shown in Table 1, the melting start detection condition of 15% (the point at which the rate of change in the transmittance of the sample became 15% or more was defined as the melting start temperature), and the local mode, and the melting start temperature and the melting end temperature were read. The average values ​​of the melting start temperature and the melting end temperature measured three times were calculated.

[0197]

[0198] [MFR] For polyphenylene sulfide and resin compositions, MFR was measured in accordance with ISO 1133 under conditions of a holding time of 5 minutes, a temperature of 320°C and a test load of 21.18N.

[0199] For polyether ether ketone and resin compositions, measurements were performed in accordance with ISO 1133 under conditions of a holding time of 5 minutes, a temperature of 380°C, and a test load of 49.03N.

[0200] [Flexural Strength and Flexural Modulus] For polyphenylene sulfide, polyether ether ketone, and resin compositions thereof, measurements were made in accordance with ISO 178.

[0201] [Raw material] OPP-Np: 2-(2-naphthoyloxy)-biphenyl represented by the following formula

[0202]

[0203] BOPPF: 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene represented by the following formula, synthesized in accordance with Example 3 of JP-A-2003-221352.

[0204]

[0205] BNF: 9,9-bis(6-hydroxy-2-naphthyl)fluorene represented by the following formula, manufactured by Osaka Gas Chemicals Co., Ltd.

[0206]

[0207] BOPPEF: 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene represented by the following formula, manufactured by Osaka Gas Chemicals Co., Ltd.

[0208]

[0209] BAF: 9,9-bis(4-aminophenyl)fluorene represented by the following formula, manufactured by Osaka Gas Chemicals Co., Ltd.

[0210]

[0211] BAF-Ac: 9,9-bis(4-acetaminophenyl)fluorene represented by the following formula

[0212]

[0213] BAF-Bz: 9,9-bis(4-benzoylaminophenyl)fluorene represented by the following formula

[0214]

[0215] PPS: Polyphenylene sulfide, "Torelina A900" manufactured by Toray Industries, Inc. PEEK: Polyether ether ketone, "VESTAKEEP L4000G" manufactured by Polypla-Evonik Co., Ltd.

[0216] Example 1: 10 g (0.02 mol) of BOPPF, 40 g of THF, and 8.4 g (0.044 mol, 2.2 eq) of 2-naphthoyl chloride were placed in a two-necked recovery flask and dissolved. After dissolving, 5.1 g (0.50 mol, 2.5 eq) of triethylamine was slowly added in an ice bath. The mixture was allowed to react at 25°C for 1 hour, and then 40 g of methanol was added. The precipitate was filtered and dried to obtain 9,9-bis[4-(2-naphthoyloxy)-3-phenylphenyl]fluorene (BOPPF-Np(2-Np), 15.8 g of a white solid, 97% yield, 97% HPLC purity) represented by the following formula:

[0217]

[0218] The obtained BOPPF-Np(2-Np) １ The H-NMR spectrum is shown below.

[0219] ​１ H-NMR (CDCl ３ , 300MHz): δ (ppm) 7.2-7.5 (m, 20H), 7.5-7.7 (m, 6H), 7.8-8.0 (m, 8H), 8.05 (dd, 2H), 8.6 (s, 2H)

[0220] Example 2: 5.0 g (0.01 mol) of BOPPF, 20 g of THF, and 5.2 g (0.027 mol, 2.7 eq) of 1-naphthoyl chloride were placed in a 200 mL recovery flask and dissolved, followed by slowly adding 3.0 g (0.030 mol, 3.0 eq) of triethylamine. The mixture was allowed to react at 25°C for 3 hours, and then 80 g of methanol was added. The precipitate was filtered and dried to obtain 9,9-bis[4-(1-naphthoyloxy)-3-phenylphenyl]fluorene (BOPPF-Np(1-Np), 8.0 g of a white solid, 99% yield, 95% HPLC purity) represented by the following formula:

[0221]

[0222] The obtained BOPPF-Np(1-Np) １ The H-NMR spectrum is shown below.

[0223] １ H-NMR (CDCl ３ , 300MHz): δ (ppm) 7.2-7.6 (m, 28H), 7.8-7.9 (m, 4H), 8.0 (d, 2H), 8.11 (dd, 2H), 8.69 (dd, 2H)

[0224] Example 3: 10.1 g (0.02 mol) of BOPPF, 80 g of THF, and 10.4 g (0.074 mol, 3.7 eq) of benzoyl chloride were placed in a 500 mL recovery flask and dissolved, followed by slowly adding 8.1 g (0.080 mol, 4.0 eq) of triethylamine. The mixture was allowed to react at 25°C for 5.5 hours, after which 160 g of methanol was added. The precipitate was filtered and dried to obtain 9,9-bis(4-benzoyloxy-3-phenylphenyl)fluorene (BOPPF-Bz) represented by the following formula (13.9 g of white solid, 97% yield, 98% HPLC purity).

[0225]

[0226] ​The obtained BOPPF-Bz １ The H-NMR spectrum is shown below.

[0227] １ H-NMR (CDCl ３ , 300MHz): δ (ppm) 7.2-7.4 (m, 24H), 7.5-7.6 (m, 4H), 7.78 (d, 2H), 7.98 (dd, 4H)

[0228] Example 4: A 500 mL separable flask was charged with 28.9 g (0.064 mol) of BNF, 97.4 g of MIBK, and 25.1 g (0.132 mol, 2.05 eq) of 2-naphthoyl chloride, which was then heated and stirred at 40°C to dissolve the mixture. Then, 14.7 g (0.145 mol, 2.26 eq) of triethylamine was slowly added. After reacting at 40°C for 1 hour, 50 g of water was added. Further, 97.4 g of THF and 146.2 g of phenoxyethanol were added to dissolve the reaction product, and the resulting solution was added to 389.8 g of methanol. The precipitate was filtered and dried to obtain 9,9-bis[6-(2-naphthoyloxy)-2-naphthyl]fluorene represented by the following formula (BNF-Np(2-Np), 37.0 g of a white solid, yield 76%, HPLC purity 99%).

[0229]

[0230] The obtained BNF-Np (2-Np) １ The H-NMR spectrum is shown below.

[0231] １ H-NMR (CDCl ３ , 300MHz): δ (ppm) 7.3-8.0 (m, 30H), 8.23 ​​(dd, 2H), 8.8 (s, 2H)

[0232] ​​Example 5: 4.5 g (0.01 mol) of BNF, 38 g of THF, and 5.2 g (0.027 mol, 2.7 eq) of 1-naphthoyl chloride were placed in a 200 mL recovery flask and dissolved, followed by slowly adding 3.0 g (0.030 mol, 3.0 eq) of triethylamine. The mixture was allowed to react at 25°C for 3 hours, and then 80 g of methanol was added. The precipitate was filtered and dried to obtain 9,9-bis[6-(1-naphthoyloxy)-2-naphthyl]fluorene (BNF-Np(1-Np), 7.6 g of a white solid, 100% yield, 98% HPLC purity) represented by the following formula:

[0233]

[0234] The obtained BNF-Np (1-Np) １ The H-NMR spectrum is shown below.

[0235] １ H-NMR (CDCl ３ , 300MHz): δ (ppm) 7.3-8.0 (m, 28H), 8.1 (d, 2H), 8.53 (dd, 2H), 9.0 (d, 2H)

[0236] Example 6: 3.8 g (0.01 mol) of BCF, 11.4 g of THF, and 5.1 g (0.027 mol, 2.7 eq) of 2-naphthoyl chloride were placed in a recovery flask and dissolved. After dissolving, 3.0 g (0.03 mol, 3.0 eq) of triethylamine was slowly added in an ice bath. The mixture was allowed to react at 25°C for 1 hour, and then 60 g of methanol was added. The precipitate was filtered and dried to obtain 9,9-bis[4-(2-naphthoyloxy)-3-methylphenyl]fluorene (BCF-Np(2-Np), 6.6 g of a white solid, 96% yield, 97% HPLC purity) represented by the following formula:

[0237]

[0238] The obtained BCF-Np(2-Np) １ The H-NMR spectrum is shown below.

[0239] １ H-NMR (CDCl ３ ​​, 300MHz): δ (ppm) 2.2 (s, 6H), 7.1-7.2 (m, 6H), 7.3-7.5 (m, 6H), 7.5-7.7 (m, 4H), 7.8 (d, 2H), 7.90-8.01 (m, 6H), 8.18 (dd, 2H), 8.8 (s, 2H)

[0240] Example 7: 11.4 g (0.03 mol) of BCF, 34 g of THF, and 14.3 g (0.075 mol, 2.5 eq) of 1-naphthoyl chloride were placed in a recovery flask and dissolved. After dissolving, 9.1 g (0.09 mol, 3.0 eq) of triethylamine was slowly added in an ice bath. The mixture was allowed to react at 25°C for 1 hour, and then 80 g of methanol was added. The precipitate was filtered and dried to obtain 9,9-bis[4-(1-naphthoyloxy)-3-methylphenyl]fluorene (BCF-Np(1-Np), 19.9 g of a white solid, 97% yield, 96% HPLC purity) represented by the following formula:

[0241]

[0242] The obtained BCF-Np (1-Np) １ The H-NMR spectrum is shown below.

[0243] １ H-NMR (CDCl ３ , 300MHz): δ (ppm) 2.2 (s, 6H), 7.1-7.2 (m, 6H), 7.3-7.7 (m, 12H), 7.8 (d, 2H), 7.9 (d, 2H), 8.1 (d, 2H), 8.46 (dd, 2H), 9.0 (d, 2H)

[0244] Reference Example 1: 11.4 g (0.03 mol) of BCF, 34 g of THF, and 10.5 g (0.075 mol, 2.5 eq) of benzoyl chloride were placed in a recovery flask and dissolved. After dissolving, 9.1 g (0.09 mol, 3.0 eq) of triethylamine was slowly added in an ice bath. The mixture was allowed to react at 25°C for 1 hour, and then 300 g of methanol was added. The precipitate was filtered and dried to obtain 9,9-bis(4-benzoyloxy-3-methylphenyl)fluorene represented by the following formula, BCF-Bz (white solid, 16.8 g, yield 96%, HPLC purity 98%).

[0245] ​

[0246] The obtained BCF-Bz １ The H-NMR spectrum is shown below.

[0247] １ H-NMR (CDCl ３ , 300MHz): δ (ppm) 2.1 (s, 6H), 7.0-7.1 (m, 6H), 7.3-7.5 (m, 10H), 7.6-7.7 (m, 2H), 7.8 (d, 2H), 8.18 (dd, 4H)

[0248] Example 8: 11.8 g (0.02 mol) of BOPPEF, 47 g of THF, and 12.2 g (0.064 mol, 3.2 eq) of 2-naphthoyl chloride were placed in a three-necked recovery flask and dissolved. 7.1 g (0.07 mol, 3.5 eq) of triethylamine was then slowly added in an ice bath. The mixture was allowed to react at 25°C for 2.5 hours, and 196 g of methanol was added. The precipitate was filtered and dried to obtain 9,9-bis{4-[2-(2-naphthoyloxy)ethoxy]-3-phenylphenyl}fluorene (BOPPEF-Np(2-Np), 11.7 g of a white solid, 65% yield, 97% HPLC purity) represented by the following formula:

[0249]

[0250] The obtained BOPPEF-Np(2-Np) １ The H-NMR spectrum is shown below.

[0251] １ H-NMR (CDCl ３ , 300MHz): δ (ppm) 4.3 (t, 4H), 4.6 (t, 4H), 6.86 (d, 2H), 7.1-7.6 (m, 24H), 7.7-8.0 (m, 10H), 8.6 (s, 2H)

[0252] ​​Reference Example 2: A 300 mL separable flask was charged with 17.4 g (0.05 mol) of BAF, 89 g of THF, and 15.2 g (0.15 mol, 2.3 eq) of triethylamine, and then 21 g (0.11 mol, 2.2 eq) of 2-naphthoyl chloride was added at 10° C. or lower, followed by reaction at 25° C. for 3 hours, after which 50 g of water was added. The precipitate was filtered and dried to obtain 9,9-bis[4-(2-naphthoyl)aminophenyl]fluorene (BAF-Np(2-Np), 17.8 g of a white solid, 54% yield, 99% HPLC purity) represented by the following formula:

[0253]

[0254] The obtained BAF-Np (2-Np) １ The H-NMR spectrum is shown below.

[0255] １ H-NMR (DMSO-d ６ , 300MHz): δ (ppm) 7.16 (d, 4H), 7.34-7.47 (m, 4H), 7.53 (d, 2H), 7.60- 7.67 (m, 4H), 7.74 (d, 4H), 7.96-8.10 (m, 10H), 8.6 (s, 2H), 10.5 (s, 2H)

[0256] The 5% weight loss temperatures and melting points of the fluorene compounds obtained in Examples 1 to 8 and Reference Examples 1 and 2, and the compounds of Comparative Examples 1 to 7 shown in Table 2 were measured, and the results are shown in Table 2.

[0257]

[0258] As is clear from the results in Table 2, the fluorene compounds of Examples 1 to 8 and Reference Example 1 have a low melting point of 306°C or less, which makes them easy to handle, and also have a high 5% weight loss temperature and excellent heat resistance. In particular, the fluorene compounds of Examples 1 to 2 and 4 to 5 have a 5% weight loss temperature that is about 100°C higher than that of the fluorene compounds of Comparative Examples 2 and 3, demonstrating high heat resistance.

[0259] On the other hand, the compounds of Comparative Examples 6 and 7 showed a 5% weight loss temperature of around 400° C., but also had a high melting point and were difficult to handle.

[0260] ​Example 9 5 parts by mass of BOPPF-Np (2-Np) obtained in Example 1 was added as an additive to 95 parts by mass of PPS, and the mixture was kneaded at a temperature of 320 ° C. and a screw rotation speed of 200 rpm using a twin-screw extruder (Thermo Fisher Scientific Co., Ltd. "Process 11", L / D ratio 40, screw diameter 11 mm) to prepare a pellet-shaped resin composition. The obtained resin composition was injection molded using an injection molding machine (Thermo Fisher Scientific Co., Ltd. "HAAKE MiniJet Pro") under conditions of a cylinder temperature of 330 ° C. and a mold temperature of 140 ° C. to obtain a strip-shaped test piece.

[0261] Example 10: 5 parts by mass of BOPPF-Np (2-Np) obtained in Example 1 was added as an additive to 95 parts by mass of PEEK, and the mixture was kneaded using a twin-screw extruder ("Process 11" manufactured by Thermo Fisher Scientific Co., Ltd., L / D ratio 40, screw diameter 11 mm) at a temperature of 400 ° C. and a screw rotation speed of 200 rpm to prepare a pellet-shaped resin composition. The obtained resin composition was injection molded using an injection molding machine ("HAAKE MiniJet Pro" manufactured by Thermo Fisher Scientific Co., Ltd.) at a cylinder temperature of 430 ° C. and a mold temperature of 200 ° C. to obtain a strip-shaped test piece.

[0262] Example 11 A pellet-shaped resin composition was prepared in the same manner as in Example 10, except that 5 parts by mass of BNF-Np(2-Np) obtained in Example 4 was used as the additive instead of BOPPF-Np(2-Np), and a strip-shaped test piece was obtained.

[0263] The MFR of the resin compositions obtained in Examples 9 to 11 was measured, and the flexural strength and flexural modulus of the test specimens were measured. The results are shown in Table 3. The results for only the PPS used in Example 9 and only the PEEK used in Examples 10 and 11 are shown as Reference Examples 3 and 4, respectively.

[0264]

[0265] As is clear from the results in Table 3, the flowability was improved without significantly decreasing (maintaining or improving) the mechanical properties of the resin compositions of Examples 9 to 11. In particular, the flowability of Example 9 was improved by nearly three times compared to Reference Example 3, which did not contain any additives.

[0266] Example 12 95 parts by mass of PPS was added to 5 parts by mass of BCF-Np (2-Np) obtained in Example 6 as an additive, and a twin-screw extruder (Thermo Fisher Scientific Co., Ltd. "Process 11", L / D ratio 40, screw diameter 11 mm) was used to knead at a temperature of 320 ° C. and a screw rotation speed of 200 rpm to prepare a pellet-shaped resin composition. The obtained resin composition was injection molded using an injection molding machine (Thermo Fisher Scientific Co., Ltd. "HAAKE MiniJet Pro") under conditions of a cylinder temperature of 330 ° C. and a mold temperature of 140 ° C. to obtain a strip-shaped test piece.

[0267] Example 13 A pellet-shaped resin composition was prepared in the same manner as in Example 12, except that BCF-Bz obtained in Reference Example 1 was used as the additive instead of BCF-Np (2-Np), and strip-shaped test pieces were obtained.

[0268] Example 14 5 parts by mass of BOPPF-Np(1-Np) obtained in Example 2 was added as an additive to 95 parts by mass of PEEK, and the mixture was kneaded using a twin-screw extruder ("Process 11" manufactured by Thermo Fisher Scientific Co., Ltd., L / D ratio 40, screw diameter 11 mm) at a temperature of 400 ° C. and a screw rotation speed of 200 rpm to prepare a pellet-shaped resin composition. The obtained resin composition was injection molded using an injection molding machine ("HAAKE MiniJet Pro" manufactured by Thermo Fisher Scientific Co., Ltd.) at a cylinder temperature of 430 ° C. and a mold temperature of 200 ° C. to obtain a strip-shaped test piece.

[0269] Example 15 A pellet-shaped resin composition was prepared in the same manner as in Example 14, except that BNF-Np(1-Np) obtained in Example 5 was used as the additive instead of BOPPF-Np(1-Np), and a strip-shaped test piece was obtained.

[0270] Example 16 A pellet-shaped resin composition was prepared in the same manner as in Example 14, except that BCF-Np(2-Np) obtained in Example 6 was used as the additive instead of BOPPF-Np(1-Np), and a strip-shaped test piece was obtained.

[0271] The MFR of the resin compositions obtained in Examples 12 to 16 was measured, and the flexural strength and flexural modulus of the test pieces were measured. The results are shown in Table 4. The results for only the PPS used in Examples 12 to 13 and only the PEEK used in Examples 14 to 16 are shown as Reference Examples 5 and 6, respectively. The PPS and PEEK in Reference Examples 5 and 6 are the same products as the PPS and PEEK in Reference Examples 3 and 4, but are materials from different lots.

[0272]

[0273] As is clear from the results in Table 4, the resin compositions of Examples 12 to 16 were able to improve the flowability without significantly decreasing (maintaining or improving) the mechanical properties.

[0274] The fluorene compound of the present disclosure can improve the properties of resins and can therefore be used as a resin additive, and in particular, can improve the fluidity of resin components and can therefore be used as a flowability improver.Furthermore, the fluorene compound of the present disclosure can improve the heat resistance, refractive index, strength, etc. of resins and can therefore also be used as a heat resistance improver, refractive index improver, strength improver, etc.

[0275] The resin composition comprising the fluorene compound of the present disclosure can be used as various molded articles according to the type of resin.In particular, the resin composition of engineering plastics such as polyarylene sulfide resin or polyether ketone resin can be used for aerospace and aviation materials such as aircraft parts; automobile parts such as exhaust gas treatment valves, carburetors, manifolds, distributors, ignition, terminal connectors; electrical and electronic parts such as connectors, switches, coil bobbins, relays, printed circuit boards, integrated circuit parts; office automation equipment parts such as printer claws, copier bearings, computer parts, 3D printer parts; home appliances such as microwave oven parts, iron parts, induction cooker coil bases, rice cooker valves; mechanical parts such as gears, piston rings, valves, pump parts; medical equipment such as spinal rods, dental materials, trauma treatment plates; fiber materials such as fiber for bag filters.

[0276] The novel fluorene compounds of the present disclosure can also be used as raw materials for various resins, for example, as monomers for thermoplastic resins and thermosetting resins such as polyester-based resins, polycarbonate-based resins, polyester carbonate-based resins, and polyurethane-based resins.

Claims

1. The following formula (1) (In the formula, Z １ and Z ２ each independently represents an arene ring; １ and A ２ each independently represents an alkylene group, n1 and n2 independently represent an integer of 0 or more, R １ and R ２ each independently represents a hydrocarbon group; R ３ and R ４ each independently represents a substituent, m1 and m2 independently represent an integer of 0 or more, R ５ represents a substituent, and k represents an integer of 0 to 8.

2. In the formula (1), Z １ and Z ２ The resin additive according to claim 1, wherein each independently represents a fused polycyclic arene ring or a ring-assembled arene ring.

3. In the formula (1), Z １ and Z ２ The resin additive according to claim 1, wherein each independently represents a naphthalene ring or a biphenyl ring.

4. In the formula (1), R １ and R ２ The resin additive according to any one of claims 1 to 3, wherein each independently represents an aryl group which may have a substituent.

5. In the formula (1), R １ and R ２ The resin additive according to any one of claims 1 to 3, wherein each independently represents a naphthyl group.

6. A resin additive according to any one of claims 1 to 3, wherein n1 and n2 in formula (1) are 0.

7. The resin additive according to any one of claims 1 to 3, wherein the 5% weight loss temperature of the fluorene compound is 350°C or higher.

8. The resin additive according to claim 7, wherein the melting point of said fluorene compound is 350°C or less.

9. The resin additive according to any one of claims 1 to 3, which is a flowability improver for a resin component.

10. The following formula (2) (In the formula, Z １ , Z ２ , A １ , A ２ , n1, n2, R ３ , R ４ , m1, m2, R ５ , k is the same as in formula (1) above), and a compound represented by the following formulas (3) and (4): (In the formula, X １ and X ２ each independently represents a halogen atom, a hydroxyl group, or an alkoxy group; R １ and R ２ is the same as the formula (1)) to obtain the fluorene compound represented by the formula (1).

11. A resin composition comprising a resin component and the resin additive according to any one of claims 1 to 3.

12. The resin composition according to claim 11, wherein the resin component is a thermoplastic resin.

13. The resin composition according to claim 12, wherein the thermoplastic resin comprises an engineering plastic.

14. The resin composition according to claim 13, wherein the engineering plastic comprises a polyarylene sulfide resin and / or a polyether ketone resin.

15. The resin composition according to claim 11, wherein the resin additive is present in an amount of 0.1 to 100 parts by mass per 100 parts by mass of the resin component.

16. A method for improving the fluidity of a resin component by adding the resin additive according to any one of claims 1 to 3 to the resin component.

17. In formula (1) of claim 1, Z １ and Z ２ represents a benzene ring, and R １ and R ２ are independently fused polycyclic arene rings or ring-assembled arene rings.

18. In formula (1) of claim 1, Z １ and Z ２ are independently fused polycyclic arene rings or ring-assembled arene rings.

Images