Fluorene compounds, methods of making and uses thereof

Abstract

When the fluorene compound represented by formula (1) is used as an additive to the resin component, the flowability of the resin component can be improved. (In formula (1), Z...) 1 and Z 2 Independently representing aromatic hydrocarbon rings, A 1 and A 2 Independently representing alkylene groups, n1 and n2 independently representing integers greater than 0, R 1 and R 2 Independently representing a hydrocarbon group, R 3 and R 4 Substituents are represented independently, m1 and m2 independently represent integers greater than 0, R 5 (This represents a substituent, and k represents an integer from 0 to 8.)

Description

Technical Field

[0001] This disclosure relates to a fluorene compound having a 9,9-bis(acyloxyaryl)fluorene skeleton, a method for its manufacture, and its use. Background Technology

[0002] Compounds with a fluorene skeleton exhibit excellent heat resistance and optical properties, and are therefore primarily used in the optical field as raw materials for resins, or as resin additives such as refractive index enhancers and heat resistance improvers. In particular, recent years have seen significant technological innovations in the optical field, leading to increasingly stringent requirements for optical properties and heat resistance. Consequently, fluorene compounds have been proposed to further improve functionality by introducing substituents into the fluorene skeleton.

[0003] Japanese Patent Application Publication No. 2020-169144 (Patent Document 1) discloses a fluorene compound with high heat resistance that can be used as a raw material for polyester resin, namely a biphenyl derivative having a 9,9-diarylfluorene skeleton and an oxonide.

[0004] Japanese Patent Application Publication No. 2021-187768 (Patent Document 2) discloses 9,9-bis(4-benzoyloxyphenyl)fluorene as a raw material for obtaining polyester resins with high purity and excellent heat resistance.

[0005] Japanese Patent Application Publication No. 2022-143442 (Patent Document 3) discloses a fluorene compound that has high refractive index and heat resistance and can be used as a resin raw material or resin additive, namely a dicarboxylic acid or its derivative having a structure in which a fused tetra- to hexacyclic aryl group is attached at positions 1 to 8 of the fluorene skeleton.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2020-169144

[0009] Patent Document 2: Japanese Patent Application Publication No. 2021-187768

[0010] Patent Document 3: Japanese Patent Application Publication No. 2022-143442 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] On the other hand, when fluorene compounds are used as additives in resin components, it is necessary to improve the function of the resin component without impairing its moldability, and it is also required to ensure flowability during molding. In addition, for resin components that need to be molded at high temperatures, it is also required that they function without deterioration due to thermal decomposition or other factors.

[0013] In this regard, neither Patent Documents 1 nor 2 disclose the use of fluorene compounds as resin additives. On the other hand, while Patent Document 3 discloses the use of fluorene compounds as resin additives, it does not disclose any method for improving resin flowability.

[0014] Therefore, the purpose of this disclosure is to provide a fluorene compound that can improve the flowability of resin components, a method for manufacturing the same, and its uses.

[0015] Methods for solving problems

[0016] In order to achieve the above-mentioned objective, the inventors conducted in-depth research and found that by reacting a dihydroxy compound having a 9,9-bis(acylaryl)fluorene skeleton with a carboxylic acid or its ester-forming derivative, a fluorene compound having a 9,9-bis(acyloxyaryl)fluorene skeleton that can improve resin flowability can be provided, thereby completing the present invention (or this disclosure).

[0017] That is, this disclosure includes the following schemes.

[0018] Scheme [1]: A resin additive comprising a fluorene compound represented by formula (1),

[0019] [Chemistry 1]

[0020]

[0021] (In the formula,

[0022] Z 1 and Z 2 Independently representing aromatic rings,

[0023] A 1 and A 2 Independently representing alkylene groups, n1 and n2 independently represent integers greater than 0.

[0024] R 1 and R 2 Independently representing hydrocarbon groups,

[0025] R 3 and R 4 Each substituent can be represented independently, and m1 and m2 can represent integers greater than or equal to 0.

[0026] R 5 (This represents a substituent, and k represents an integer from 0 to 8).

[0027] Scheme [2]: The resin additive according to Scheme [1] above, wherein, in the above formula (1), Z 1 and Z 2 Independently represents fused polycyclic aromatic rings or cyclic aromatic rings.

[0028] Scheme [3]: The resin additive according to Scheme [1] or [2] above, wherein, in the above formula (1), Z 1 and Z 2 It can be used to represent either a naphthalene ring or a biphenyl ring independently.

[0029] Scheme [4]: ​​The resin additive according to any one of Schemes [1] to [3] above, wherein, in the above formula (1), R 1 and R 2 Independently represents aryl groups that may have substituents.

[0030] Scheme [5]: The resin additive according to any one of the above schemes [1] to [4], wherein, in the above formula (1), R 1 and R 2 The naphthyl group can be represented independently.

[0031] Scheme [6]: The resin additive according to any one of the above schemes [1] to [5], wherein n1 and n2 represent 0 in the above formula (1).

[0032] Scheme [7]: The resin additive according to any one of the above schemes [1] to [6], wherein the 5% weight reduction temperature of the fluorene compound is above 350°C.

[0033] Scheme [8]: The resin additive according to any one of the above schemes [1] to [7], wherein the melting point of the fluorene compound is below 350°C.

[0034] Scheme [9]: The resin additive according to any one of the above schemes [1] to [8] is a flowability improver of the resin component.

[0035] Scheme

[10] : A method for manufacturing a resin additive according to any one of the above schemes [1] to [9], comprising the step of reacting a compound represented by formula (2) with a compound represented by formulas (3) and (4) to obtain a fluorene compound represented by formula (1).

[0036] [Chemistry 2]

[0037]

[0038] (where Z) 1 Z 2 A 1 A 2 n1, n2, R 3 R 4 m1, m2, R 5 (and k has the same meaning as in equation (1) above)

[0039] [Chemistry 3]

[0040]

[0041] (where X) 1 and X 2 Independently representing a halogen atom, hydroxyl group, or alkoxy group, R 1 and R 2 It has the same meaning as in equation (1) above.

[0042] Scheme

[11] : A resin composition comprising a resin component and a resin additive as described in any one of Schemes [1] to [9] above.

[0043] Solution

[12] : The resin composition according to Solution

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

[0044] Solution

[13] : The resin composition according to Solution

[12] above, wherein the thermoplastic resin comprises engineering plastics.

[0045] Scheme

[14] : The resin composition according to Scheme

[13] above, wherein the engineering plastic comprises poly(arylene sulfide) resin and / or polyether ketone resin.

[0046] Scheme

[15] : A resin composition according to any one of the above schemes

[11] to

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

[0047] Solution

[16] : A method for improving the flowability of a resin component, comprising adding the resin additive described in any one of Solutions [1] to [8] above to the resin component.

[0048] Scheme

[17] : A fluorene compound represented by formula (1) as described in Scheme [1] above, wherein, in formula (1) above, Z 1 and Z 2 Represents a benzene ring, and R 1 and R 2 Independently represents fused polycyclic aromatic rings or cyclic aromatic rings.

[0049] Scheme

[18] : A fluorene compound represented by formula (1) as described in Scheme [1] above, wherein, in formula (1) above, Z 1 and Z 2 This indicates a fused polycyclic aromatic ring or a ring-based aromatic ring.

[0050] It should be noted that the following secondary objectives can also be achieved (solved) in this disclosure.

[0051] Another object of this disclosure is to provide a fluorene compound that can improve the flowability (especially melt flowability) of a resin component without excessively reducing the mechanical properties of the resin component, as well as a method for manufacturing the same and its uses.

[0052] Another object of this disclosure is to provide a fluorene compound with high heat resistance, which does not easily deteriorate even when melted at high temperatures, and which is easily melted so as to effectively function in resin compositions (especially with the function of improving flowability), as well as a method for manufacturing the same and its use.

[0053] Another object of this disclosure is to provide a novel fluorene compound that can be used as an additive or resin raw material and a method for manufacturing the same.

[0054] It should be noted that in this specification and claims, C1, C6, C are sometimes used. 10 "etc." indicates the number of carbon atoms in the substituents, etc. For example, "C1 alkyl" refers to an alkyl group with 1 carbon atom ... and "C1 alkyl" refers to an alkyl group with 1 carbon atom. 6-10 "Aryl" refers to an aryl group with 6 to 10 carbon atoms.

[0055] In this specification and claims, "independently" means that the two constituent elements are each independent constituent elements, for example, in alkylene A 1 and A 2 In this case, it means A 1 and A 2 They do not have to be the same alkylene group; they can also be different alkylene groups.

[0056] Furthermore, when using "X~Y" to represent a numerical range in this specification and claims, the endpoints X and Y may also be included.

[0057] Invention Effects

[0058] According to this disclosure, a fluorene compound having a 9,9-bis(acyloxyaryl)fluorene skeleton can be provided to improve resin flowability. Detailed Implementation

[0059] [Fluorene compounds represented by formula (1)]

[0060] The fluorene compound represented by formula (1) of this disclosure (hereinafter also referred to as "fluorene compound (1)") can improve the fluidity of resins and can therefore be used as a fluidity improver and other resin additives (resin additives). In addition, the fluorene compound (1) of this disclosure can achieve high heat resistance by selecting specific structures, etc., and can also be used as an additive for engineering plastics, for example. In particular, although the fluorene compound (1) of this disclosure has high heat resistance, its melting point can be controlled at a low level, so when melt-blended with resin components, it is easy to melt and uniformly blend or disperse in the resin components to perform its function, and its workability is also excellent.

[0061] In the above equation (1), Z is... 1 and Z 2 The aromatic hydrocarbon rings referred to include: monocyclic aromatic hydrocarbon rings such as benzene rings, and polycyclic aromatic hydrocarbon rings. Examples of polycyclic aromatic hydrocarbon rings include: fused polycyclic aromatic hydrocarbon rings (fused polycyclic aromatic hydrocarbon rings) and cyclic aromatic hydrocarbon rings (cyclic cyclic aromatic hydrocarbon rings).

[0062] Examples of fused polycyclic aromatic rings include fused bicyclic aromatic rings, fused tricyclic aromatic rings, and fused bicyclic to tetracyclic aromatic rings. Examples of fused bicyclic aromatic rings include naphthalene rings and indene rings. 8-20 Aromatic rings, etc. Examples of fused tricyclic aromatic rings include: acenaphthene rings, fluorene rings, phenaene rings, anthracene rings, phenanthrene rings, etc. 12-20 Aromatic rings, etc. Examples of fused tetracyclic aromatic rings include: pyrene rings, fused tetrabenzene rings, etc. 16-22 Aromatic rings, etc.

[0063] Examples of aromatic rings in cyclic aggregates include: biphenyl rings, phenylnaphthalene rings, binaphthalene rings, and other biaromatic rings; terphenyl rings and other teraromatic rings.

[0064] It should be noted that in this specification and claims, "cyclic aromatic ring" refers to a ring in which two or more ring systems (aromatic ring systems) are directly connected by single or double bonds, and the number of bonds directly connecting the rings is one less than the ring coefficient. For example, as mentioned above, even if phenylnaphthalene rings, binaphthalene rings, etc. have a fused polycyclic aromatic ring skeleton, they are classified as cyclic aromatic rings, which are clearly distinguished from "fused polycyclic aromatic rings" (such as naphthalene rings (acyclic aromatic rings)).

[0065] Ring Z 1 Can be used with ring Z 2 Different, but preferably the same. In the above aromatic rings, ring Z is used as ring Z. 1 and Ring Z 2Preferably, benzene rings, fused polycyclic aromatic rings, and cyclic aggregate aromatic rings are preferred. From the viewpoint of improving heat resistance and refractive index, fused polycyclic aromatic rings and cyclic aggregate aromatic rings are more preferred, and fused polycyclic aromatic rings such as naphthalene rings are even more preferred. 10-14 Aromatic rings, biphenyl rings, etc. 12-18 The preferred ring is a biaromatic ring, with a naphthalene ring being the most desirable.

[0066] To clarify, the Z-bonded at the 9-position of the fluorene ring... 1 and Z 2 The substitution position is not particularly limited; for example, when Z... 1 and Z 2 When it is a benzene ring, the substitution position can be any position, when Z 1 and Z 2 When it is a naphthalene ring, the substitution position can be either position 1 (1-naphthyl) or position 2 (2-naphthyl), preferably position 2, when Z 1 and Z 2 When it is a biphenyl ring, the substitution position can be any of the 2, 3, or 4 positions, with the 3 position being preferred.

[0067] As A 1 and A 2 Examples of alkylene compounds (straight-chain or branched-chain) include: ethylene, propylene, trimethylene, 1,2-butanediol, and tetramethylene. 2-6 Alkyl groups, etc. Among them, C is preferred. 2-6 Alkylene, more preferably C 2-4 Alkylene, more preferably ethylene, propylene, etc. 2-3 Alkylene, with ethylene being the most preferred. Alkylene A 1 Can be with alkylene A 2 They are different, but the preferred ones are the same.

[0068] The repetition numbers n1 and n2 are each 0 or higher, and can be selected from an integer range of 0 to 15, preferably progressively from 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, and 0 to 1. From the viewpoint of improving heat resistance, 0 is the most preferred. When n1 and n2 are below the above upper limits, heat resistance and refractive index tend to improve. Furthermore, the repetition number n1 can be the same as or different from the repetition number n2. When n1 and n2 are both integers of 2 or higher, there are two or more alkylene groups A. 1 and A 2 The types can be the same or different.

[0069] It should be noted that in this specification and claims, "repetition number (additional mole number)" can be an average value (arithmetic mean, summative average) or an average addition of moles, and the preferred range can be the same as the preferred integer range described above.

[0070] Group [-O-(A1 O) n1 -] and the group [-O-(A 2 O) n2 -] (also known as "ether-containing group") in the Z-ring 1 and Ring Z 2 There are no specific restrictions on the replacement position.

[0071] When ring Z 1 and Ring Z 2 When it is a benzene ring, the group [-O-(A 1 O) n1 -] and the group [-O-(A 2 O) n2 -] In the Z ring 1 and Ring Z 2 The substitution position can be any of the 2, 3, or 4 positions of the phenyl group bonded to the 9-position of the fluorene ring, with the 3 or 4 position being preferred, and the 4 position being particularly preferred.

[0072] When ring Z 1 and Ring Z 2 When it is a naphthalene ring, the group [-O-(A 1 O) n1 -] and the group [-O-(A 2 O) n2 -] In the Z ring 1 and Ring Z 2 The substitution positions are mostly at any 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 naphthyl ring is substituted relative to the 9 position of the fluorene ring (the fluorene ring has a 1-naphthyl or 2-naphthyl substituent), and each ether-containing group is bonded to the 5-position relative to the corresponding 1-naphthyl substituent (in a 1, 5 relationship) or to the 6-position relative to the corresponding 2-naphthyl substituent (in a 2, 6 relationship), with a 2, 6 relationship being particularly preferred.

[0073] When ring Z 1 and Ring Z 2 When it is a cyclic aromatic ring, the group [-O-(A 1 O) n1 -] and the group [-O-(A 2 O) n2 The substitution position of [-] is not particularly limited; for example, substitution can occur on an aromatic ring bonded to the 9-position of the fluorene ring or on an aromatic ring adjacent to that ring. For example, when ring Z... 1 and Ring Z 2 When the biphenyl ring is present, the 3rd or 4th position, preferably the 3rd position, of the biphenyl ring can bond with the 9th position of the fluorene ring. When the 3rd position of the biphenyl ring bonds with the 9th position of the fluorene ring, the group [-O-(A 1 O) n1 -] and the group [-O-(A2 O) n2 The substitution position of -] can be any position among 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.

[0074] As R 1 and R 2 Examples of hydrocarbon groups that can be represented include alkyl, cycloalkyl, aryl, and aralkyl groups.

[0075] Examples of alkyl groups (straight-chain or branched alkyl groups) include: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, hexyl, 2-ethylhexyl, octyl, decyl, etc. 1-12 Alkyl groups, etc.

[0076] Examples of cycloalkyl groups include: cyclopentyl, cyclohexyl, cyclooctyl, bicycloheptyl, decahydronaphthyl, adamantyl, etc. 5-14 Cycloalkyl groups, etc.

[0077] The aryl group may have one or more as R (described later). 3 and R 4 Examples of substituents. Examples of aryl groups include: phenyl, alkylphenyl, biphenyl, alkylbiphenyl, naphthyl, alkylnaphthyl, etc. 6-12 Aryl or C 1-6 Alkyl C 6-12 Aryl. Examples of alkylphenyl groups include: methylphenyl (or tolyl), dimethylphenyl (or xylyl), etc., with one to three carbon atoms. 1-4 Alkyl-phenyl, etc. Examples of alkyl biphenyls include: methyl biphenyl, dimethyl biphenyl, etc., with one to four carbon atoms. 1-4 Alkyl-biphenyl, etc. Examples of alkylnaphthyl groups include: methylnaphthyl, dimethylnaphthyl, etc. (mono- to tetracarbon). 1-4 Alkyl-naphthyl, etc.

[0078] Examples of aryl alkyl groups include: benzyl, phenethyl, etc. 6-10 Aryl-C 1-4 Alkyl groups, etc.

[0079] Among them, as R 1 and R 2 From the viewpoint of easily improving fluidity, heat resistance and refractive index, aryl groups that can have substituents are preferred, biphenyl, alkyl biphenyl, naphthyl, alkyl naphthyl are more preferred, naphthyl and alkyl naphthyl are even more preferred, naphthyl is even more preferred, and 2-naphthyl is the most preferred.

[0080] As R 3 and R 4Examples of substituents include: halogen atoms, hydrocarbon groups, alkoxy groups, cycloalkyloxy groups, aryloxy groups, arylalkyloxy groups, alkylthio groups, cycloalkylthio groups, arylthio groups, arylalkylthio groups, acyl groups, mono- or disubstituted amino groups, nitro groups, cyano groups, etc.

[0081] Examples of halogen atoms include: fluorine, chlorine, bromine, and iodine.

[0082] Examples of hydrocarbon groups include: as R 1 and R 2 Examples include hydrocarbon groups, etc.

[0083] Examples of alkoxy groups (straight-chain or branched-chain alkoxy groups) include: methoxy, ethoxy, propoxy, n-butoxy, tert-butoxy, etc. 1-10 Alkyl groups, etc.

[0084] Examples of cycloalkyloxy groups include: cyclohexyloxy, etc. 5-10 Cycloalkyloxy groups, etc.

[0085] Examples of aryloxy groups include: phenoxy groups, etc. 6-10 Aryloxy groups, etc.

[0086] Examples of aralkyloxy groups include: benzyloxy, etc. 6-10 Aryl-C 1-4 Alkyloxy groups, etc.

[0087] Examples of alkylthio groups include: methylthio, ethylthio, propylthio, n-butylthio, tert-butylthio, etc. 1-10 Alkylthio groups, etc.

[0088] Examples of cycloalkyl thio groups include: cyclohexyl thio group, etc. 5-10 Cycloalkyl thiols, etc.

[0089] Examples of aryl thio groups include: thiophenoxy (phenylthio) and others. 6-10 Aryl thiols, etc.

[0090] Examples of aralkyl thio groups include benzyl thiols, etc. 6-10 Aryl-C 1-4 Alkyl thiols, etc.

[0091] Examples of acyl groups include: acetyl group, etc. 1-6 alkyl-carbonyl, benzoyl, and other C 6-10 Aryl-carbonyl, etc.

[0092] Examples of mono- or disubstituted amino groups include dialkylamino and bis(alkylcarbonyl)amino. Examples of dialkylamino groups include dimethylamino and other dicarbonylamino compounds. 1-4 Alkylamino groups, etc. Examples of bis(alkylcarbonyl)amino groups include: diacetylamino, etc. 1-4Alkyl-carbonyl)amino, etc.

[0093] These substituents may be contained individually or in combination of two or more. Preferably, hydrocarbon groups are preferred, particularly alkyl and aryl groups, and more preferably C10 groups. 1-4 Alkyl, C 6-12 Aryl, and more preferably methyl and other C 1-2 Alkyl, phenyl, etc. C 6-10 Aryl, and more preferably methyl and other C 1-2 Alkyl group, with methyl group being the most preferred.

[0094] The substitution numbers m1 and m2 are both integers greater than or equal to 0, which can be determined according to the ring Z. 1 or ring Z 2 The type of substitution can be an integer from 0 to 8, preferably progressively from 0 to 4, 0 to 3, 0 to 2, and 0 to 1, with 0 being the most preferred. When the substitution numbers m1 and m2 are integers of 2 or more, two or more groups R 3 and R 4 The types can be the same or different.

[0095] Substituent R 3 and R 4 The substitution position is not particularly limited to a specific location. (Replacement of R) 3 Or R 4 Usually in Z 1 and Z 2 At least the adjacent position of the ether-containing group is substituted (or the carbon atom adjacent to the bonding position of the ether-containing group is substituted).

[0096] As R 5 The substituents represented can be exemplified as: as R 3 and R 4 Examples of substituents, etc. The substituents may be contained individually or in combination of two or more. Among the substituents, substituent R... 5 Preferably hydrocarbon groups, more preferably alkyl groups (especially C10 groups such as methyl groups). 1-2 Alkyl and aryl groups are preferred from the viewpoint of easily improving heat resistance, with aryl groups being the most preferred, and phenyl, biphenyl, and naphthyl groups being the most preferred.

[0097] The substitution number k can be an integer from 0 to 8, but preferably it is an integer from 0 to 6, from 0 to 4, from 0 to 3, from 0 to 2, more preferably 0 or 2, and most preferably 0. It should be noted that in the two benzene rings constituting the fluorene ring, the group R... 5 The substitution numbers can be different from each other, but are preferably the same.

[0098] It should be noted that when group R 5When the substitution number k is 2 or more, two or more groups R on the same benzene ring are substituted in the two benzene rings constituting the fluorene ring. 5 The types can be the same or different, substituting more than two groups R on different benzene rings. 5 The types can be the same or different. Furthermore, the group R... 5 There are no particular restrictions as long as the bonding position (substitution position) is at position 1 to 8 of the fluorene ring. For example, positions 2, 7, and 2,7 of the fluorene ring are possible, with position 2,7 being preferred.

[0099] The preferred fluorene compound (1) can be one in the above formula (1) with ring Z 1 and Ring Z 2 Represents a benzene ring, and R 1 and R 2 Fluorene compound (1A) independently represents a fused polycyclic aromatic ring or a ring-aggregate aromatic ring. In fluorene compound (1A), A in the above formula (1) 1 A 2 n1, n2, R 3 R 4 m1, m2, R 5 And k, including the preferred manner, are the same as those of the above-mentioned fluorene compound (1).

[0100] This fluorene compound (1A) is a novel compound, wherein, preferably, it is in the form of the above formula (1).

[0101] Ring Z 1 and Ring Z 2 A represents a benzene ring. 1 and A 2 Independently represent C 2-6 Alkylene, n1 and n2 independently represent integers from 0 to 10, R 1 and R 2 Independently representing biphenyl, alkylbiphenyl, naphthyl, or alkylnaphthyl, R 3 and R 4 The hydrocarbon group is represented independently, and m1 and m2 independently represent integers from 0 to 8. R 5 The compound represents a hydrocarbon group, and k represents an integer from 0 to 6.

[0102] More preferably, ring Z 1 and Ring Z 2 A represents a benzene ring. 1 and A 2 Independently represent C 2-4 Alkylene, n1 and n2 independently represent integers from 0 to 4, R 1 and R 2 Independently representing naphthyl or alkylnaphthyl, R 3 and R 4Independently representing alkyl or aryl, m1 and m2 independently represent integers from 0 to 4, R 5 Compounds that represent alkyl or aryl groups, where k represents an integer from 0 to 4;

[0103] Further optimization of ring Z 1 and Ring Z 2 A represents a benzene ring. 1 and A 2 Independently represent C 2-3 Alkylene, n1 and n2 independently represent integers from 0 to 2, R 1 and R 2 Independently representing the naphthyl group, R 3 and R 4 Independently representing alkyl groups, m1 and m2 independently representing integers from 0 to 2, R 5 denoted by aryl, and k represents compounds with integers from 0 to 2;

[0104] Further optimization of ring Z 1 and Ring Z 2 A represents a benzene ring. 1 and A 2 Represents vinyl, n1 and n2 independently represent integers from 0 to 1, R 1 and R 2 Independently representing the naphthyl group, R 3 and R 4 Independently represent C 1-4 Alkyl groups, m1 and m2 independently represent integers from 0 to 2, R 5 Compounds that independently represent phenyl, biphenyl, or naphthyl groups, where k represents an integer from 0 to 2;

[0105] Optimal selection ring Z 1 and Ring Z 2 Represents a benzene ring, n1 and n2 represent 0, R 1 and R 2 Represents 2-naphthyl, R 3 and R 4 Independently represent C 1-2 Alkyl groups, m1 and m2 independently represent integers from 0 to 1, and k represents a compound with a value of 0.

[0106] The preferred fluorene compound (1) can be one in the above formula (1) with ring Z 1 and Ring Z 2 Fluorene compound (1B) independently represents a fused polycyclic aromatic ring. In fluorene compound (1B), Z in formula (1) above... 1 Z 2 A 1 A 2 n1, n2, R 1 R 2 R3 R 4 m1, m2, R 5 And k, including the preferred manner, are the same as those of the above-mentioned fluorene compound (1).

[0107] This fluorene compound (1B) is a novel compound, wherein, preferably, it is in the form of the above formula (1).

[0108] Ring Z 1 and Ring Z 2 Independently representing fused polycyclic aromatic rings, A 1 and A 2 Independently represent C 2-6 Alkylene, n1 and n2 independently represent integers from 0 to 10, R 1 and R 2 Independently representing aryl, R 3 and R 4 The hydrocarbon group is represented independently, and m1 and m2 independently represent integers from 0 to 8. R 5 The compound represents a hydrocarbon group, and k represents an integer from 0 to 6.

[0109] More preferably, ring Z 1 and Ring Z 2 Independently representing fused polycyclic C 10-14 Aromatic ring, A 1 and A 2 Independently represent C 2-4 Alkylene, n1 and n2 independently represent integers from 0 to 4, R 1 and R 2 Independently representing aryl, R 3 and R 4 Independently representing alkyl or aryl, m1 and m2 independently represent integers from 0 to 4, R 5 Compounds that represent alkyl or aryl groups, where k represents an integer from 0 to 4;

[0110] Further optimization of ring Z 1 and Ring Z 2 Indicates naphthalene ring, A 1 and A 2 Independently represent C 2-3 Alkylene, n1 and n2 independently represent integers from 0 to 2, R 1 and R 2 Independently representing biphenyl, alkylbiphenyl, naphthyl, or alkylnaphthyl, R 3 and R 4 Independently representing alkyl groups, m1 and m2 independently representing integers from 0 to 2, R 5 denoted by aryl, and k represents compounds with integers from 0 to 2;

[0111] Further optimization of ring Z1 and Ring Z 2 Indicates naphthalene ring, A 1 and A 2 Represents vinyl, n1 and n2 independently represent integers from 0 to 1, R 1 and R 2 Independently representing naphthyl or alkylnaphthyl, R 3 and R 4 Independently represent C 1-4 Alkyl groups, m1 and m2 independently represent integers from 0 to 2, R 5 Compounds that independently represent phenyl, biphenyl, or naphthyl groups, where k represents an integer from 0 to 2;

[0112] Optimal selection ring Z 1 and Ring Z 2 Represents the naphthalene ring, n1 and n2 represent 0, R 1 and R 2 Represents naphthyl, R 3 and R 4 Independently represent C 1-2 Alkyl groups, m1 and m2 independently represent integers from 0 to 1, and k represents a compound with a value of 0.

[0113] The preferred fluorene compound (1) can be one in the above formula (1) with ring Z 1 and Ring Z 2 Fluorene compounds (1C) independently represent cyclic aromatic rings. In fluorene compounds (1C), Z in the above formula (1) 1 Z 2 A 1 A 2 n1, n2, R 1 R 2 R 3 R 4 m1, m2, R 5 And k, including the preferred manner, are the same as those of the above-mentioned fluorene compound (1).

[0114] This fluorene compound (1C) is a novel compound, preferably in the form of formula (1) above.

[0115] Ring Z 1 and Ring Z 2 Independently representing the ring set of aromatic hydrocarbon rings, A 1 and A 2 Independently represent C 2-6 Alkylene, n1 and n2 independently represent integers from 0 to 10, R 1 and R 2 Independently representing aryl, R 3 and R 4 The hydrocarbon group is represented independently, and m1 and m2 independently represent integers from 0 to 8. R5 The compound represents a hydrocarbon group, and k represents an integer from 0 to 6.

[0116] More preferably, ring Z 1 and Ring Z 2 A represents a biphenyl ring. 1 and A 2 Independently represent C 2-4 Alkylene, n1 and n2 independently represent integers from 0 to 4, R 1 and R 2 Independently representing aryl, R 3 and R 4 Independently representing alkyl or aryl, m1 and m2 independently represent integers from 0 to 4, R 5 Compounds that represent alkyl or aryl groups, where k represents an integer from 0 to 4;

[0117] Further optimization of ring Z 1 and Ring Z 2 A represents a biphenyl ring. 1 and A 2 Independently represent C 2-3 Alkylene, n1 and n2 independently represent integers from 0 to 2, R 1 and R 2 Independently representing biphenyl, alkylbiphenyl, naphthyl, or alkylnaphthyl, R 3 and R 4 Independently representing alkyl groups, m1 and m2 independently representing integers from 0 to 2, R 5 denoted by aryl, and k represents compounds with integers from 0 to 2;

[0118] Further optimization of ring Z 1 and Ring Z 2 A represents a biphenyl ring. 1 and A 2 Represents vinyl, n1 and n2 independently represent integers from 0 to 1, R 1 and R 2 Independently representing naphthyl or alkylnaphthyl, R 3 and R 4 Independently represent C 1-4 Alkyl groups, m1 and m2 independently represent integers from 0 to 2, R 5 Compounds that independently represent phenyl, biphenyl, or naphthyl groups, where k represents an integer from 0 to 2;

[0119] Optimal selection ring Z 1 and Ring Z 2 Independently representing the biphenyl ring, n1 and n2 represent 0, R 1 and R 2 Represents naphthyl, R 3 and R 4 Independently represent C1-2 Alkyl groups, m1 and m2 independently represent integers from 0 to 1, and k represents a compound with a value of 0.

[0120] Specifically, a preferred fluorene compound (1A) can be cited as an example: in the above formula (1), ring Z 1 and Ring Z 2 It is a benzene ring, and the substituent R 1 and R 2 Compounds with a naphthyl group, for example, 9,9-bis[4-(2-naphthyloxy)-phenyl]fluorene, 9,9-bis[4-(1-naphthyloxy)-phenyl]fluorene, etc.; 9,9-bis[4-(2-naphthyloxy)-3-methylphenyl]fluorene, 9,9-bis[4-(1-naphthyloxy)-3-methylphenyl]fluorene, etc.; 9,9-bis{4-[2-(2-naphthyloxy)ethoxy]-phenyl}fluorene, etc.; 9,9-bis(naphthyloxy(poly)alkoxy-phenyl)fluorene, etc.

[0121] Specifically, preferred fluorene compounds (1B) include those in formula (1) above, where ring Z... 1 and Ring Z 2 It is a naphthalene ring, and the substituent R 1 and R 2 Compounds with a naphthyl group include, for example, 9,9-bis[6-(2-naphthyloxy)-2-naphthyl]fluorene, 9,9-bis[6-(1-naphthyloxy)-2-naphthyl]fluorene, 9,9-bis[5-(2-naphthyloxy)-1-naphthyl]fluorene, etc.; 9,9-bis{6-[2-(2-naphthyloxy)ethoxy]-2-naphthyl}fluorene, 9,9-bis{5-[2-(2-naphthyloxy)ethoxy]-1-naphthyl}fluorene, etc.; 9,9-bis(naphthyloxy(poly)alkoxy-naphthyl)fluorene, etc.

[0122] Specifically, preferred fluorene compounds (1C) include those in formula (1) above, where ring Z... 1 and Ring Z 2 It is a biphenyl ring, and the substituent R 1 and R 2 Compounds with a naphthyl group, such as 9,9-bis[4-(2-naphthyloxy)-3-phenylphenyl]fluorene, 9,9-bis[4-(1-naphthyloxy)-3-phenylphenyl]fluorene, etc.; 9,9-bis{4-[2-(2-naphthyloxy)ethoxy]-3-phenylphenyl}fluorene, etc.; 9,9-bis(naphthyloxy(poly)alkoxy-phenylphenyl)fluorene, etc.

[0123] Among these fluorene compounds, fluorene compound (1B) and fluorene compound (1C) are preferred from the viewpoint of excellent heat resistance. From the viewpoint of excellent high heat resistance, fluorene compound (1B) is particularly preferred. From the viewpoint of excellent balance between heat resistance and flowability, fluorene compound (1C) is particularly preferred.

[0124] More preferably, the fluorene compound (1) may be the fluorene compound represented by formula (1a) [fluorene compound (1a)], the fluorene compound represented by formula (1b) [fluorene compound (1b)] or the fluorene compound represented by formula (1c) [fluorene compound (1c)].

[0125] [Chemistry 4]

[0126]

[0127] (where R) 6 and R 7 Substituents are represented independently, p1 and p2 independently represent integers from 0 to 7, A 1 A 2 n1, n2, R 3 R 4 m1, m2, R 5 (and k has the same meaning as in equation (1) above)

[0128] [Chemistry 5]

[0129]

[0130] (where R) 6 and R 7 Substituents are represented independently, p1 and p2 independently represent integers from 0 to 7, A 1 A 2 n1, n2, R 3 R 4 m1, m2, R 5 (and k has the same meaning as in equation (1) above)

[0131] [Chemistry 6]

[0132]

[0133] (where R) 6 and R 7 Substituents are represented independently, p1 and p2 independently represent integers from 0 to 7, A 1 A 2 n1, n2, R 3 R 4 m1, m2, R 5 (and k has the same meaning as in equation (1) above)

[0134] In equations (1a) to (1c) above, R is... 6 and R 7 The substituents represented can be exemplified as: as R 3 and R 4 Examples of substituents, etc. The substituents may be contained individually or in combination of two or more. Alkyl groups are preferred, and C10 groups are more preferred. 1-4 Alkyl groups, more preferably methyl groups, etc. 1-2 alkyl.

[0135] The substitution numbers p1 and p2 are each integers greater than or equal to 0, preferably integers from 0 to 7, and preferably integers from 0 to 4, 0 to 3, 0 to 2, and 0 to 1, with 0 being the most preferred. When the substitution numbers p1 and p2 are integers greater than or equal to 2, there are two or more groups R. 6 and R 7 The types can be the same or different.

[0136] Among the fluorene compounds (1a), (1b), and (1c), from the viewpoint of excellent heat resistance, fluorene compounds (1b) and (1c) are preferred, from the viewpoint of excellent high heat resistance, fluorene compound (1b) is particularly preferred, and from the viewpoint of excellent balance between heat resistance and flowability, fluorene compound (1c) is particularly preferred.

[0137] 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 above the lower limit, the heat resistance tends to be improved, and when it is below the upper limit, the flowability tends to be improved.

[0138] Fluorene compound (1) has excellent heat resistance. With a 5% weight reduction, the temperature can be above 250°C, preferably above 350°C, more preferably above 400°C, and even more preferably above 450°C. Specifically, it is around 250 to 550°C, and more preferably gradually 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.

[0139] The fluorene compound (1) can be amorphous or crystalline, but is preferably crystalline.

[0140] The melting point of the fluorene compound (1) can be below 350°C, preferably below 320°C, more preferably below 310°C, and even more preferably below 300°C, specifically around 50–330°C, and preferably gradually decreasing to 60–320°C, 70–310°C, 80–300°C, 100–290°C, 120–280°C, and 150–270°C. Despite its high temperature reduction of 5% by weight and excellent heat resistance, the fluorene compound (1) of this disclosure has a melting point that can be controlled at such a low level, making it a rare fluorene compound with excellent workability. In particular, when used as an additive in the preparation of resin compositions, it is advantageous not only because it readily melts during molding, thus improving fluidity, but also because it is not easily thermally decomposed at molding temperatures.

[0141] It should be noted that, in this specification and claims, the 5% weight reduction temperature and melting point of fluorene compound (1) can be determined by the methods described in the examples below.

[0142] The fluorene compound (1) can have a 5% weight reduction temperature of 250°C or higher and a melting point of 350°C or lower (the 5% weight reduction temperature can be 250°C or higher and the melting point can be 350°C or lower), preferably the 5% weight reduction temperature is 350°C or higher and the melting point is 320°C or lower, more preferably the 5% weight reduction temperature is 400°C or higher and the melting point is 300°C or lower, and even more preferably the 5% weight reduction temperature is 450°C or higher and the melting point is 280°C or lower.

[0143] The 5% weight reduction temperature of fluorene compound (1A) [especially fluorene compound (1a)] can be 300-550°C and the melting point can be 100-350°C, preferably 350-500°C and the melting point can be 150-300°C, more preferably 370-450°C and the melting point can be 230-270°C.

[0144] The 5% weight reduction temperature of fluorene compound (1B) [especially fluorene compound (1b)] can be 350-550°C and the melting point can be 80-350°C, preferably 400-520°C and the melting point can be 100-300°C, more preferably 430-500°C and the melting point can be 130-250°C, and even more preferably 460-480°C and the melting point can be 150-210°C.

[0145] The 5% weight reduction temperature of fluorene compound (1C) [especially fluorene compound (1C)] can be 300-550°C and the melting point is 150-350°C, preferably 350-520°C and the melting point is 200-350°C, more preferably 400-500°C and the melting point is 230-300°C, and even more preferably 450-480°C and the melting point is 250-280°C.

[0146] [Method for manufacturing fluorene compound (1) or resin additive]

[0147] The method for manufacturing fluorene compound (1) (or resin additive) is not particularly limited. It can be obtained by esterification reaction of the compound represented by formula (2) above with the compound represented by formulas (3) and (4) above or their ester-forming derivatives (such as acid anhydrides). As the esterification reaction method, conventional ester synthesis or transesterification methods can be used depending on the type of compound represented by formulas (3) and (4) above.

[0148] In equations (3) and (4) above, X is... 1 and X 2 Examples of halogen atoms that can be represented include chlorine atoms, bromine atoms, and iodine atoms. Among these, chlorine atoms and bromine atoms are preferred, with chlorine atoms being particularly preferred.

[0149] As X 1 and X 2 Examples of alkoxy groups (straight-chain or branched-chain alkoxy groups) include: methoxy, ethoxy, propoxy, n-butoxy, tert-butoxy, etc. 1-4 Alkoxy groups, etc. Among them, methyl, ethyl, etc., are preferred. 1-3 Alkoxy, particularly C 1-2 Alkyl group.

[0150] It should be noted that in this specification and claims, when X 1 and X 2 When the hydroxyl group is used, the compounds represented by the above formulas (3) and (4) can be acid anhydrides.

[0151] X is the preferred option 1 and X 2 From the perspective of easily improving reactivity, halogen atoms are preferred, and chlorine is particularly preferred.

[0152] The compound represented by formula (3) above may be different from the compound represented by formula (4) above, but is preferably the same.

[0153] Examples of preferred compounds represented by the above formulas (3) and (4) include: 2-naphthoic acid (2-naphthoic acid), 1-naphthoic acid, 2-naphthoyl chloride, and other naphthoic acids or their ester-forming derivatives.

[0154] The total amount of the compounds represented by formulas (3) and (4) above is, for example, 2 to 10 moles of the compound represented by formula (2) above, preferably 2 to 5 moles, more preferably 2 to 3 moles, even more preferably 2 to 2.5 moles, and most preferably 2.05 to 2.3 moles.

[0155] Esterification can be carried out in the presence of conventional esterification catalysts or without using esterification catalysts.

[0156] In particular, in equations (3) and (4) above, when using X 1 and X 2 In the production methods of compounds containing halogen atoms (hereinafter referred to as "acyl halides (3) and (4)"), the reaction can be carried out in the presence of a base in order to capture the hydrogen halide generated in the reaction and make it also act as a catalyst. Bases can be broadly classified into inorganic bases and organic bases.

[0157] Examples of inorganic bases include: metal hydroxides, specifically hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide and calcium hydroxide; metal carbonates, specifically carbonates of alkali metals or alkaline earth metals such as sodium carbonate and calcium carbonate; and metal bicarbonates, specifically bicarbonates of alkali metals or alkaline earth metals such as sodium bicarbonate.

[0158] 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.

[0159] Bases can be contained alone or in combination of two or more. Among these bases, amines are frequently used, such as trialkylamines like triethylamine and heterocyclic amines like pyridine.

[0160] The amount of base used is 1 to 5 moles, for example, 1 to 4 moles, more preferably 1.5 to 3.5 moles, even more preferably 1.5 to 3 moles, and most preferably 2 to 3 moles, relative to the total amount of the compounds represented by formulas (3) and (4) above.

[0161] Esterification reactions can be carried out in the presence or absence of a solvent that is inert to the reaction. Any organic solvent that is inert to the reaction can 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); and dimethyl ethyl ketone (MEK). Ethers such as alkanes, 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 contained individually or in two or more forms. Ketones such as MIBK and ethers such as THF are preferred. Alternatively, the organic base may also be used as a solvent.

[0162] The esterification reaction can be carried out at 0–100°C, preferably 15–65°C. The reaction time is, for example, 0.5–24 hours, preferably 1–12 hours.

[0163] Esterification reactions can be carried out in air or in an inert atmosphere such as nitrogen or rare gases. From the viewpoint of reactivity, it is preferred to carry out the reaction in an inert atmosphere.

[0164] Esterification can be carried out under stirring, or under normal pressure, pressure, or reduced pressure.

[0165] After the reaction is complete, separation and purification can be carried out as needed using conventional separation and purification methods, such as neutralization, washing, extraction, filtration, dehydration, concentration, decantation, drying, crystallization, reprecipitation, column chromatography, adsorption, and combinations thereof.

[0166] [Resin Additives]

[0167] The resin additive disclosed herein only needs to contain fluorene compound (1). In the resin additive of this disclosure, the proportion of fluorene compound (1) can be 10% by mass or more, preferably gradually increasing to 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 can also be used as a masterbatch, which contains a resin component of the same kind (especially identical) as the resin component described later and a high concentration of fluorene compound (1). In the masterbatch, the concentration of fluorene compound (1) is, for example, 10 to 90% by mass, preferably 20 to 80% by mass, more preferably 30 to 60% by mass.

[0168] The resin additives disclosed herein can also be used as flow improvers or flow enhancers, refractive index improvers, heat resistance improvers, strength improvers, etc.

[0169] [Resin Composition]

[0170] The resin composition disclosed herein comprises a resin component and said resin additive. The resin component may be a curable resin (heat- or light-curable resin) or a thermoplastic resin.

[0171] Examples of curable resins include: phenolic resins such as methyl phenolic resin and linear phenolic resin; amino resins such as urea resin, melamine resin, and guanidine resin; furan resin; unsaturated polyester resin; diallyl phthalate resin; vinyl ester resin (or epoxy (meth)acrylate resin); polyfunctional (meth)acrylate resin; epoxy resin; polyurethane resin; polyimide resin such as bismaleimide resin; and silicone resin.

[0172] Examples of thermoplastic resins include: polyolefin resins such as chain 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 polymethyl methacrylate (PMMA), (meth)acrylic acid-(meth)acrylate copolymer, etc. Acrylic resins; vinyl acetate resins such as polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), and polyvinyl alcohol acetal (polyvinyl alcohol formaldehyde (PVF), polyvinyl alcohol butyral (PVB), etc.); vinyl chloride homopolymers (PVC); vinyl chloride-vinyl acetate copolymers; vinylidene chloride-vinyl chloride copolymers, vinylidene chloride-acrylonitrile copolymers, etc.; fluoropolymers such as polytetrafluoroethylene (PTFE); polyalkylene aryl resins, polyaryl ester resins, and liquid crystal polyesters (LCP). Polyester-based resins; bisphenol A type polycarbonate-based resins; aliphatic polyamide resins, aromatic polyamide resins, or aramid resins; polyacetal resins (POM); polyphenylene ether (PPE) resins; polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ether ketone ketone (PEKEKK) resins; phenoxy resins; aliphatic polyketone resins; poly(aryl sulfide) resins (PPS); polysulfone (PSF), polyethersulfone (PES) Polysulfone resins; cellulose esters such as nitrocellulose, cellulose acetate, and cellulose acetate propionate; cellulose ethers such as ethyl cellulose and carboxymethyl cellulose; thermoplastic polyimide resins such as polyetherimide (PEI) and polyamideimide; polyether nitrile resins; thermoplastic elastomers such as polystyrene-based thermoplastic elastomers (polystyrene-based TPE), polyolefin-based TPE (TPO), polydiene-based TPE, chlorinated TPE, fluorinated TPE, polyurethane-based TPE (TPU), polyester-based TPE (TPEE), and polyamide-based TPE (TPA), etc.

[0173] These resin components can be used alone or in combination of two or more. From the viewpoint of easily improving flowability (melt flowability), thermoplastic resins are preferred. From the viewpoint of being able to significantly exert the effect of the resin additives of the present invention that can be used at high temperatures, engineering plastics are more preferred. Polyester resins, polyacetal resins, polyphenylene ether resins, poly(aryl sulfide) resins, polyetherketone resins, polysulfone resins, and thermoplastic polyimide resins are more preferred. Poly(aryl sulfide) resins and polyetherketone resins are most preferred.

[0174] The proportion of thermoplastic resin in the resin composition can be, for example, about 10% by mass or more, preferably gradually increasing to 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.

[0175] The proportion of engineering plastics (especially poly(arylene sulfide) resins and / or polyetherketone resins) in the resin composition can be, for example, about 10% by mass or more, preferably gradually increasing to 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.

[0176] (Poly(arylene sulfide) resin)

[0177] Poly(arylene sulfide) resins can be resins having repeating units represented by the following formula (5).

[0178] [Chemistry 7]

[0179]

[0180] (where Z) 3 R represents an aromatic ring. 8 (This represents a substituent, and s represents an integer greater than or equal to 0.)

[0181] In the above equation (5), as ring Z 3 Examples of aromatic rings (or aromatic hydrocarbon rings) represented by ring Z include: 1 and Ring Z 2 Examples include aromatic rings.

[0182] The aromatic rings can be used alone or in combination of two or more. Among these aromatic rings, benzene rings and biphenyl rings are preferred, with benzene rings being particularly preferred. Ring Z 3 The phenylene ring can be any one of 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene, but it is preferred to contain at least 1,4-phenylene. From the viewpoint of being able to form a linear polyphenylene sulfide resin and improve mechanical properties, 1,4-phenylene is particularly preferred.

[0183] When ring Z 3 When it is a benzene ring, it can have a substituent R. 8 The proportion of 1,4-phenylene sulfide units (p-phenylene sulfide units) in the units represented by the above formula (5) can be 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more, and most preferably 100 mol%.

[0184] As R 8 The substituents represented can be exemplified as: as R 3 and R 4 Examples of substituents, etc. The substituents may be used alone or in combination of two or more. Alkyl groups are preferred among the substituents. Examples of alkyl groups include: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc., which are straight-chain or branched C-type groups. 1-6 Alkyl groups, etc. These alkyl groups can be used alone or in combination of two or more. Among them, methyl groups, etc., are preferred. 1-4 alkyl.

[0185] R 8 The substitution number s can be any integer greater than or equal to 0, and can be determined according to the ring Z. 3 The type can be appropriately selected, for example, it can be an integer from 0 to 8, preferably an integer from 0 to 4, an integer from 0 to 3, an integer from 0 to 2, more preferably 0 or 1, and most preferably 0.

[0186] In poly(aryl sulfide) resins, the proportion of repeating units represented by the above formula (5) can be 50 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, and even more preferably 100 mol% in all constituent units.

[0187] Other examples include units containing aromatic rings, such as phenylene ether units, phenylene carbonyl units, phenylene sulfonyl units, phenylene sulfone units, etc.

[0188] From the perspective of mechanical properties, poly(aryl sulfide) resins are preferred, especially polyphenylene sulfide (PPS) resins. Examples of PPS resins include polyphenylene sulfide (PPS), polyphenylene sulfide ketone (PPSK), polyphenylene sulfide sulfone (PPSS), and polydiphenylene sulfide (PBPS). Among these, PPS is preferred, and linear PPS is particularly preferred.

[0189] The weight-average molecular weight (Mw) of the poly(aryl sulfide) resin can be 1,000 or more, for example, 1,000 to 500,000, preferably 5,000 to 300,000, more preferably 10,000 to 100,000, further preferably 15,000 to 80,000, and most preferably 20,000 to 60,000. When the molecular weight is above the lower limit, the mechanical properties of the resin composition tend to be easily improved. The range of the weight-average molecular weight can also be the range of the weight-average molecular weight of polyphenylene sulfide resins.

[0190] It should be noted that, in this specification and claims, the weight-average molecular weight of poly(aryl sulfide) resins can be determined by gel permeation chromatography (standard resin: polystyrene).

[0191] The melt flow rate (MFR) of poly(aryl sulfide) resins (especially polyphenylene sulfide resins) is, for example, 1 to 100 g / 10 min, preferably 5 to 70 g / 10 min, more preferably 10 to 50 g / 10 min, even more preferably 20 to 40 g / 10 min, and most preferably 30 to 40 g / 10 min.

[0192] It should be noted that, in this specification and claims, the MFR of poly(arylene sulfide) resins or resin compositions can be determined by the methods described in the examples below.

[0193] The melting point of poly(aryl sulfide) resins (especially polyphenylene sulfide resins) is, for example, 200–350°C, preferably 230–320°C, more preferably 250–300°C, even more preferably 260–290°C, and most preferably 270–280°C. The melting point range can also be the range of melting points for polyphenylene sulfide resins.

[0194] The glass transition temperature of poly(aryl sulfide) resins (especially polyphenylene sulfide resins) is, for example, 50–150°C, preferably 60–130°C, more preferably 70–120°C, even more preferably 80–110°C, and most preferably 90–100°C. The range of glass transition temperatures can also be the range of glass transition temperatures for polyphenylene sulfide resins.

[0195] It should be noted that, in this specification and claims, the melting point and glass transition temperature of poly(aryl sulfide) resins can be determined by differential scanning calorimetry (DSC).

[0196] The proportion of poly(arylene sulfide) resin (especially polyphenylene sulfide resin) in the resin composition can be, for example, about 10% by mass or more, preferably gradually increasing to 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.

[0197] The proportion of poly(arylene sulfide) resin (especially polyphenylene sulfide resin) in the resin composition can be, for example, 10% by mass or more, for example, 10 to 99.9% by mass, preferably 30 to 99% by mass, more preferably 50 to 98% by mass, even more preferably 60 to 97% by mass, and most preferably 65 to 96% by mass.

[0198] (Polyetherketone resin)

[0199] Polyetherketone resins can be resins containing repeating units, which are composed of arylene groups that may have substituents and ether groups and carbonyl groups between a plurality of said arylene groups.

[0200] Examples of aryl groups include: phenylene, naphthylene, etc. 6-10 Arenes; biphenyls and other di-C 6-10 Aryl groups, etc. Examples of phenylene groups include 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene. Examples of biphenylene groups include 2,2'-biphenylene, 3,3'-biphenylene, and 4,4'-biphenylene. These aryl groups can be used alone or in combination of two or more. Among these aryl groups, 1,4-phenylene and other phenylene groups are preferred, as are 4,4'-biphenylene and other biphenylene groups, with 1,4-phenylene being particularly preferred.

[0201] Examples of substituents for the aryl group include: halogen atoms, haloalkyl groups, alkyl groups, hydroxyl groups, alkoxy groups, mercapto groups, alkylthio groups, carboxyl groups, sulfonyl groups, amino groups, N-substituted amino groups, cyano groups, etc. These substituents can be used alone or in combination of two or more. Among these substituents, C10 groups such as methyl and ethyl are preferred. 1-6 Alkyl, more preferably C 1-4 Alkyl groups, preferably C 1-2 alkyl.

[0202] Examples of polyetherketone (PEK) resins include: polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone, polyetherketoneetherketoneketone (PEKEKK), polyetheretherketoneketone (PEEKK), and polyether-diphenyl-ether-phenyl-ketone-phenyl. These polyetherketone resins can be conventional polyetherketone (PEK) or polyetheretherketone (PEEK) resins (or polyetherketone resins). These polyetherketone resins can be used alone or in combination of two or more. Among them, polyetherketone and polyetheretherketone are preferred, and polyetheretherketone is particularly preferred.

[0203] Polyether ether ketone can be a resin obtained by the condensation polymerization of dihalobenzophenone and hydroquinone, having repeating units represented by the formula [-Ph-C(=O)-Ph-O-Ph-O-] (where Ph represents phenylene).

[0204] The weight-average molecular weight of polyether ketone resins (especially 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 above the lower limit, the mechanical properties of the resin composition tend to be improved more easily.

[0205] It should be noted that, in this specification and claims, the weight-average molecular weight of polyetherketone resins can be determined by gel permeation chromatography (standard resin: polystyrene).

[0206] The melt flow rate (MFR) of polyether ketone resins (especially polyether ether ketone) is, for example, 1 to 100 g / 10 min, preferably 5 to 50 g / 10 min, more preferably 10 to 40 g / 10 min, even more preferably 14 to 30 g / 10 min, and most preferably 15 to 20 g / 10 min.

[0207] It should be noted that, in this specification and claims, the MFR of polyetherketone resins or resin compositions can be determined by the methods described in the examples below.

[0208] The proportion of polyether ketone resin (especially polyether ether ketone) in the resin composition can be, for example, about 10% by mass or more, preferably gradually increasing to 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.

[0209] The proportion of polyetherketone resin (especially polyetheretherketone) 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, further preferably 80% by mass or more, most preferably 90% by mass or more, and may also be 90 to 99% by mass. When the resin composition contains filler, the proportion of polyetherketone resin in the resin composition may be, for example, 10 to 99% by mass, preferably 30 to 98% by mass, more preferably 50 to 95% by mass, further preferably 70 to 93% by mass, and most preferably 80 to 90% by mass.

[0210] (A combination of poly(arylene sulfide) resins and polyetherketone resins)

[0211] Poly(aryl sulfide) resins and polyetherketone resins can be used in combination. The mass ratio of poly(aryl sulfide) resin to polyetherketone resin can be 99 / 1 to 1 / 99, preferably 90 / 10 to 10 / 90, more preferably 80 / 20 to 20 / 80, and even more preferably in the range of 70 / 30 to 30 / 70.

[0212] The total amount of poly(arylene sulfide) resin and polyetherketone resin in the resin composition may be, for example, about 10% by mass or more, preferably gradually increasing to 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.

[0213] (fluorene compound (1))

[0214] Because the resin composition of this disclosure contains a fluorene compound (1) as a resin additive, at least one property selected from flowability, refractive index, and strength (especially flowability) can be improved. In particular, in resin compositions containing poly(aryl sulfide) resins, by using Z in the above formula (1) 1 and Z 2 Fluorene compounds representing benzene rings or biphenyl rings (especially biphenyl rings) can significantly improve fluidity.

[0215] The proportion of fluorene compound (1) can be selected from approximately 0.01 to 1000 parts by mass relative to 100 parts by mass of the resin component, preferably gradually increasing to 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 fluorene compound (1) is above the lower limit, the flowability and heat resistance of the resin composition tend to improve; when it is below the upper limit, the mechanical properties of the resin composition tend to improve. These proportions can be relative to 100 parts by mass of thermoplastic resins such as poly(aryl sulfide) resins (especially polyphenylene sulfide resins) and polyetherketone resins (especially polyetheretherketone). In addition, the ratio may also be a ratio of at least one selected from fluorene compound (1A) [especially fluorene (1a)], fluorene compound (1B) [especially fluorene (1b)] and fluorene compound (1C) [especially fluorene (1c)].

[0216] The proportion of the resin additive disclosed herein can be selected from approximately 0.01 to 1000 parts by weight relative to 100 parts by weight of the resin component, preferably gradually increasing to 0.05 to 500 parts by weight, 0.1 to 100 parts by weight, 0.3 to 50 parts by weight, 0.5 to 30 parts by weight, 1 to 10 parts by weight, 3 to 8 parts by weight, and 4 to 7 parts by weight. When the proportion of the resin additive is above the lower limit, the flowability and heat resistance of the resin composition tend to improve; when it is below the upper limit, the mechanical properties of the resin composition tend to improve.

[0217] (Other ingredients)

[0218] The resin composition disclosed herein may, as needed, further comprise at least one selected from other resin components, fillers, and conventional additives.

[0219] As other resin components, when the resin component is a poly(aryl sulfide) resin or a polyetherketone resin, other thermoplastic resins can be mentioned. Examples of other thermoplastic resins include the aforementioned thermoplastic resins other than poly(aryl sulfide) resins or polyetherketone resins. The proportion of other thermoplastic resins 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.

[0220] 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 proportion, relative to 100 parts by weight of the resin component, is, for example, 1 to 200 parts by weight, preferably gradually increasing to 3 to 150 parts by weight, 5 to 100 parts by weight, 10 to 80 parts by weight, and 15 to 50 parts by weight. These proportions can also be relative to 100 parts by weight of thermoplastic resins such as poly(aryl sulfide) resins (especially polyphenylene sulfide resins) and polyetherketone resins (especially polyetheretherketone).

[0221] As a conventional additive, it may include colorants such as dyes and pigments, conductive agents, flame retardants, plasticizers, lubricants, stabilizers, release agents, antistatic agents, dispersants, leveling agents, defoamers, surface modifiers, low-stress agents, etc. The total proportion of these additives in the resin composition may be less than 30% by mass, preferably less than 10% by mass, for example, 0.1 to 10% by mass.

[0222] [Resin composition and molded article]

[0223] The resin composition disclosed herein can be prepared by mixing resin components and fluorene compounds (1) as resin additives, as well as other components as needed, by conventional methods such as dry mixing and melt mixing. The resin composition can be in the form of particles or the like.

[0224] The resin composition disclosed herein exhibits high melt flowability, with an MFR (melt flow rate) of 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 above the lower limit, the moldability tends to improve.

[0225] When the resin composition contains poly(aryl sulfide) resin (especially polyphenylene sulfide resin) as the main component, the MFR of the resin composition is, for example, 10-200 g / 10 min, preferably 30-180 g / 10 min, more preferably 45-170 g / 10 min, further preferably 50-150 g / 10 min, even more preferably 60-130 g / 10 min, and most preferably 80-120 g / 10 min. These MFR ranges can also be the ranges of the MFR of resin compositions that do not contain fibrous reinforcing agents.

[0226] When the resin composition contains a polyetherketone resin (especially polyetheretherketone) as the main component, the mean filtration rate (MFR) of the resin composition is, for example, 10–150 g / 10 min, preferably 12–100 g / 10 min, more preferably 15–70 g / 10 min, further preferably 17–60 g / 10 min, even more preferably 18–50 g / 10 min, and most preferably 20–30 g / 10 min. These MFR ranges can also be the ranges of the MFR of resin compositions that do not contain fibrous reinforcing agents.

[0227] Preferred resin compositions may be poly(aryl sulfide) resin compositions containing poly(aryl sulfide) resins, wherein, from the viewpoint of excellent heat resistance and flowability,

[0228] Preferred: A poly(aryl sulfide) resin composition containing a resin component of a poly(aryl sulfide) resin, a fluorene compound (1) containing a fluorene compound (1A), a fluorene compound (1B) or a fluorene compound (1C), and a fluorene compound (1) in a ratio of 0.1 to 100 parts by weight of the resin component, and a resin composition MFR of 45 to 200 g / 10 min;

[0229] More preferably: a poly(aryl sulfide) resin composition in which the resin component is a poly(aryl sulfide) resin, the fluorene compound (1) is a fluorene compound (1A) or a fluorene compound (1C), the proportion of the fluorene compound (1) relative to 100 parts by weight of the resin component is 0.3 to 50 parts by weight, and the MFR of the resin composition is 50 to 180 g / 10 min;

[0230] Further preferred: a poly(aryl sulfide) resin composition in which the resin component is a polyphenylene sulfide resin, the fluorene compound (1) is fluorene compound (1a) or fluorene compound (1c), the proportion of fluorene compound (1) relative to 100 parts by mass of the resin component is 1 to 10 parts by mass, and the MFR of the resin composition is 60 to 150 g / 10 min.

[0231] The preferred option is a poly(arylene sulfide) resin composition in which the resin component is a polyphenylene sulfide resin, the fluorene compound (1) is a fluorene compound (1c), the ratio of the fluorene compound (1) to 100 parts by weight of the resin component is 3 to 8 parts by weight, and the MFR of the resin composition is 80 to 120 g / 10 min.

[0232] The preferred resin composition may be a polyetherketone resin composition containing a polyetherketone resin, wherein,

[0233] Preferred: A polyetherketone resin composition in which the resin component contains a polyetherketone resin, a fluorene compound (1) contains a fluorene compound (1A), a fluorene compound (1B) or a fluorene compound (1C), and the fluorene compound (1) is present in a ratio of 0.1 to 100 parts by weight of the resin component, and the MFR of the resin composition is 10 to 150 g / 10 min.

[0234] In particular, as a polyetherketone resin composition, it exhibits excellent heat resistance.

[0235] More preferably: a polyetherketone resin composition in which the resin component is a polyetherketone resin, the fluorene compound (1) is a fluorene compound (1B) or a fluorene compound (1C), the proportion of the fluorene compound (1) relative to 100 parts by weight of the resin component is 0.3 to 50 parts by weight, and the MFR of the resin composition is 12 to 100 g / 10 min.

[0236] Further preferred: a polyether ketone resin composition in which the resin component is polyether ketone, the fluorene compound (1) is fluorene compound (1b) or fluorene compound (1c), the proportion of fluorene compound (1) relative to 100 parts by mass of the resin component is 1 to 10 parts by mass, and the MFR of the resin composition is 15 to 50 g / 10 min.

[0237] The preferred option is a polyether ketone resin composition in which the resin component is polyether ketone resin, the fluorene compound (1) is fluorene compound (1b), the ratio of fluorene compound (1) to 100 parts by mass of the resin component is 3 to 8 parts by mass, and the MFR of the resin composition is 20 to 30 g / 10 min.

[0238] Furthermore, as a polyetherketone resin composition, it offers an excellent balance between heat resistance and flowability.

[0239] More preferably: a polyetherketone resin composition in which the resin component is a polyetherketone resin, the fluorene compound (1) is a fluorene compound (1B) or a fluorene compound (1C), the proportion of the fluorene compound (1) relative to 100 parts by weight of the resin component is 0.3 to 50 parts by weight, and the MFR of the resin composition is 12 to 100 g / 10 min.

[0240] Further preferred: a polyether ketone resin composition in which the resin component is polyether ketone, the fluorene compound (1) is fluorene compound (1b) or fluorene compound (1c), the proportion of fluorene compound (1) relative to 100 parts by mass of the resin component is 1 to 10 parts by mass, and the MFR of the resin composition is 15 to 50 g / 10 min.

[0241] The preferred option is a polyether ketone resin composition in which the resin component is polyether ketone resin, the fluorene compound (1) is fluorene compound (1c), the ratio of fluorene compound (1) to 100 parts by mass of the resin component is 3 to 8 parts by mass, and the MFR of the resin composition is 20 to 30 g / 10 min.

[0242] Furthermore, as a polyetherketone-based resin composition, from the viewpoint of excellent flowability,

[0243] More preferably: a polyetherketone resin composition in which the resin component is a polyetherketone resin, the fluorene compound (1) is a fluorene compound (1A) or a fluorene compound (1C), the proportion of the fluorene compound (1) relative to 100 parts by weight of the resin component is 0.3 to 50 parts by weight, and the MFR of the resin composition is 12 to 100 g / 10 min;

[0244] Further preferred: a polyether ketone resin composition in which the resin component is polyether ketone, the fluorene compound (1) is fluorene compound (1a) or fluorene compound (1c), the proportion of fluorene compound (1) relative to 100 parts by mass of the resin component is 1 to 10 parts by mass, and the MFR of the resin composition is 15 to 50 g / 10 min.

[0245] The preferred option is a polyether ketone resin composition in which the resin component is polyether ketone resin, the fluorene compound (1) is fluorene compound (1a), the ratio of fluorene compound (1) to 100 parts by mass of the resin component is 3 to 8 parts by mass, and the MFR of the resin composition is 25 to 30 g / 10 min.

[0246] The resin compositions disclosed herein, despite containing the aforementioned fluorene compound (1) with a low molecular weight, exhibit excellent mechanical properties. The flexural modulus of the resin compositions disclosed herein can be 1 GPa or higher, for example, 1000 to 100000 MPa, preferably 2000 to 10000 MPa, and more preferably 3000 to 5000 MPa. These ranges of flexural modulus can also be the ranges of flexural modulus of resin compositions without fibrous reinforcing agents.

[0247] The flexural strength of the resin compositions disclosed herein is, for example, 50 to 1000 MPa, preferably 100 to 500 MPa, and more preferably 130 to 300 MPa. These ranges of flexural strength can also be the ranges of flexural strength of resin compositions without fibrous reinforcing agents.

[0248] It should be noted that, in this specification and claims, the flexural modulus and flexural strength of the resin composition can be determined by the methods described in the examples below.

[0249] The molded article disclosed herein can be manufactured by molding the above-described resin composition using conventional molding methods. Examples of conventional molding methods include compression molding, injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, pressure molding, and casting. In these molding methods, the heating temperature (molding temperature) used for molding, such as the melt mixing temperature, only needs to be a temperature above or equal to the melting point or melting temperature of the resin component. Preferably, the temperature is 5 to 80°C higher than the melting point or melting temperature; more preferably, it is 10 to 60°C higher; and most preferably, it is 20 to 50°C higher.

[0250] The shape of the molded body disclosed herein is not particularly limited and can be selected according to the application. Examples include: one-dimensional structures such as linear, fibrous or filamentous structures; two-dimensional structures such as membrane, sheet, or plate structures; and three-dimensional structures such as block, rod, tubular or cylindrical, hollow, or lens-shaped (concave or convex lens, etc.).

[0251] Example

[0252] The present disclosure will now be described in more detail based on embodiments, but the present disclosure is not limited to these embodiments. Details of the evaluation items and raw materials are shown below.

[0253] [LC purity (HPLC purity)]

[0254] The Shimadzu Corporation LC-20AD was used as the HPLC (High Performance Liquid Chromatography) apparatus, and the Phenomenex Kinetex XB-C18 column was used as the chromatographic column. The sample was dissolved in THF and diluted with acetonitrile for determination. The HPLC purity [area %] was calculated.

[0255] [5% weight reduction in temperature]

[0256] Using a thermogravimetric-differential thermal analysis apparatus (TG-DTA) (TA Instruments "DiscoveryTGA550"), under a nitrogen atmosphere and a heating rate of 10°C / min, the temperature at which the mass of the sample decreases by 5% was determined.

[0257] [Melting Point]

[0258] Using a melting point measuring apparatus (BUCHI's "Melting Point M-565"), measurements were performed at the starting temperatures and heating rates shown in Table 1, under the 15% melting start detection condition (the point where the rate of change of the sample's transmittance reaches 15% or more is taken as the melting start temperature), and in pharmacopoeia mode. The melting start temperature and melting end temperature were recorded. The average melting start temperature and melting end temperature of the three measurements were calculated.

[0259] [Table 1]

[0260]

[0261] [MFR]

[0262] For polyphenylene sulfide and resin compositions, the MFR was determined according to ISO 1133 under the conditions of a retention time of 5 minutes, a temperature of 320°C, and a test load of 21.18 N.

[0263] For polyetheretherketone and resin compositions, the MFR was determined according to ISO 1133 under the conditions of a retention time of 5 minutes, a temperature of 380°C, and a test load of 49.03 N.

[0264] [Flexural strength and flexural modulus]

[0265] For polyphenylene sulfide, polyether ether ketone and their resin compositions, determination shall be performed in accordance with ISO 178.

[0266] [raw material]

[0267] OPP-Np: 2-(2-naphthyloxy)-biphenyl represented by the following formula

[0268] [Chemistry 8]

[0269]

[0270] BOPPF: Synthesized according to Example 3 of Japanese Patent Application Publication No. 2003-221352, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene represented by the following formula.

[0271] [Chemistry 9]

[0272]

[0273] BNF: 9,9-bis(6-hydroxy-2-naphthyl)fluorene represented by the following formula, manufactured by Osaka Gas Chemical Co., Ltd.

[0274] [Chemistry 10]

[0275]

[0276] BOPPEF: 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, manufactured by Osaka Gas Chemical Co., Ltd.

[0277] [Chemistry 11]

[0278]

[0279] BAF: 9,9-bis(4-aminophenyl)fluorene represented by the following formula, manufactured by Osaka Gas Chemical Co., Ltd.

[0280] [Chemistry 12]

[0281]

[0282] BAF-Ac: 9,9-bis(4-acetaminophenyl)fluorene represented by the following formula

[0283] [Chemistry 13]

[0284]

[0285] BAF-Bz: 9,9-bis(4-benzoylaminophenyl)fluorene represented by the following formula

[0286] [Chemistry 14]

[0287]

[0288] PPS: Polyphenylene sulfide, manufactured by Toray Industries, Inc. as "Torelina A900".

[0289] PEEK: Polyetheretherketone, "VESTAKEEP L4000G" manufactured by Polyplastics-Evonik.

[0290] Example 1

[0291] In a two-necked flask, 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 added and dissolved. Then, 5.1 g (0.50 mol, 2.5 eq) of triethylamine was slowly added in an ice bath. After reacting at 25 °C for 1 hour, 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 white solid, 97% yield, 97% HPLC purity).

[0292] [Chemistry 15]

[0293]

[0294] The obtained BOPPF-Np(2-Np) 1 The H-NMR spectrum is shown below.

[0295] 1 H-NMR (CDCl3, 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)

[0296] Example 2

[0297] In a 200 mL round-bottom flask, 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 added and dissolved. Then, 3.0 g (0.030 mol, 3.0 eq) of triethylamine was slowly added. After reacting at 25 °C for 3 hours, 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 white solid, 99% yield, 95% HPLC purity).

[0298] [Chemistry 16]

[0299]

[0300] The obtained BOPPF-Np(1-Np) 1 The H-NMR spectrum is shown below.

[0301] 1 H-NMR (CDCl3, 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)

[0302] Example 3

[0303] In a 500 mL round-bottom flask, 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 added and dissolved. Then, 8.1 g (0.080 mol, 4.0 eq) of triethylamine was slowly added. After reacting at 25 °C for 5.5 hours, 160 g of methanol was added. The precipitate was filtered and dried to obtain 9,9-bis(4-benzoyloxy-3-phenylphenyl)fluorene (BOPPF-Bz, 13.9 g, white solid, 97% yield, 98% HPLC purity).

[0304] [Chemistry 17]

[0305]

[0306] The obtained BOPPF-Bz 1 The H-NMR spectrum is shown below.

[0307] 1 H-NMR (CDCl3, 300MHz): δ (ppm) 7.2-7.4 (m, 24H), 7.5-7.6 (m, 4H), 7.78 (d, 2H), 7.98 (dd, 4H)

[0308] Example 4

[0309] In a 500 mL separable flask, 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 were added. After dissolving the compounds by heating and stirring at 40 °C, 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. 97.4 g of THF and 146.2 g of phenoxyethanol were then added to dissolve the reactants. This solution was then added to 389.8 g of methanol. The precipitate was filtered and dried to obtain 9,9-bis[6-(2-naphthoyloxy)-2-naphthyl]fluorene (BNF-Np(2-Np), 37.0 g, white solid, 76% yield, 99% HPLC purity).

[0310] [Chemistry 18]

[0311]

[0312] The obtained BNF-Np(2-Np) 1 The H-NMR spectrum is shown below.

[0313] 1 H-NMR (CDCl3, 300MHz): δ (ppm) 7.3-8.0 (m, 30H), 8.23 ​​(dd, 2H), 8.8 (s, 2H)

[0314] Example 5

[0315] In a 200 mL round-bottom flask, 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 added and dissolved. Then, 3.0 g (0.030 mol, 3.0 eq) of triethylamine was slowly added. After reacting at 25 °C for 3 hours, 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 white solid, 100% yield, 98% HPLC purity).

[0316] [Chemistry 19]

[0317]

[0318] The obtained BNF-Np(1-Np) 1 The H-NMR spectrum is shown below.

[0319] 1 H-NMR (CDCl3, 300MHz): δ (ppm) 7.3-8.0 (m, 28H), 8.1 (d, 2H), 8.53 (dd, 2H), 9.0 (d, 2H)

[0320] Example 6

[0321] In a round-bottom flask, 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 added and dissolved. Then, 3.0 g (0.03 mol, 3.0 eq) of triethylamine was slowly added in an ice bath. After reacting at 25 °C for 1 hour, 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 white solid, 96% yield, 97% HPLC purity).

[0322] [Chemistry 20]

[0323]

[0324] The obtained BCF-Np(2-Np) 1 The H-NMR spectrum is shown below.

[0325] 1H-NMR (CDCl3, 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)

[0326] Example 7

[0327] In a round-bottom flask, 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 added and dissolved. Then, 9.1 g (0.09 mol, 3.0 eq) of triethylamine was slowly added in an ice bath. After reacting at 25 °C for 1 hour, 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 white solid, 97% yield, 96% HPLC purity).

[0328] [Chemistry 21]

[0329]

[0330] The obtained BCF-Np(1-Np) 1 The H-NMR spectrum is shown below.

[0331] 1 H-NMR (CDCl3, 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)

[0332] Reference Example 1

[0333] In a round-bottom flask, 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 added and dissolved. Then, 9.1 g (0.09 mol, 3.0 eq) of triethylamine was slowly added in an ice bath. After reacting at 25 °C for 1 hour, 300 g of methanol was added. The precipitate was filtered and dried to obtain 9,9-bis(4-benzoyloxy-3-methylphenyl)fluorene, BCF-Bz (16.8 g white solid, 96% yield, 98% HPLC purity).

[0334] [Chemistry 22]

[0335]

[0336] The obtained BCF-Bz 1 The H-NMR spectrum is shown below.

[0337] 1 H-NMR (CDCl3, 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)

[0338] Example 8

[0339] In a three-necked flask, 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 added and dissolved. Then, 7.1 g (0.07 mol, 3.5 eq) of triethylamine was slowly added in an ice bath. After reacting at 25 °C for 2.5 hours, 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 white solid, yield 65%, HPLC purity 97%).

[0340] [Chemistry 23]

[0341]

[0342] The obtained BOPPEF-Np(2-Np) 1 The H-NMR spectrum is shown below.

[0343] 1 H-NMR (CDCl3, 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)

[0344] See Example 2

[0345] In a 300 mL separable flask, 17.4 g (0.05 mol) of BAF, 89 g of THF, and 15.2 g (0.15 mol, 2.3 eq) of triethylamine were added. 21 g (0.11 mol, 2.2 eq) of 2-naphthoyl chloride was added below 10 °C. After reacting at 25 °C for 3 hours, 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 white solid, yield 54%, HPLC purity 99%).

[0346] [Chemistry 24]

[0347]

[0348] The obtained BAF-Np(2-Np) 1 The H-NMR spectrum is shown below.

[0349] 1 H-NMR (DMSO-d6, 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)

[0350] The results of measuring the 5% weight reduction temperature and melting point for the fluorene compounds obtained in Examples 1-8 and Reference Examples 1-2, as well as the compounds in Comparative Examples 1-7 shown in Table 2, are presented in Table 2.

[0351] [Table 2]

[0352]

[0353] As shown in Table 2, the fluorene compounds of Examples 1-8 and Reference Example 1 have melting points as low as below 306°C, exhibiting excellent workability, while also demonstrating high temperatures with a 5% weight reduction and excellent heat resistance. In particular, the fluorene compounds of Examples 1-2 and 4-5 show approximately 100°C higher temperatures with a 5% weight reduction compared to the fluorene compounds of Comparative Examples 2 and 3, demonstrating high heat resistance.

[0354] On the other hand, although the compounds of Comparative Examples 6 and 7 showed a 5% weight reduction temperature of around 400°C, they also had high melting points and low operability.

[0355] Example 9

[0356] Relative to 95 parts by weight of PPS, 5 parts by weight of BOPPF-Np(2-Np) obtained in Example 1 as an additive were added, and a granular resin composition was prepared by mixing using a twin-screw extruder (Thermo Fisher Scientific "Process 11", L / D ratio 40, screw diameter 11 mm) at a temperature of 320°C and a screw speed of 200 rpm. The resulting resin composition was then injection molded using an injection molding machine (Thermo Fisher Scientific "HAAKE MiniJet Pro") at a barrel temperature of 330°C and a die temperature of 140°C to obtain strip-shaped test pieces.

[0357] Example 10

[0358] Relative to 95 parts by weight of PEEK, 5 parts by weight of BOPPF-Np(2-Np) obtained in Example 1 as an additive were added, and a granular resin composition was prepared by mixing using a twin-screw extruder (Thermo Fisher Scientific "Process 11", L / D ratio 40, screw diameter 11 mm) at a temperature of 400°C and a screw speed of 200 rpm. The resulting resin composition was then injection molded using an injection molding machine (Thermo Fisher Scientific "HAAKE MiniJet Pro") at a barrel temperature of 430°C and a die temperature of 200°C to obtain strip-shaped test pieces.

[0359] Example 11

[0360] Except that 5 parts by mass of BNF-Np(2-Np) obtained in Example 4 were used instead of BOPPF-Np(2-Np) as an additive, the same procedure as in Example 10 was followed to prepare a granular resin composition and obtain strip test pieces.

[0361] The MFR of the resin compositions obtained in Examples 9-11 was determined, and the flexural strength and flexural modulus of the test pieces were measured. The results are shown in Table 3. It is noted that the results using only the PPS used in Example 9 and the results using only the PEEK used in Examples 10-11 are shown as Reference Examples 3 and 4, respectively.

[0362] [Table 3]

[0363]

[0364] As shown in Table 3, the resin compositions of Examples 9-11 improved flowability without significantly reducing (maintaining or improving) mechanical properties. In particular, in Example 9, the flowability was improved by nearly 3 times compared to Reference Example 3 without additives.

[0365] Example 12

[0366] Relative to 95 parts by weight of PPS, 5 parts by weight of BCF-Np(2-Np) obtained in Example 6 as an additive were added, and a granular resin composition was prepared by mixing using a twin-screw extruder (Thermo Fisher Scientific "Process 11", L / D ratio 40, screw diameter 11 mm) at a temperature of 320°C and a screw speed of 200 rpm. The resulting resin composition was then injection molded using an injection molding machine (Thermo Fisher Scientific "HAAKE MiniJet Pro") at a barrel temperature of 330°C and a die temperature of 140°C to obtain strip-shaped test pieces.

[0367] Example 13

[0368] Except that BCF-Bz obtained in Reference Example 1 was used instead of BCF-Np (2-Np) as an additive, the same procedure as in Example 12 was followed to prepare a granular resin composition and obtain strip test pieces.

[0369] Example 14

[0370] Relative to 95 parts by weight of PEEK, 5 parts by weight of BOPPF-Np(1-Np) obtained in Example 2 as an additive were added, and a granular resin composition was prepared by mixing using a twin-screw extruder (Thermo Fisher Scientific "Process 11", L / D ratio 40, screw diameter 11 mm) at a temperature of 400°C and a screw speed of 200 rpm. The resulting resin composition was then injection molded using an injection molding machine (Thermo Fisher Scientific "HAAKE MiniJet Pro") at a barrel temperature of 430°C and a die temperature of 200°C to obtain strip-shaped test pieces.

[0371] Example 15

[0372] Except that BNF-Np(1-Np) obtained in Example 5 was used instead of BOPPF-Np(1-Np) as an additive, the same procedure as in Example 14 was followed to prepare a granular resin composition and obtain strip test pieces.

[0373] Example 16

[0374] Except that BCF-Np (2-Np) obtained in Example 6 was used instead of BOPPF-Np (1-Np) as an additive, the same procedure as in Example 14 was followed to prepare a granular resin composition and obtain strip test pieces.

[0375] The MFR of the resin compositions obtained in Examples 12-16 was determined, and the flexural strength and flexural modulus of the test pieces were measured. The results are shown in Table 4. Note that the results using only the PPS used in Examples 12-13 and only the PEEK used in Examples 14-16 are shown as Reference Examples 5 and 6, respectively. Note that the PPS and PEEK in Reference Examples 5 and 6 are the same commercial products as those in Reference Examples 3 and 4, but from different batches.

[0376] [Table 4]

[0377]

[0378] As can be seen from the results in Table 4, the resin compositions of Examples 12-16 can improve flowability without significantly reducing (maintaining or improving) mechanical properties.

[0379] Industrial practicality

[0380] Since the fluorene compounds of this disclosure can improve the properties of resins, they can be used as resin additives, especially as flow improvers, as they can improve the flowability of resin components. Furthermore, since the fluorene compounds of this disclosure can also improve the heat resistance, refractive index, and strength of resins, they can also be used as heat resistance improvers, refractive index improvers, and strength improvers.

[0381] Resin compositions containing the fluorene compounds disclosed herein can be used as various molded bodies depending on the type of resin. In particular, resin compositions as engineering plastics such as poly(aryl sulfide) resins or polyetherketone resins can be used in: aerospace materials such as aircraft parts; automotive parts such as exhaust gas treatment valves, carburetors, manifolds, distributors, igniters, and terminal connectors; electrical / electronic parts such as connectors, switches, coil frames, relays, printed circuit boards, and integrated circuit components; OA equipment parts such as printer separators, copier bearings, computer parts, and 3D printer parts; household appliances such as microwave oven parts, iron parts, induction cooker cooktops, and rice cooker valves; mechanical parts such as gears, piston rings, valves, and pump parts; medical equipment such as spinal fixation rods, dental materials, and trauma treatment fixation plates; and fibrous materials such as fibers for bag filters.

[0382] The novel fluorene compounds disclosed herein can also be used as raw materials for various resins, for example, as monomers for thermoplastic resins or thermosetting resins such as polyester resins, polycarbonate resins, poly(ester carbonate) resins, and polyurethane resins.

Claims

1. A resin additive comprising a fluorene compound represented by formula (1), In the formula, Z 1 and Z 2 Independently representing aromatic rings, A 1 and A 2 Independently representing alkylene groups, n1 and n2 independently represent integers greater than 0. R 1 and R 2 Independently representing hydrocarbon groups, R 3 and R 4 Each substituent can be represented independently, and m1 and m2 can represent integers greater than or equal to 0. R 5 represents a substituent, and k represents an integer from 0 to 8.

2. The resin additive according to claim 1, wherein, In the above equation (1), Z 1 and Z 2 Independently represents fused polycyclic aromatic rings or cyclic aromatic rings.

3. The resin additive according to claim 1, wherein, In the above equation (1), Z 1 and Z 2 It can be used to represent either a naphthalene ring or a biphenyl ring independently.

4. The resin additive according to any one of claims 1 to 3, wherein, In the above equation (1), R 1 and R 2 Independently represents aryl groups that may have substituents.

5. The resin additive according to any one of claims 1 to 3, wherein, In the above equation (1), R 1 and R 2 The naphthyl group can be represented independently.

6. The resin additive according to any one of claims 1 to 3, wherein, In the above equation (1), n1 and n2 represent 0.

7. The resin additive according to any one of claims 1 to 3, wherein, The fluorene compound is reduced by 5% by weight at a temperature above 350°C.

8. The resin additive according to claim 7, wherein, The fluorene compound has a melting point below 350°C.

9. The resin additive according to any one of claims 1 to 3, wherein it is a flowability improver for resin components.

10. A method for manufacturing a resin additive according to any one of claims 1 to 3, comprising the step of reacting a compound represented by formula (2) with compounds represented by formulas (3) and (4) to obtain the fluorene compound represented by formula (1). In the formula, Z 1 Z 2 A 1 A 2 n1, n2, R 3 R 4 m1, m2, R 5 and k have the same meaning as in equation (1). In the formula, X 1 and X 2 Independently representing a halogen atom, hydroxyl group, or alkoxy group, and R 1 and R 2 It has the same meaning as in equation (1).

11. A resin composition comprising a resin component and a 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 includes engineering plastics.

14. The resin composition according to claim 13, wherein, The engineering plastics comprise poly(arylene sulfide) resins and / or polyetherketone resins.

15. The resin composition according to claim 11, wherein, The proportion of the resin additive relative to 100 parts by weight of the resin component is 0.1 to 100 parts by weight.

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

17. A fluorene compound represented by formula (1) according to claim 1, wherein, In equation (1), Z 1 and Z 2 Represents a benzene ring, and R 1 and R 2 Independently represents fused polycyclic aromatic rings or cyclic aromatic rings.

18. A fluorene compound represented by formula (1) according to claim 1, wherein, In equation (1), Z 1 and Z 2 Independently represents fused polycyclic aromatic rings or cyclic aromatic rings.

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