Composition containing a fluorene compound and a carboxylic acid component

Abstract

The present invention provides a composition (or fluidity improver) capable of forming a resin composition with excellent fluidity (melt fluidity, moldability, or processability) without excessively reducing heat aging resistance (heat resistance or thermal stability), a resin composition and masterbatch containing this composition, and methods and applications for producing the same. [Solution] A composition (A) is prepared that contains at least a fluorene compound (a1) represented by the following formula (1) and a carboxylic acid component (a2), wherein the carboxylic acid component (a2) contains a carboxylic acid having 5 or more carbon atoms or a salt thereof. TIFF2026068710000020.tif46154

Description

[Technical Field]

[0001] This disclosure relates to compositions (flow improvers and / or heat aging improvers) comprising a specific fluorene compound (or fluorene derivative) and a specific carboxylic acid component, resin compositions and masterbatches comprising this composition (or the specific fluorene compound and the specific carboxylic acid component), and methods for producing and using these (molded articles, methods for improving flowability, etc.). [Background technology]

[0002] U.S. Patent No. 2,299,948 (Patent Document 1) states that 9,9-di-(β-carbamoyl-ethyl)fluorene, represented by the following formula, is useful as an intermediate for preparing synthetic resins.

[0003] [ka]

[0004] International Publication No. 2021 / 172300 (Patent Document 2) and International Publication No. 2021 / 171756 (Patent Document 3) disclose resin compositions comprising a specific fluorene derivative and a resin, and describe that the fluorene derivative can be used as a fluidity improver for the resin, etc. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] U.S. Patent No. 2,299,948 [Patent Document 2] International Publication No. 2021 / 172300 [Patent Document 3] International Publication No. 2021 / 171756 [Overview of the project] [Problems that the invention aims to solve]

[0006] In the example described in Patent Document 1, 9,9-di-(β-cyanoethyl)fluorene is reacted with sulfuric acid under predetermined conditions to prepare the above-mentioned 9,9-di-(β-carbamoyl-ethyl)fluorene.

[0007] However, there is no mention or suggestion of using 9,9-di-(β-carbamoyl-ethyl)fluorene as a resin additive.

[0008] On the other hand, the embodiments described in Patent Documents 2 and 3 describe the use of specific fluorene derivatives as resin additives.

[0009] However, the present inventors have discovered that the resin compositions of Patent Documents 2 and 3 may exhibit significantly reduced heat aging resistance, as detailed in the Examples section.

[0010] Accordingly, the object of this disclosure is to provide a composition (or fluidity improver) capable of forming a resin composition with excellent fluidity (melt fluidity, moldability, or processability) without excessively reducing heat aging resistance (heat resistance or thermal stability), a resin composition and masterbatch containing this composition, and methods for producing and using these. [Means for solving the problem]

[0011] As a result of diligent research to achieve the above objectives, the present inventors have found that by combining a specific fluorene compound with a specific carboxylic acid component, fluidity can be effectively improved while suppressing (and in some cases maintaining or improving) the decrease in heat aging resistance, and have completed the present invention (or this disclosure). That is, this disclosure may include the following embodiments, etc.

[0012] Appearance [1]: It comprises at least a fluorene compound (a1) represented by the following formula (1) and a carboxylic acid component (a2), Composition (A), wherein the carboxylic acid component (a2) comprises a carboxylic acid having 5 or more carbon atoms or a salt thereof.

[0013] [Chemistry]

[0014] [In the formula, R 2d , , 1 , , 4 , , , 5 ,

[0017] , 3a , ,

[0016] , 2a , , 5 , , ,

[0015] , 2b , , , 4 , , 3b , , , 2c , 5 , 4 , represents a substituent, m1 represents an integer from 0 to 8, R 2a R 2b R 2c and R 2d each independently represent a hydrogen atom or a substituent, R 3a and R 3b each independently represent a hydrogen atom or a substituent, X 1a and X 1b each independently represent a group represented by the following formula (X1)

[0015] [Chemistry]

[0016] (In the formula, R 4 and R 5 each independently represent a hydrogen atom or a hydrocarbon group, or R 4 and R 5 are bonded to each other to form a heterocyclic ring together with the adjacent nitrogen atom.) represents a group represented by.

[0017] Aspect [2]: In the above formulas (1) and (X1), R 1 represents an alkyl group, an aryl group or an acyl group, m1 represents an integer from 0 to 4, R 2a R 2b R 2c and R 2d each independently represent a hydrogen atom or an alkyl group, R 3a and R 3b each independently represent a hydrogen atom or an alkyl group, R 4 and R 5This independently represents a hydrogen atom or an alkyl group; The composition (A) according to embodiment [1], wherein the carboxylic acid component (a2) is a polycarboxylic acid having 5 or more carbon atoms or a salt thereof.

[0018] Appearance [3]: In equations (1) and (X1) above, R 1 is C 1-6 Alkyl or C 6-10 It indicates an aryl group, and m1 is an integer between 0 and 2. R 2a , R 2b , R 2c and R 2d These are independently hydrogen atoms or C 1-6 It shows an alkyl group, R 3a and R 3b These are independently hydrogen atoms or C 1-6 It shows an alkyl group, R 4 and R 5 These are independently hydrogen atoms or C 1-6 This indicates an alkyl group; The composition (A) according to embodiment [1] or [2], wherein the carboxylic acid component (a2) is a dicarboxylic acid having 5 to 12 carbon atoms or a salt thereof.

[0019] Appearance [4]: A composition (A) according to any one of embodiments [1] to [3], wherein the ratio of the fluorene compound (a1) to the carboxylic acid component (a2) is the former / latter (mass ratio) = 25 / 75 to 99 / 1.

[0020] Appearance [5]: A fluidity improver comprising composition (A) as described in any of embodiments [1] to [4].

[0021] Appearance [6]: A method for improving fluidity by adding a fluorene compound (a1) and a carboxylic acid component (a2) [or composition (A)] described in any of embodiments [1] to [4] to a resin (b).

[0022] Appearance [7]: The method according to embodiment [6], which improves fluidity while suppressing a decrease in heat aging resistance.

[0023] Appearance [8]: A resin composition (B) comprising a fluorene compound (a1) and a carboxylic acid component (a2) [or composition (A)] according to any of embodiments [1] to [4], and a resin (b).

[0024] Appearance [9]: The resin composition (B) according to embodiment [8], wherein the resin (b) comprises at least one selected from polyester resins, polyamide resins, and polyurethane resins.

[0025] Appearance

[10] : A resin composition (B) according to embodiment [8] or [9], wherein the ratio of the total amount of the fluorene compound (a1) and the carboxylic acid component (a2) [or composition (A)] to the resin (b) is the former / latter (mass ratio) = 0.01 / 99.99 to 10 / 90.

[0026] Appearance

[11] : A method for producing a resin composition (B) by mixing a fluorene compound (a1) and a carboxylic acid component (a2) [or composition (A)] described in any of embodiments [1] to [4] with a resin (b).

[0027] Appearance

[12] : A molded article comprising the resin composition (B) described in any of embodiments [8] to

[10] .

[0028] Appearance

[13] : A masterbatch (C) comprising a fluorene compound (a1) and a carboxylic acid component (a2) [or composition (A)] according to any of embodiments [1] to [4], and a first resin (b1).

[0029] Appearance

[14] : A masterbatch (C) according to an embodiment

[13] in which the ratio of the total amount of the fluorene compound (a1) and the carboxylic acid component (a2) [or composition (A)] to the first resin (b1) is the former / latter (mass ratio) = 5 / 95 to 90 / 10.

[0030] Appearance

[15] : A resin composition (B) comprising a masterbatch (C) according to embodiment

[13] or

[14] and a second resin (b2).

[0031] Appearance

[16] : A method for producing a resin composition (B) by mixing a masterbatch (C) according to embodiment

[13] or

[14] with a second resin (b2).

[0032] Appearance

[17] : A molded article comprising the resin composition (B) described in embodiment

[15] .

[0033] Appearance

[18] : A method for improving fluidity by adding the masterbatch (C) described in embodiment

[13] or

[14] to a second resin (b2).

[0034] Appearance

[19] : The method according to embodiment

[18] , which improves fluidity while suppressing a decrease in heat aging resistance.

[0035] Furthermore, this disclosure may achieve the following secondary objectives (or solve the following secondary problems):

[0036] In other words, another object of this disclosure is to provide a composition (or fluidity improver) capable of forming a resin composition with excellent fluidity even with a small amount of additive, a resin composition and masterbatch containing this composition, and methods for producing and using these.

[0037] Furthermore, in this specification and the claims, the number of carbon atoms in the substituent is defined as C1, C6, C 10 These are sometimes used to indicate this. For example, an alkyl group with 1 carbon atom is called a "C1 alkyl group," and an aryl group with 6 to 10 carbon atoms is called a "C1 alkyl group."6-10 It is indicated as "aryl group," etc.

[0038] In this specification and in the claims, “independently” means that the two components are independent components, R 2a , R 2b , R 2c and R 2d In this case, it means that each element does not need to be the same group (hydrogen atom or substituent) as the others, and they may be different.

[0039] In this specification and in the claims, numerical ranges indicated as "X~Y" etc. may include the numerical values ​​X and Y. [Effects of the Invention]

[0040] This disclosure provides a composition (or fluidity improver) capable of forming a resin composition with excellent fluidity (melt fluidity, moldability, or processability) without excessively reducing heat aging resistance (heat resistance or thermal stability), a resin composition and masterbatch containing this composition, and methods for producing and using these. [Modes for carrying out the invention]

[0041] Composition (A) of the present disclosure can form a resin composition (B) with excellent fluidity (melt fluidity, moldability, or processability) without excessively reducing heat aging resistance (heat resistance or thermal stability), and can therefore be effectively used as a fluidity improver and / or heat aging resistance improver. In addition to composition (A) and resin composition (B), the present disclosure also includes a masterbatch (C) containing composition (A) [or a fluorene compound (a1) and a carboxylic acid component (a2) described later].

[0042] Furthermore, composition (A) of the present disclosure [or the fluorene compound (a1) and carboxylic acid component (a2) described later] can effectively improve fluidity even when added in small amounts.

[0043] [Composition (A)] Composition (A) (flowability improver and / or heat aging resistance improver) contains at least a fluorene compound (a1) represented by the following formula (1) and a carboxylic acid component (a2).

[0044] (Fluorene compound (a1))

[0045] [ka]

[0046] [In the formula, R 1 represents a substituent, and m1 represents an integer from 0 to 8. R 2a , R 2b , R 2c and R 2d These independently represent a hydrogen atom or a substituent. R 3a and R 3b These independently represent a hydrogen atom or a substituent. X 1a and X 1b The following equation (X1) is independent of the above

[0047] [ka]

[0048] (In the formula, R 4 and R 5 This independently represents a hydrogen atom or a hydrocarbon group, or R 4 and R 5 (This shows a heterocycle formed by the bonding of two atoms with adjacent nitrogen atoms.) This indicates the group represented by [ ].

[0049] In the above equation (1), R 1 The substituent represented by may be an inactive (or nonpolymerizable) group that is inert to the reaction. 1 Examples of substituents represented by [-OR] include halogen atoms, hydrocarbon groups, and groups. h ](where R h (represents a hydrocarbon group), group [-SRh ](where R h Examples include hydrocarbon groups, acyl groups, nitro groups, cyano groups, and substituted amino groups (mono or disubstituted amino groups).

[0050] In this specification and in the claims, R h The hydrocarbon groups represented by each symbol represent independent hydrocarbon groups, which may be identical or different from one another.

[0051] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0052] Hydrocarbon group (or R h ) may be a saturated or unsaturated hydrocarbon group, an aliphatic (including alicyclic) or aromatic hydrocarbon group, and a hydrocarbon group with a linear (linear or branched) or cyclic structure, or a combination of linear and cyclic structures. Note that the hydrocarbon group (or R) h The number of carbon atoms constituting the group is not particularly limited, but may be as low as 20, for example, and preferably in the following order: 1-16, 1-12, 1-10, 1-8, 1-6. Typical hydrocarbon group (or R h Examples of alkyl groups include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups.

[0053] Examples of alkyl groups (linear or branched alkyl groups) include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl groups. 1-10 Examples include alkyl groups, preferably C 1-6 C such as an alkyl group, more preferably a methyl group. 1-4 It is an alkyl group.

[0054] Examples of cycloalkyl groups include cyclopentyl groups, cyclohexyl groups, and other C groups. 5-10 Examples include cycloalkyl groups.

[0055] Examples of aryl groups include phenyl groups, alkylphenyl groups, biphenylyl groups, naphthyl groups, etc. 6-12 Examples include aryl groups. Alkylphenyl groups include mono- or tri-C groups such as methylphenyl (or tolyl) and dimethylphenyl (or xylyl) groups. 1-4 Examples include alkylphenyl groups.

[0056] Examples of aralkyl groups include benzyl groups, phenethyl groups, and other C groups. 6-10 Aryl-C 1-4 Examples include alkyl groups.

[0057] The group [-OR h ] and base [-SR h In ], R h As a hydrocarbon group represented by R 1 Examples of hydrocarbon groups include those similar to the hydrocarbon groups exemplified above, including preferred embodiments, such as alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. The aforementioned group [-OR h ] and base [-SR h For example, the hydrocarbon group (or R h Examples of the corresponding bases are given, and representative bases [-OR h Examples include alkoxy groups, cycloalkyloxy groups, aryloxy groups, and aralkyloxy groups; representative groups [-SR] h Examples of these groups include alkylthio groups, cycloalkylthio groups, arylthio groups, and aralkylthio groups.

[0058] Examples of alkoxy groups (linear or branched alkoxy groups) include methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, and t-butoxy groups. 1-10 Examples include alkoxy groups. Cycloalkyloxy groups include, for example, cyclohexyloxy groups and other C groups. 5-10 Examples include cycloalkyloxy groups. Examples of aryloxy groups include phenoxy groups and other C groups. 6-10An aryloxy group can be mentioned. Examples of the aralkyloxy group include a C 6-10 aryl-C 1-4 alkyloxy group can be mentioned.

[0059] Examples of the alkylthio group include a C such as a methylthio group, an ethylthio group, a propylthio group, an n-butylthio group, a t-butylthio group, etc. 1-10 alkylthio group can be mentioned. Examples of the cycloalkylthio group include a C 5-10 cycloalkylthio group can be mentioned. Examples of the arylthio group include a C such as a phenylthio group (or thiophenoxy group), etc. 6-10 arylthio group can be mentioned. Examples of the aralkylthio group include a C such as a benzylthio group, etc. 6-10 aryl-C 1-4 alkylthio group can be mentioned.

[0060] Examples of the acyl group include a C 1-12 acyl group, etc., and specifically, a C such as an acetyl group, etc. 1-6 alkyl-carbonyl group, etc., can be mentioned.

[0061] Examples of the mono- or di-substituted amino group include a mono- or dialkylamino group, a mono- or diacylamino group, etc. Examples of the mono- or dialkylamino group include a mono- or diC such as a mono- or dimethylamino group, etc. 1-4 alkylamino group, etc., can be mentioned. Examples of the mono- or diacylamino group include a mono- or diC such as a mono- or diacetylamino group, etc. 1-5 acylamino group, etc., can be mentioned.

[0062] Typical R 1 include a halogen atom, a hydrocarbon group (for example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, etc.), a group [-OR hExamples include alkoxy groups, acyl groups, and preferably alkyl groups (linear or branched alkyl groups), hydrocarbon groups such as aryl groups, and acyl groups such as acetyl groups. More preferably alkyl groups (methyl groups, ethyl groups, t-butyl groups, etc.) 1-6 (such as alkyl groups) or aryl groups (such as phenyl groups) 6-10 These are hydrocarbon groups such as aryl groups, and in particular alkyl groups (such as methyl groups). 1-4 (An alkyl group, etc.) is preferred.

[0063] R 1 The number of substitutions m1 is an integer between 0 and 8, for example, an integer between 0 and 6, preferably in increments of 0 to 4, then 0 to 2, more preferably 0 or 1, or 0 or 2, and especially 0. Note that if m1 is 2 or more, then 2 or more R 1 The types may be the same or different from each other. Also, of the two benzene rings that form the fluorene skeleton, both benzene rings may have R 1 When substitution occurs, the R of one of the benzene rings 1 The type and the R of the other benzene ring 1 The types may be the same or different from each other. Also, R 1 The substitution position is not particularly limited as long as it is at positions 1 to 8 of the fluorene ring, for example, it may be at positions 2, 3, 2,7, etc.

[0064] R 2a , R 2b , R 2c or R 2d The substituent represented by may be an inactive (or nonpolymerizable) group that is inert to the reaction. 2a , R 2b , R 2c or R 2d Examples of substituents represented by include hydrocarbon groups. 2a , R 2b , R 2c or R 2d Examples of hydrocarbon groups represented by R 1Examples of hydrocarbon groups include those similar to the hydrocarbon groups exemplified above (e.g., alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, etc.). Preferred hydrocarbon groups include alkyl groups, and preferred alkyl groups are listed below in order: C 1-6 Alkyl alkyl group, C 1-5 Alkyl alkyl group, C 1-4 Alkyl alkyl group, C 1-3 It is an alkyl group, and more preferably C 1-2 It is an alkyl group, and more specifically, a methyl group.

[0065] Preferred R 2a , R 2b , R 2c and R 2d This is a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. At least R 2c and R 2d Preferably, R is a hydrogen atom, and in this embodiment, preferred R 2a and R 2b is a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and especially a hydrogen atom (i.e., R 2a , R 2b , R 2c and R 2d It is preferable that all of them are hydrogen atoms.

[0066] Also, R 2a , R 2b , R 2c and R 2d The types may be different from each other, R 2a and R 2b They are identical, R 2c and R 2d It is preferable that they are identical.

[0067] R 3a or R 3b The substituent represented by may be an inactive (or nonpolymerizable) group that is inert to the reaction. 3a or R 3b Examples of substituents represented by include hydrocarbon groups. 3aor R 3b Examples of hydrocarbon groups represented by R 1 Examples of hydrocarbon groups include those similar to the hydrocarbon groups exemplified above (e.g., alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, etc.). Preferred hydrocarbon groups include alkyl groups, and preferred alkyl groups are listed below in order: C 1-6 Alkyl alkyl group, C 1-5 Alkyl alkyl group, C 1-4 Alkyl alkyl group, C 1-3 It is an alkyl group, and more preferably C 1-2 It is an alkyl group, and more specifically, a methyl group.

[0068] Preferred R 3a and R 3b The element is a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom. 3a and R 3b The types may be different from each other, but it is preferable that they be the same.

[0069] X 1a and X 1b [or equation (X1)], R 4 and R 5 Examples of hydrocarbon groups in this context include R 1 Examples of hydrocarbon groups include those similar to the hydrocarbon groups exemplified above (e.g., alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, etc.). Preferred hydrocarbon groups include aliphatic hydrocarbon groups such as alkyl groups and cycloalkyl groups, with alkyl groups (linear or branched alkyl groups) being particularly preferred, and even more preferred alkyl groups are, in the following steps, C 1-8 Alkyl alkyl group, C 1-6 Alkyl alkyl group, C 1-4 Alkyl alkyl group, C 1-3 These are alkyl groups (methyl group, ethyl group, isopropyl group, etc.).

[0070] Also, R 4 and R 5 and bond to each other, and adjacent nitrogen atoms [the first heteroatom, i.e., R4 , R 5 When a heterocycle (N-containing heterocycle) is formed with a nitrogen atom that combines with a carbonyl group to form an amide group (amide bond or carboxylic acid amide), the heterocycle may contain only the nitrogen atom (first heteroatom) as a heteroatom, or it may contain one or more additional heteroatoms (second heteroatoms) in addition to the nitrogen atom as needed. Examples of the type of second heteroatom include nitrogen, oxygen, and sulfur atoms, and it may contain at least one selected from these (at least an oxygen atom). The number of heteroatoms constituting the heterocycle (total number of first and second heteroatoms) may be, for example, about 1 to 3, preferably 1 to 2, and more preferably 2. The heterocycle is often, for example, a 5 to 7-membered ring (5 to 7-membered heterocycle), preferably a 5 or 6-membered ring, and more preferably a 6-membered ring. The heterocycle may be aromatic, but it is preferably non-aromatic.

[0071] Typical heterocycles include, for example, heterocycles containing one or more nitrogen atoms such as pyrrolidine rings, piperidine rings, homopiperidine rings (azepane rings, hexahydroazepine rings, or hexamethyleneimine rings), and heterocycles containing a nitrogen atom and a different heteroatom such as a morpholine ring. Preferably, they are non-aromatic 5-7 membered heterocycles containing a nitrogen atom and a different heteroatom, particularly an oxygen atom.

[0072] Preferred R 4 and R 5 This can be a hydrogen atom or a hydrocarbon group such as an aliphatic hydrocarbon group, and in this case, R 4 and R 5 The types may be the same or different from each other. A more preferred R 4 and R 5 These are hydrogen atoms or alkyl groups (linear or branched alkyl groups), and more preferably, in the following steps, hydrogen atoms or C 1-6 Alkyl alkyl group, hydrogen atom or C 1-5 Alkyl alkyl group, hydrogen atom or C1-4 Alkyl alkyl group, hydrogen atom or C 1-3 It is an alkyl group (methyl group, ethyl group, isopropyl group, etc.), and is particularly preferably a hydrogen atom, R 4 and R 5 It is most preferable that both are hydrogen atoms.

[0073] X 1a and X 1b The types may be different from each other, but it is preferable that they be the same.

[0074] Typical fluorene compounds (a1) include, for example, in formulas (1) and (X1), R 1 C is an alkyl group, aryl group or acyl group (such as an acetyl group). 1-3 (e.g., alkyl-carbonyl group), m1 represents an integer from 0 to 4. R 2a , R 2b , R 2c and R 2d These independently represent a hydrogen atom or an alkyl group. R 3a and R 3b These independently represent a hydrogen atom or an alkyl group. R 4 and R 5 Examples include compounds that independently exhibit a hydrogen atom or a hydrocarbon group such as an aliphatic hydrocarbon group (preferably a hydrogen atom or an alkyl group);

[0075] Preferably, R 1 is C 1-6 Alkyl or C 6-10 It indicates an aryl group, and m1 is an integer between 0 and 2. R 2a , R 2b , R 2c and R 2d These are independently hydrogen atoms or C 1-6 Alkyl alkyl group (preferably a hydrogen atom or C 1-4 (Alkyl alkyl group) R 3a and R 3bThese are independently hydrogen atoms or C 1-6 Alkyl alkyl group (preferably a hydrogen atom or C 1-4 (Alkyl alkyl group) R 4 and R 5 These are independently hydrogen atoms or C 1-6 Examples of compounds exhibiting alkyl groups include:

[0076] More preferably, R 1 is C 1-4 It represents an alkyl group or a phenyl group, and m1 represents an integer from 0 to 2. R 2a , R 2b , R 2c and R 2d These are independently hydrogen atoms or C 1-2 It represents an alkyl group (preferably a hydrogen atom), R 3a and R 3b These are independently hydrogen atoms or C 1-2 It represents an alkyl group (preferably a hydrogen atom or a methyl group), R 4 and R 5 These are independently hydrogen atoms or C 1-4 Examples of compounds exhibiting alkyl groups include:

[0077] Particularly preferred, R 1 is C 1-4 It represents an alkyl group, and m1 represents an integer between 0 and 2. R 2a , R 2b , R 2c and R 2d This represents a hydrogen atom. R 3a and R 3b These independently represent a hydrogen atom or a methyl group. R 4 and R 5 These are independently hydrogen atoms or C 1-3 Examples include compounds exhibiting alkyl groups (preferably hydrogen atoms).

[0078] Specific examples of fluorene compounds (a1) include 9,9-bis[(2-carbamoyl)alkyl]fluorene, 9,9-bis[2-(N-alkylcarbamoyl)alkyl]fluorene, 9,9-bis[2-(N,N-dialkylcarbamoyl)alkyl]fluorene, and 9,9-bis[2-(N-containing heterocyclic-N-yl-carbonyl)alkyl]fluorene.

[0079] Examples of 9,9-bis[(2-carbamoyl)alkyl]fluorene include 9,9-bis(2-carbamoylethyl)fluorene, 9,9-bis(2-carbamoylpropyl)fluorene, and other 9,9-bis[(2-carbamoyl)C 2-3 Examples include alkylfluorene.

[0080] Examples of 9,9-bis[2-(N-alkylcarbamoyl)alkyl]fluorene include 9,9-bis[2-(N-methylcarbamoyl)ethyl]fluorene, 9,9-bis[2-(N-methylcarbamoyl)propyl]fluorene, 9,9-bis[2-(N-ethylcarbamoyl)ethyl]fluorene, 9,9-bis[2-(N-isopropylcarbamoyl)ethyl]fluorene, 9,9-bis[2-(N-isopropylcarbamoyl)propyl]fluorene, 9,9-bis[2-(N-butylcarbamoyl)ethyl]fluorene, and other 9,9-bis[2-(NC 1-6 (Alkyl-carbamoyl)C 2-3 Examples include alkylfluorene.

[0081] Examples of 9,9-bis[2-(N,N-dialkylcarbamoyl)alkyl]fluorene include 9,9-bis[2-(N,N-dimethylcarbamoyl)ethyl]fluorene, 9,9-bis[2-(N,N-dimethylcarbamoyl)propyl]fluorene, 9,9-bis[2-(N,N-diethylcarbamoyl)ethyl]fluorene, 9,9-bis[2-(N,N-diethylcarbamoyl)propyl]fluorene, 9,9-bis[2-(N,N-diisopropylcarbamoyl)ethyl]fluorene, 9,9-bis[2-(N,N-dibutylcarbamoyl)ethyl]fluorene, etc. 1-6 (Alkyl-carbamoyl)C 2-3 Examples include alkylfluorene.

[0082] Examples of 9,9-bis[2-(N-containing heterocyclic-N-yl-carbonyl)alkyl]fluorene include 9,9-bis[2-(morpholine-4-yl-carbonyl)ethyl]fluorene, 9,9-bis[2-(morpholine-4-yl-carbonyl)propyl]fluorene, and other 9,9-bis[2-(N-containing heterocyclic-N-yl-carbonyl)C 2-3 Examples include alkylfluorene.

[0083] The molecular weight of the fluorene compound (a1) may be, for example, around 308 to 2000, and preferably in the following increments: 308 to 1000, 308 to 800, 308 to 500, 308 to 450, 308 to 400, and 308 to 350. A molecular weight within a moderate range that is not too large tends to improve fluidity.

[0084] Furthermore, the 5% weight loss temperature of the fluorene compound (a1) may be, for example, around 200-400°C, and preferably, in stages, 230-380°C, 250-360°C, 280-350°C, 300-340°C, and 310-330°C. Thus, the fluorene compound (a1) has high heat resistance. Therefore, it can be effectively used as a fluidity improver without decomposing even in high-temperature environments.

[0085] In this specification and in the claims, the 5% weight loss temperature can be measured using thermogravimetric (TG), specifically by the method described in the examples of International Publication No. 2021 / 171756.

[0086] The fluorene compound (a1) may be in crystalline or amorphous form, and the melting point in the crystalline form may be, for example, around 50 to 300°C (e.g., 100 to 300°C), preferably 150 to 300°C (e.g., 200 to 290°C), and more preferably 230 to 280°C (e.g., 240 to 270°C).

[0087] In this specification and in the claims, the melting point can be measured using a melting point analyzer, specifically by the method described in the examples of International Publication No. 2021 / 171756.

[0088] The fluorene compound (a1) may be included alone or in combination of two or more. Among the fluorene compounds (a1), R 4 and R 5 Fluorene compounds in which the atom is a hydrogen atom are preferred, and in particular, 9,9-bis[(2-carbamoyl)alkyl]fluorenes such as 9,9-bis(2-carbamoylethyl)fluorene are preferred.

[0089] (Carboxylic acid component (a2)) In this disclosure, it appears that fluidity can be further improved while suppressing a decrease in heat aging resistance (heat resistance or thermal stability) by combining a specific carboxylic acid component (a2), i.e., a carboxylic acid component with 5 or more carbon atoms, with a fluorene compound (a1).

[0090] In this specification and claims, unless otherwise specified, the term "carboxylic acid component" includes not only carboxylic acids but also salts of carboxylic acids.

[0091] When preparing the resin composition (B) (e.g., by melt kneading), forming it into a molded body, or using the molded body in a high-temperature environment, the number of carbon atoms constituting the carboxylic acid component (a2) may be, for example, 5 or more (e.g., about 5 to 20), preferably in the following increments: 5 to 15, 5 to 14, 5 to 13, 5 to 12, 5 to 11, 5 to 10, 5 to 9, 5 to 8 (e.g., 6 to 8 or 5 to 7), and more preferably 6, more preferably in the following increments: 5 to 12, 6 to 12 (e.g., 7 to 10), 6 to 11 (e.g., 8 to 10), 6 to 10 (e.g., 9 to 10). These number of carbon atoms may also be the number of carbon atoms constituting the monocarboxylic acid component, polycarboxylic acid component (especially dicarboxylic acid components such as aliphatic dicarboxylic acid components, alicyclic dicarboxylic acid components, and aromatic dicarboxylic acid components) described later. When the number of carbon atoms constituting the carboxylic acid component (a2) is within a moderate range, not too few, it tends to be easier to effectively suppress the vaporization and / or decomposition of the carboxylic acid component (a2) as described above, and thus has excellent handling properties. Furthermore, when the number of carbon atoms is within a moderate range, not too many, it may be easier to effectively improve fluidity even with a small amount of additive.

[0092] A carboxylic acid component having 5 or more carbon atoms (preferably a polycarboxylic acid component having 5 or more carbon atoms, and especially a dicarboxylic acid component having about 5 to 12 carbon atoms) may be the main component of the carboxylic acid component (a2), and its proportion may be, for example, about 30 to 100% by mass relative to the total carboxylic acid component (a2), preferably in stages of 50% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, and substantially 100% by mass or more.

[0093] Examples of the carboxylic acid component (a2) include carboxylic acids or salts thereof containing one or more carboxyl groups in their chemical structure, and the chemical structure may be linear (linear or branched), cyclic, or a combination of linear and cyclic structures. The carboxylic acid component (a2) may be a linear or branched aliphatic carboxylic acid component, an alicyclic carboxylic acid component having an alicyclic skeleton (non-aromatic ring skeleton), or an aromatic carboxylic acid component having an aromatic ring skeleton. Furthermore, the carboxylic acid component (a2) may be a saturated or unsaturated (preferably saturated) carboxylic acid component.

[0094] Carboxylic acid components (a2) can be broadly classified into monocarboxylic acids or their salts containing one carboxyl group (monocarboxylic acid components) and polycarboxylic acids or their salts containing multiple carboxyl groups (polycarboxylic acid components). These may be included individually or in combination of two or more types.

[0095] Examples of monocarboxylic acid components include aliphatic monocarboxylic acid components, alicyclic monocarboxylic acid components, and aromatic monocarboxylic acid components.

[0096] Examples of aliphatic monocarboxylic acid components include alkanic acid (linear or branched alkanic acid) components. Examples of alkanic acid (linear or branched alkanic acid) components include alkanic acid with 5 or more carbon atoms, specifically valeric acid (pentanoic acid), isovaleric acid (3-methylbutanoic acid), 2-methylbutanoic acid, pivalic acid (2,2-dimethylpropionic acid), caproic acid (hexanoic acid), 2-methylpentanoic acid, 3-methylpentanoic acid, 4-methylpentanoic acid, 2-ethylbutanoic acid, 2,2-dimethylbutanoic acid, 3,3-dimethylbutanoic acid, and enan. Heptanoic acid, 2-methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid, 2,2-dimethylpentanoic acid, caprylic acid (octanoic acid), 2-methylheptanoic acid, 2-ethylhexanoic acid, 2,2-dimethylhexanoic acid, pelargonic acid (nonanoic acid), 4-methyloctanoic acid, 3,5,5-trimethylhexanoic acid, decanoic acid, 4-methylnonanoic acid, 7,7-dimethyloctanoic acid, undecanoic acid, lauric acid (dodecanoic acid), tri Decanoic acid, myristic acid (tetradecanoic acid), 12-methyltridecanoic acid, pentadecanoic acid, 12-methyltetradecanoic acid, palmitic acid (hexadecanoic acid), 14-methylpentadecanoic acid, 2-hexyldecanoic acid, margaric acid (heptadecanoic acid), 2-methylhexadecanoic acid, 14-methylhexadecanoic acid, stearic acid (octadecanoic acid), 16-methylheptadecanoic acid, 2-(1,3,3-trimethylbutyl)-5,7,7-tri C, such as methyloctanoic acid, nonadecanoic acid, arachidic acid (eicosanoic acid), henicosanoic acid, behenic acid (docosanoic acid), tricosanoic acid, lignoceric acid (tetracosanoic acid), pentacosanoic acid, cerotic acid (hexacosanoic acid), heptacosanoic acid, montanic acid (octacosanoic acid), nonacosanoic acid, melisinic acid (triacontanoic acid), laxeronic acid (dotriacontanoic acid), gedaic acid (tetratriacontanoic acid), and 2-hexadecyloctadecanoic acid. 5-50 Alkane-carboxylic acid component, preferably C 5-20 Examples include alkane-carboxylic acid components.

[0097] Examples of alicyclic monocarboxylic acid components include cycloalkanecarboxylic acid components, crosslinked cyclic alkanecarboxylic acid components, alkyl-cycloalkanecarboxylic acid components, alkyl-crosslinked cyclic alkanecarboxylic acid components, cycloalkyl-alkanecarboxylic acid components, crosslinked cyclic alkyl-alkanecarboxylic acid components, and alkyl-cycloalkyl-alkanecarboxylic acid components.

[0098] Examples of cycloalkanecarboxylic acid components include cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cycloheptanecarboxylic acid, and C 4-12 Examples include cycloalkane-carboxylic acid components.

[0099] Examples of crosslinked cyclic alkanecarboxylic acid components include bicyclo[1.1.1]pentane-1-carboxylic acid and tricyclo[3.3.1.0 3,7 ]nonane-3-carboxylic acid (noadamantan-3-carboxylic acid), tricyclo[3.3.1.1 3,7 ] Decane-1-carboxylic acid (adamantane-1-carboxylic acid), pentacyclo[4.2.0.0 2,5 .0 3,8 .0 4,7 Examples include octane-1-carboxylic acid (cubane-1-carboxylic acid) and other bi- or pentacycloalkanecarboxylic acid components.

[0100] Examples of alkyl-cycloalkanecarboxylic acid components include mono- or tetraC compounds such as 1-methylcyclopropane-1-carboxylic acid, 2,2,3,3-tetramethylcyclopropanecarboxylic acid, 1-methyl-1-cyclohexanecarboxylic acid, 4-methyl-1-cyclohexanecarboxylic acid, 4-ethyl-1-cyclohexanecarboxylic acid, 4-propyl-1-cyclohexanecarboxylic acid, 4-isopropyl-1-cyclohexanecarboxylic acid, 4-butyl-1-cyclohexanecarboxylic acid, 4-isobutyl-1-cyclohexanecarboxylic acid, 4-t-butyl-1-cyclohexanecarboxylic acid, and 4-pentyl-1-cyclohexanecarboxylic acid. 1-6 Alkyl-C 3-10Examples include cycloalkane-carboxylic acid components.

[0101] Examples of alkyl-crosslinked cyclic alkanecarboxylic acid components include mono- or tetra-C, such as 3-methyl-bicyclo[1.1.1]pentane-1-carboxylic acid. 1-6 Examples include alkyl-bi or pentacycloalkanecarboxylic acid components.

[0102] Examples of cycloalkyl-alkanecarboxylic acid components include cyclopropylacetic acid, cyclobutylacetic acid, cyclopentylacetic acid, 3-cyclopentylpropionic acid, cyclohexylacetic acid, 3-cyclohexylpropionic acid, and 4-cyclohexylbutanoic acid. 3-10 Cycloalkyl-C 1-6 Examples include alkane-carboxylic acid components.

[0103] Examples of crosslinked cyclic alkyl-alkanecarboxylic acid components include bi- or tricycloalkyl-C such as 1-adamantylacetic acid. 1-4 Examples include alkane-carboxylic acid components.

[0104] Examples of alkyl-cycloalkyl-alkanecarboxylic acid components include C3-(3-ethylcyclopentyl)propionic acid. 1-4 Alkyl-C 5-10 Cycloalkyl-C 1-4 Examples include alkane-carboxylic acid components.

[0105] Aromatic monocarboxylic acid components may include, for example, benzoic acid, methylbenzoic acid, naphthalenecarboxylic acid, and C which may have substituents (such as alkyl groups). 6-10 Examples include arene-carboxylic acid components.

[0106] The monocarboxylic acid component may be included alone or in combination of two or more types, and may also be a naphthenic acid component, etc.

[0107] The carboxylic acid component (a2) may be a monocarboxylic acid component, but a polycarboxylic acid component (especially a dicarboxylic acid component) is preferred because it is easier to effectively suppress the vaporization and / or decomposition of the carboxylic acid component (a2) and is easier to handle when preparing the resin composition (B) (e.g., by melt kneading) or forming it into a molded article.

[0108] Examples of polycarboxylic acid components include aliphatic polycarboxylic acid components [aliphatic dicarboxylic acid components; alkanetri or hexacarboxylic acid components (propanetricarboxylic acid, butanetricarboxylic acid, pentanetricarboxylic acid, butanetetracarboxylic acid, etc.) C 2-6 Alkane tri or tetracarboxylic acid components, etc.; trivalent or higher aliphatic polycarboxylic acid components such as ethylenediaminetetraacetic acid, etc.; Alicyclic polycarboxylic acid components [Alicyclic dicarboxylic acid components; Cycloalkane tri or hexacarboxylic acid components (Cyclobutanetetracarboxylic acid, cyclohexanetetracarboxylic acid, etc.) 4-8 [Cycloalkane-tri or tetracarboxylic acid components, etc.]; Alicyclic polycarboxylic acid components with a valency of 3 or higher, such as cycloalkane-tri or tetracarboxylic acid components; Aromatic polycarboxylic acid components [Aromatic dicarboxylic acid components; Arene tri or hexacarboxylic acid components (such as trimellitic acid, pyromellitic acid, meritolic acid, etc. C 6-10 Examples include trivalent or higher aromatic polycarboxylic acid components (such as arene-tri or tetracarboxylic acid components). The polycarboxylic acid components may be used alone or in combination of two or more types. The polycarboxylic acid components may also be trivalent or higher polycarboxylic acid components, and in particular, dicarboxylic acid components such as aliphatic dicarboxylic acid components, alicyclic dicarboxylic acid components, and aromatic dicarboxylic acid components are preferred because they offer an excellent balance between fluidity and heat aging resistance in the resin composition (B).

[0109] Examples of aliphatic dicarboxylic acid components include alkanedicarboxylic acid (linear or branched alkanedicarboxylic acid) components, specifically glutaric acid, adipic acid, pimelic acid, azelaic acid, suberic acid, sebacic acid, decanedicarboxylic acid, etc. 3-12Alkane-dicarboxylic acid components, etc.; Unsaturated aliphatic dicarboxylic acid (linear or branched unsaturated aliphatic dicarboxylic acid) components, specifically C such as itaconic acid. 3-10 Examples include alkene-dicarboxylic acid components.

[0110] Examples of alicyclic dicarboxylic acid components include cycloalkane dicarboxylic acid components, specifically cyclohexanedicarboxylic acid (e.g., 1,4-cyclohexanedicarboxylic acid, etc.) and C 3-10 Cycloalkane-dicarboxylic acid components, etc.; crosslinked cyclic cycloalkane-dicarboxylic acid components, specifically decalindicarboxylic acid, norbornanedicarboxylic acid, adamantanedicarboxylic acid, tricyclodecanedicarboxylic acid, etc. or tricycloalkane-dicarboxylic acid components, etc.; cycloalkenedicarboxylic acid components, specifically cyclohexenedicarboxylic acid, etc. 5-10 Examples include cycloalkene-dicarboxylic acid components; specifically, bi- or tricycloalkenedicarboxylic acid components such as norbornenedicarboxylic acid.

[0111] Preferred alicyclic dicarboxylic acid components include cycloalkane dicarboxylic acid components; more preferably C 4-8 It is a cycloalkane-dicarboxylic acid component; in particular, C such as cyclohexanedicarboxylic acid (1,4-cyclohexanedicarboxylic acid, etc.) 5-8 Cycloalkane-dicarboxylic acid components are preferred.

[0112] Examples of aromatic dicarboxylic acid components include monocyclic aromatic dicarboxylic acid components and polycyclic aromatic dicarboxylic acid components.

[0113] Examples of monocyclic aromatic dicarboxylic acid components include benzenedicarboxylic acid components such as phthalic acid, terephthalic acid, and isophthalic acid; and alkylbenzenedicarboxylic acid components, specifically C such as 4-methylisophthalic acid. 1-4 Examples include alkylbenzene dicarboxylic acid components.

[0114] Examples of polycyclic aromatic dicarboxylic acid components include condensed polycyclic aromatic dicarboxylic acid components, specifically naphthalenedicarboxylic acid (e.g., 1,2-, 1,4-, 1,5-, 1,8-, 2,3-, or 2,6-naphthalenedicarboxylic acid), anthracenedicarboxylic acid, phenantradicarboxylic acid, and other condensed polycyclic C 10-14 Allene-dicarboxylic acid components, etc.; biaryldicarboxylic acid components, specifically biphenyldicarboxylic acid components such as 2,2'- or 4,4'-biphenyldicarboxylic acid; diarylalkanedicarboxylic acid components, specifically diC such as 4,4'-diphenylmethanedicarboxylic acid. 6-10 Aryl C 1-6 Alkane-dicarboxylic acid components, etc.; diarylketonedicarboxylic acid components, specifically, di(C) such as 4,4'-diphenylketonedicarboxylic acid. 6-10 Aryl)ketone-dicarboxylic acid components, etc.; diaryl ether dicarboxylic acid components, specifically, di(C) such as 4,4'-diphenyl ether dicarboxylic acid. 6-10 aryl) ether-dicarboxylic acid components, etc.; diaryl sulfone dicarboxylic acid components, specifically, di(C) such as 4,4'-diphenyl sulfone dicarboxylic acid. 6-10 Examples include aryl)sulfone-dicarboxylic acid components.

[0115] Preferred aromatic dicarboxylic acid components include monocyclic aromatic dicarboxylic acid components, condensed polycyclic aromatic dicarboxylic acid components, and arene dicarboxylic acid components that may have substituents (such as alkyl groups), such as biaryl dicarboxylic acid components (such as biphenyl dicarboxylic acid components); more preferably substituents (C) such as terephthalic acid and naphthalenedicarboxylic acid. 1-6 C may have alkyl groups, etc. 6-10 Arene-dicarboxylic acid component; particularly preferably substituents such as terephthalic acid (C) 1-4 Examples include benzenedicarboxylic acid components that may have alkyl groups (or similar).

[0116] Polycarboxylic acid components (especially dicarboxylic acid components) may be included individually or in combination of two or more types.

[0117] Preferred polycarboxylic acid components (especially dicarboxylic acid components) include aliphatic dicarboxylic acid components such as alkanedicarboxylic acid components and alicyclic dicarboxylic acid components such as cycloalkanedicarboxylic acid components (C 8-12 Aromatic dicarboxylic acid components (C) include alicyclic dicarboxylic acid components, monocyclic aromatic dicarboxylic acid components, polycyclic aromatic dicarboxylic acid components (condensed polycyclic aromatic dicarboxylic acid components, biaryl dicarboxylic acid components, etc.) 8-12 Examples include aromatic dicarboxylic acid components; more preferably, aliphatic dicarboxylic acid components such as alkane dicarboxylic acid components. Preferred aliphatic dicarboxylic acid components are, in order below, C 5-12 Aliphatic dicarboxylic acid component (C 3-10 (Alkane-dicarboxylic acid components, etc.), C 5-10 Aliphatic dicarboxylic acid component (C 3-8 (Alkane-dicarboxylic acid components, etc.), C 5-8 Aliphatic dicarboxylic acid components (such as adipic acid) 3-6 It may also be an alkane-dicarboxylic acid component, etc.; more preferably, taking into consideration ease of handling and productivity, C 6-12 Aliphatic dicarboxylic acid components (such as adipic acid and sebacic acid) 4-10 (Alkane-dicarboxylic acid components, etc.), C 6-11 Aliphatic dicarboxylic acid component (C 4-9 (Alkane-dicarboxylic acid components, etc.), C 7-10 Aliphatic dicarboxylic acid component (C 5-8 (Alkane-dicarboxylic acid components, etc.), C 8-10 Aliphatic dicarboxylic acid components (C 6-8 (Alkane-dicarboxylic acid components, etc.), C 9-10 Aliphatic dicarboxylic acid components (such as sebacic acid) 7-8 These include alkane-dicarboxylic acid components.

[0118] The polycarboxylic acid component (preferably a dicarboxylic acid component such as an aliphatic dicarboxylic acid component, an alicyclic dicarboxylic acid component, and an aromatic dicarboxylic acid component, particularly an aliphatic dicarboxylic acid component) may be the main component of the carboxylic acid component (a2), and its proportion may be, for example, about 30 to 100% by mass relative to the total carboxylic acid component (a2), preferably in stages of 50% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, and substantially 100% by mass or more.

[0119] The carboxylic acid component (a2) suppresses vaporization and / or decomposition in high-temperature environments [for example, when mixed or kneaded with a resin (e.g., melt kneaded), or when used in a high-temperature environment as a molded article of the resin composition (B) described later], and thus effectively improves the heat aging resistance and fluidity of the resin composition (B). Therefore, its boiling point (or sublimation or thermal decomposition temperature) at normal pressure (1 atm) may be, for example, 150°C or higher (e.g., around 200-400°C), preferably 230°C or higher (e.g., 250-380°C), and more preferably 280°C or higher (e.g., 300-350°C).

[0120] The carboxylic acid component (a2) may also be in the form of a salt (carboxylate salt), and examples of salts include metal salts, specifically alkali metal salts such as sodium salts, alkaline earth metal salts such as magnesium salts and calcium salts; and ammonium salts. It is preferable that the carboxylic acid component (a2) is in the form of an acid rather than a salt.

[0121] The ratio of the fluorene compound (a1) to the carboxylic acid component (a2) may be, for example, the former / latter (mass ratio) = approximately 10 / 90~99.9 / 0.1, and from the standpoint of more effectively suppressing the decrease in heat aging resistance in the resin composition (B) (or maintaining or improving heat aging resistance), the following stepwise ratios are preferred: 25 / 75~99 / 1, 30 / 70~97 / 3, 40 / 60~95 / 5, 50 / 50~93 / 7, 55 / 45~93 / 7, 60 / 40~93 / 7, and 65 / 35~93 / 7; and from the standpoint of particularly excellent balance between fluidity and heat aging resistance in the resin composition (B), the following stepwise ratios are preferred: 50 / 50~90 / 10, 55 / 45~85 / 15, 60 / 40~80 / 20, and 65 / 35~75 / 25. When the ratio of the carboxylic acid component (a2) to the fluorene compound (a1) is within a moderate range, not too high, it tends to effectively suppress the decrease in heat aging resistance (especially maintaining or improving heat aging resistance) while improving fluidity. When the ratio is within a moderate range, not too low, it tends to effectively suppress the decrease in heat aging resistance while effectively improving fluidity.

[0122] (Other components (a3)) Composition (A) may or may not contain other components (a3) ​​different from the fluorene compound (a1) and the carboxylic acid component (a2), as needed. Examples of other components (a3) ​​include other flow improvers, amides, sulfoxides, and conventional additives.

[0123] Other fluidity improvers include, for example, compounds having a 9,9-bisarylfluorene skeleton, specifically 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-phenylphenyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)fluorene, 9,9-bis(5-hydroxy-1-naphthyl)fluorene, which may have substituents (such as hydrocarbon groups like methyl groups), such as 9,9-bis(hydroxyaryl)fluorene; 9,9-bis[4- Examples include 9,9-bis[hydroxy(poly)alkoxy-aryl]fluorene, which may have substituents (such as hydrocarbon groups like methyl groups), such as (2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, and 9,9-bis[5-(2-hydroxyethoxy)-1-naphthyl]fluorene. Other fluidity improvers may be used alone or in combination of two or more.

[0124] Composition (A) may optionally contain amides. Combining the fluorene compound (a1) with amides appears to further improve fluidity while suppressing a decrease in heat aging resistance (heat resistance or thermal stability) when mixed with the resin, and also while suppressing discoloration or yellowing.

[0125] Examples of amides include N,N-dialkyl-acylamides, specifically N,N-dimethylformamide (DMF), N,N-diethylformamide, and N,N-dimethylacetamide (DMAc), which are N,N-diC 1-4 Examples include alkyl-(form or acet)amides. Amides may be included individually or in combination of two or more types.

[0126] The proportion of amides may be 10% by mass or more (for example, 10 to 30% by mass) relative to the total amount of fluorene compound (a1) and amides, but from the viewpoint of suppressing the stickiness of composition (A) and effectively improving handling, the proportion of amides is preferably less than 10% by mass (for example, 0.005 to 9% by mass) relative to the total amount of fluorene compound (a1) and amides, and more preferably, in stages, 8% by mass or less, 7% by mass or less, 6% by mass or less, 5% by mass or less, 4% by mass or less, 3% by mass or less, and 2.5% by mass or less (for example, 0.05 to 2.2% by mass), and even more preferably 0.08 to 2% by mass (for example, 0.1 to 1.8% by mass), and particularly 0.2 to 1.7% by mass (for example, 0.3 to 1.5% by mass). When the proportion of amides is within a moderate range, not too low, fluidity tends to be improved, and when it is within a moderate range, not too high, handling properties and heat aging resistance (heat resistance or thermal stability) tend to be improved.

[0127] The ratio of fluorene compound (a1) to amides may be, for example, the former / latter (mass ratio) = approximately 91 / 9 to 99.995 / 0.005, preferably in the following increments: 92 / 8 to 99.99 / 0.01, 93 / 7 to 99.98 / 0.02, 94 / 6 to 99.97 / 0.03, 95 / 5 to 99.96 / 0.04, 96 The ranges are / 4~99.95 / 0.05, 97 / 3~99.95 / 0.05, 97.5 / 2.5~99.95 / 0.05, 97.8 / 2.2~99.95 / 0.05, 98 / 2~99.92 / 0.08, 98.2 / 1.8~99.9 / 0.1, 98.3 / 1.7~99.8 / 0.2, and 98.5 / 1.5~99.7 / 0.3. When the proportion of amides is within a moderate range that is not too low, fluidity tends to be more easily improved, and when it is within a moderate range that is not too high, handling and heat aging resistance (heat resistance or thermal stability) tend to be more easily improved.

[0128] Furthermore, composition (A) may contain sulfoxides [such as dialkyl sulfoxides like dimethyl sulfoxide (DMSO)], but it is preferable that it does not contain sulfoxides in order to suppress the decrease in heat aging resistance, suppress discoloration or yellowing, suppress odor, and more easily improve fluidity. The proportion of sulfoxides may be, for example, about 0 to 5% by mass of the whole of composition (A), and preferably in the following steps: 3% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.1% by mass or less (for example, 0.001 to 0.05% by mass), and in particular, substantially 0% by mass.

[0129] Examples of commonly used additives include those similar to those exemplified as other components (b3) described later. Commonly used additives may be used alone or in combination of two or more.

[0130] Furthermore, composition (A) may contain a resin, but it is preferable that it is a composition that is substantially free of resin (a non-resin composition).

[0131] Other components (a3) ​​may be included alone or in combination of two or more. The proportion of other components (a3) ​​may be, for example, about 0 to 50% by mass relative to the whole of composition (A), preferably in stages of 30% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, and 3% by mass or less (for example, 0.01 to 1.5% by mass, 0.1 to 1% by mass, etc.), and in particular, it may be substantially 0% by mass.

[0132] The total amount of the fluorene compound (a1) and the carboxylic acid component (a2) may be the largest in composition (A) [it may be the main component, which is larger than the proportion of any other component in composition (A) individually], and may be, for example, about 30 to 100% by mass of the whole of composition (A), preferably in stages of 50% by mass or more, 70% by mass or more, 80% by mass or more, and 90% by mass or more (for example, about 95 to 99.9% by mass and about 98 to 99.5% by mass), and in particular, substantially 100% by mass. When the total amount of the fluorene compound (a1) and the carboxylic acid component (a2) is within a moderate range that is not too small, it tends to improve fluidity.

[0133] The properties (or shape) of composition (A) are not particularly limited, but from the viewpoint of handling, it is preferable that it be in a solid state at 25°C and 1 atmosphere, and more preferably in a powder state.

[0134] The method for producing composition (A) is not particularly limited, and for example, it may be prepared by mixing a fluorene compound (a1), a carboxylic acid component (a2), and [other components (a3) ​​as needed]. The mixing method is not particularly limited, and examples include dry mixing, wet mixing, melt kneading, etc. Specifically, the mixture may be mixed using conventional mixers or kneaders such as extruders (single-screw, twin-screw or multi-screw extruders, etc.), kneaders, mixers (Banbury mixers, Henschel mixers, etc.), plastmills, rolls (mixing rolls), etc., or it may be mixed by placing the mixture in a predetermined container (or bag), sealing it, and shaking it.

[0135] [Resin composition (B) and masterbatch (C)] The resin composition (B) may contain at least a fluorene compound (a1), a carboxylic acid component (a2), and a resin [also called resin (b)], for example, it may contain at least composition (A) and resin (b).

[0136] (Resin (b)) The resin (b) is not particularly limited, but examples include curable resins (thermo- or photo-curable resins) and thermoplastic resins.

[0137] Examples of curable resins (thermal or photocurable resins) include phenolic resins (resol type, novolac type, etc.); amino resins (urea resin, melamine resin, guanamine resin, etc.); furan resins; unsaturated polyester resins; diallyl phthalate resins; vinyl ester resins [or epoxy (meth)acrylate resins]; polyfunctional (meth)acrylate resins; epoxy resins; urethane resins; polyimide resins; and silicone resins.

[0138] Examples of thermoplastic resins include polyolefin resins (such as chain-like or cyclic olefin resins); styrene resins [polystyrene (PS) or styrene copolymers (including high-impact polystyrene (HIPS), rubber-containing styrene resins such as ABS resin (or rubber-grafted styrene copolymers))]; (meth)acrylic resins [such as (meth)acrylic monomers alone or copolymers]; vinyl acetate resins [including polyvinyl alcohol (PVA) and polyvinyl acetal]; vinyl chloride resins (such as vinyl chloride and / or vinylidene chloride alone or copolymers); fluororesins; polyester resins [polyalkylene arylate resins, polyarylate resins, liquid crystalline polyesters, polycarbonate resins (PC) (for example, bisphenol type polycarbonates such as bisphenol A)] Examples include: nate resins, etc.; polyamide resins (PA) [aliphatic polyamide resins, aromatic polyamide resins (aramid resins), etc.]; polyurethane resins (thermoplastic polyurethane resins); polyacetal resins (POM); polyphenylene ether resins (PPE); polyphenylene sulfide resins (PPS); polysulfone resins [polysulfone resins (PSF), polyethersulfone (PES), etc.]; polyetherketone resins [polyetherketone resins (PEK), polyetheretherketone resins (PEEK), polyetherketone etherketone ketone (PEKEKK), etc.]; phenoxy resins; polyketone resins; cellulose derivatives (cellulose esters, cellulose ethers, etc.); thermoplastic polyimide resins; polyethernitrile resins; thermoplastic elastomers (TPE), etc.

[0139] Resin (b) may be included alone or in combination of two or more types. From the viewpoint of improving melt flowability, a preferred resin (b) is a thermoplastic resin, and a more preferred resin (b) is a resin that contains at least one structure selected from ester bonds [-C(=O)-O-], amide bonds [-C(=O)-NH-] and urethane bonds [-OC(=O)-NH-] in its chemical structure (particularly a resin that contains a chemical structure forming the main chain), and it is even more preferable to include at least one selected from polyester resins, polyamide resins (PA) and polyurethane resins (thermoplastic polyurethane resins), and among these, polyamide resins (PA) or polyurethane resins, particularly polyamide resins (PA), are preferred.

[0140] The ratio of polyamide resin (PA) (especially the aliphatic polyamide resin described later) to the total resin (b) [or the total amount of the first resin (b1) and the second resin (b2) described later] may be selected from a range of, for example, 10% by mass or more (for example, 30 to 100% by mass), preferably in stages of 50% 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 more preferably substantially 100% by mass.

[0141] (Polyamide resin (PA)) Conventional polyamide resins can be used as the polyamide resin (PA), and may be formed from, for example, aliphatic monomer components, alicyclic monomer components, and / or aromatic monomer components.

[0142] In this specification and in the claims, the monomer component having a carboxyl group, such as a dicarboxylic acid, described later may be an amide-forming derivative, such as an acid halide such as an acid chloride, or an acid anhydride.

[0143] Examples of aliphatic monomer components include aliphatic diamine components, aliphatic dicarboxylic acid components, aliphatic aminocarboxylic acid components, and lactam components.

[0144] Examples of aliphatic diamine components include alkylenediamines (linear or branched alkylenediamines), specifically tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, 2-methyloctamethylenediamine, trimethylhexamethylenediamine, decamethylenediamine, dodecamethylenediamine, etc. 2-20 Examples include alkylenediamines, preferably C 4-16 Alkylenediamine, more preferably C 6-12 It is an alkylenediamine.

[0145] Examples of aliphatic dicarboxylic acid components include saturated aliphatic dicarboxylic acids (alkanedicarboxylic acids) and unsaturated aliphatic dicarboxylic acids.

[0146] Examples of alkanedicarboxylic acids (linear or branched alkanedicarboxylic acids) include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and 1,10-decanedicarboxylic acid. 1-20 Examples include alkane-dicarboxylic acids, preferably C 2-16 Alkane-dicarboxylic acids, more preferably adipic acid, sebaciic acid, 1,10-decanedicarboxylic acid, etc. 4-12 It is an alkane-dicarboxylic acid.

[0147] Examples of unsaturated aliphatic dicarboxylic acids include maleic acid, fumaric acid, and itaconic acid. 2-10 Examples include alkene-dicarboxylic acids.

[0148] Examples of aliphatic aminocarboxylic acid components include amino C such as 6-aminohexanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. 2-20 Examples include alkyl carboxylic acids, preferably amino C 3-16 Alkyl carboxylic acid, more preferably amino C 5-11 It is an alkylcarboxylic acid.

[0149] The lactam component may be a lactam corresponding to the aliphatic aminocarboxylic acid, and examples thereof include lactams having a 4- to 13-membered ring such as ε-caprolactam and ω-laurolactam, and preferably lactams having a 7- to 13-membered ring.

[0150] The alicyclic monomer component only needs to have an alicyclic skeleton (or an aliphatic hydrocarbon ring skeleton), and examples thereof include an alicyclic diamine component, an alicyclic dicarboxylic acid component, and an alicyclic aminocarboxylic acid component.

[0151] Examples of the alicyclic diamine component include diaminocycloalkanes, bis(aminoalkyl)cycloalkanes, and bis(aminocyclohexyl)alkanes.

[0152] Examples of the diaminocycloalkane include diaminocyclohexane and other diaminocycloalkanes. 5-10 Such as cycloalkanes.

[0153] Examples of the bis(aminoalkyl)cycloalkane include bis(aminomethyl)cyclohexane and other bis(aminocycloalkyl)cycloalkanes. 1-4 alkyl)cycloalkanes. 5-10 Such as cycloalkanes.

[0154] Examples of the bis(aminocyclohexyl)alkane include bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, and other bis(aminocyclohexyl)alkanes; bis(4-amino-3-methylcyclohexyl)methane, bis(4-amino-3,5-dimethylcyclohexyl)methane, 2,2-bis(4-amino-3-methylcyclohexyl)propane, and other bis(amino-monoto trialkyl)-cycloalkyl)alkanes. 1-6 Such as alkanes; 1-6 alkyl-cycloalkyl)alkanes. 5-10 Such as cycloalkanes. 1-6 Such as alkanes.

[0155] Examples of alicyclic dicarboxylic acid components include cycloalkanedicarboxylic acids, crosslinked cyclic cycloalkanedicarboxylic acids, cycloalkenedicarboxylic acids, and crosslinked cyclic cycloalkenedicarboxylic acids.

[0156] Examples of cycloalkanedicarboxylic acids include C1,4-cyclohexanedicarboxylic acid. 5-10 Examples include cycloalkane-dicarboxylic acids.

[0157] Examples of crosslinked cyclic cycloalkanedicarboxylic acids include decalindicarboxylic acid, norbornanedicarboxylic acid, adamantanedicarboxylic acid, tricyclodecanedicarboxylic acid, and other bi or tricycloalkanedicarboxylic acids.

[0158] Examples of cycloalkenedicarboxylic acids include C15, such as cyclohexenedicarboxylic acid. 5-10 Examples include cycloalkene-dicarboxylic acids.

[0159] Examples of cross-linked cyclic cycloalkenedicarboxylic acids include bi- or tricycloalkenedicarboxylic acids such as norbornenedicarboxylic acid.

[0160] Examples of alicyclic aminocarboxylic acid components include aminocycloalkanecarboxylic acids, specifically aminoC, such as aminocyclohexanecarboxylic acid. 5-10 Examples include cycloalkane-carboxylic acids.

[0161] Aromatic monomer components only need to have an aromatic ring skeleton; examples include aromatic (or aromatic aliphatic) diamine components, aromatic (or aromatic aliphatic) dicarboxylic acid components, and aromatic (or aromatic aliphatic) aminocarboxylic acid components.

[0162] Examples of aromatic (or aromatic aliphatic) diamine components include diaminoarenes and bis(aminoalkyl)arenes. Examples of diaminoarenes include diaminoC such as m-phenylenediamine and p-phenylenediamine. 6-14 Examples include arenes, and bis(aminoalkyl)arenes include, for example, m-xylylenediamine and other bis(aminoC 1-4 Examples include alkylarenes.

[0163] Examples of aromatic (or aromatic aliphatic) dicarboxylic acid components include benzenedicarboxylic acid, alkylbenzenedicarboxylic acid, polycyclic arenedicarboxylic acid, diarylalkanedicarboxylic acid, diarylketonedicarboxylic acid, diaryletherdicarboxylic acid, diarylsulfidedicarboxylic acid, and diarylsulfonedicarboxylic acid.

[0164] Examples of benzenedicarboxylic acids include phthalic acid, isophthalic acid, and terephthalic acid. Examples of alkylbenzenedicarboxylic acids include 4-methylisophthalic acid and 5-methylisophthalic acid. 1-4 Examples include alkylbenzene dicarboxylic acids.

[0165] Examples of polycyclic arenedicarboxylic acids include condensed polycyclic arenedicarboxylic acids and ring-assembled arenedicarboxylic acids.

[0166] Examples of condensed polycyclic arenedicarboxylic acids include naphthalenedicarboxylic acids such as 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid; anthracenedicarboxylic acids; and condensed polycyclic C12C 10-24 Examples include arene-dicarboxylic acids, preferably condensed polycyclic C111. 10-14 Examples include allene-dicarboxylic acids.

[0167] Examples of the cyclic aromatic dicarboxylic acids include di-C such as 2,2'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, etc. 6-10 Examples also include aromatic-dicarboxylic acids.

[0168] Examples of the diarylalkane dicarboxylic acids include di-C such as 4,4'-diphenylmethanedicarboxylic acid, etc. 6-10 aryl-C 1-6 Examples also include aryl-C alkane-dicarboxylic acids.

[0169] Examples of the diarylketone dicarboxylic acids include di(C such as 4,4'-diphenylketonedicarboxylic acid, etc. 6-10 Examples also include di(aryl)ketone-dicarboxylic acids.

[0170] Examples of the diarylether dicarboxylic acids include di(C such as 4,4'-diphenyletherdicarboxylic acid, etc. 6-10 Examples also include di(aryl)ether-dicarboxylic acids.

[0171] Examples of the diarylsulfide dicarboxylic acids include di(C such as 4,4'-diphenylsulfidedicarboxylic acid, etc. 6-10 Examples also include di(aryl)sulfide-dicarboxylic acids.

[0172] Examples of the diarylsulfone dicarboxylic acids include di(C such as 4,4'-diphenylsulfonedicarboxylic acid, etc. 6-10 Examples also include di(aryl)sulfone-dicarboxylic acids.

[0173] <( Examples of the aromatic aminocarboxylic acid components include aminoarene carboxylic acids such as aminoarene carboxylic acids. Examples of the aminoarene carboxylic acids include amino-C such as aminobenzoic acid, etc. 6-12 Examples also include amino-C arene-carboxylic acids.

[0174] Polyamide resins can be formed by using these monomer components individually or in combination of two or more. For example, they may be formed by polymerization of diamine and dicarboxylic acid components, polymerization of aminocarboxylic acid and / or lactam components, or polymerization of diamine and dicarboxylic acid components with aminocarboxylic acid and / or lactam components. Furthermore, polyamide resins may be homopolyamides formed from a single monomer component (a single diamine and dicarboxylic acid component, a single aminocarboxylic acid component, or a single lactam component), or copolyamides formed by copolymerization of multiple monomer components. Typical polyamide resins include, for example, aliphatic polyamide resins, alicyclic polyamide resins, and aromatic polyamide resins.

[0175] Aliphatic polyamide resins can be formed from aliphatic monomer units derived from aliphatic monomer components. Examples include homopolyamides of aliphatic diamine components and aliphatic dicarboxylic acid components such as polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyamide 810, polyamide 1010, polyamide 1012, and polyamide 1212; homopolyamides of aliphatic aminocarboxylic acid components and / or corresponding lactam components such as polyamide 6, polyamide 11, and polyamide 12; and copolymers (copolyamides) of multiple aliphatic monomer components such as copolyamide 6 / 66, copolyamide 6 / 11, and copolyamide 66 / 12.

[0176] Alicyclic polyamide resins only need to have alicyclic monomer units derived from alicyclic monomer components, and may be formed by combining aliphatic monomer components and alicyclic monomer components. Typical examples of alicyclic polyamide resins include homopolyamides of alicyclic diamine components and aliphatic dicarboxylic acid components, such as polymers of diaminomethylcyclohexane and adipic acid.

[0177] Aromatic polyamide resins only need to have aromatic monomer units derived from at least an aromatic monomer component. Examples include semi-aromatic polyamide resins formed from an aromatic monomer component and an aliphatic or alicyclic monomer component; and fully aromatic polyamide resins formed from an aromatic monomer component and not containing an aliphatic or alicyclic monomer component.

[0178] Examples of semi-aromatic polyamide resins include homopolyamides of aromatic (or aromatic aliphatic) diamines and aliphatic dicarboxylic acids, such as polyamide MXD6 (polymer of m-xylylenediamine and adipic acid); polyamide 6T (polymer of hexamethylenediamine and terephthalic acid); polyamide 9T (polymer of nonamethylenediamine and terephthalic acid); polyamide 10T (polymer of decamethylenediamine and terephthalic acid); polyamide 12T (polymer of dodecamethylenediamine and terephthalic acid); and polyamide M5T (polymer of 2-methylpentamethylenediamine and terephthalic acid). Examples include homopolyamides of aliphatic diamines and aromatic dicarboxylic acids, such as polymers with phthalic acid, polyamide M8T (polymer of 2-methyloctamethylenediamine and terephthalic acid), polyamide 6I (polymer of hexamethylenediamine and isophthalic acid), and polymers of trimethylhexamethylenediamine and terephthalic acid; and copolymers containing at least an aliphatic diamine component and an aromatic dicarboxylic acid component, such as copolyamide 6T / 66, copolyamide 6T / M5T, copolyamide 6T / 6I, copolyamide 6T / 6I / 6, and copolyamide 6T / 6I / 66.

[0179] Examples of fully aromatic polyamide resins include homopolyamides of aromatic diamine components and aromatic dicarboxylic acid components, such as polymers of m-phenylenediamine and isophthalic acid, and polymers of p-phenylenediamine and terephthalic acid.

[0180] In this specification and in the claims, the " / " in "copolyamide" means that the monomer components (units) described before and after it are used as copolymer components (copolymer units) to form the copolyamide. That is, copolyamide 6 / 66 means that it is a copolymer having units that form polyamide 6 and units that form polyamide 66.

[0181] The polyamide resin may be a polyamide having an N-alkoxymethyl group, or a polymerized fatty acid polyamide resin in which dimer acid, a dimer of an unsaturated higher fatty acid, is used as the polymerization component. The polyamide resin may also be crystalline or amorphous, and may be a transparent polyamide resin (amorphous transparent polyamide resin). From the viewpoint of the mechanical properties of the molded product, a crystalline resin is preferred.

[0182] Polyamide resins may be included alone or in combination of two or more types. Preferred polyamide resins are aliphatic polyamide resins. Polyamide resins may also include, for example, C 4-11 Alkylene group, preferably C 4-10 Alkylene group (e.g., C 5-10 Alkylene group), more preferably C 4-8 Alkylene group (e.g., C 4-6 It is preferable that the resin be formed from a monomer component containing an aliphatic monomer component having an alkylene group in its chemical structure, and in particular, an aliphatic polyamide resin formed from an aliphatic monomer component having an alkylene group with the aforementioned number of carbon atoms is preferred. Preferred aliphatic polyamide resins include polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyamide 810, polyamide 1010, polyamide 1012, polyamide 1212, etc. 4-12 Aliphatic diamine component having an alkylene group and C 4-10 Homopolyamides, polyamide 6, polyamide 11, polyamide 12, etc., with aliphatic dicarboxylic acid components having alkylene groups. 5-11Examples include homopolyamides of aliphatic aminocarboxylic acid components having alkylene groups and / or corresponding lactam components, copolyamides of monomer components that form these homopolyamides, etc., such as polyamide 66 and C 4-8 Aliphatic diamine component having an alkylene group and C 4-8 Homopolyamides, polyamide 6, polyamide 11, etc., with aliphatic dicarboxylic acid components having alkylene groups. 5-10 Homopolyamides of aliphatic aminocarboxylic acid components having alkylene groups and / or corresponding lactam components, and copolyamides of monomer components forming these homopolyamides are even more preferred.

[0183] Aliphatic polyamide resin (preferably C) relative to the entire polyamide resin 4-12 Aliphatic diamine component having an alkylene group and C 4-10 Homopolyamide with an aliphatic dicarboxylic acid component having an alkylene group, C 5-11 Homopolyamides of aliphatic aminocarboxylic acid components having alkylene groups and / or corresponding lactam components, and the total amount of copolyamides of monomer components forming these homopolyamides; in particular, C 4-8 Aliphatic diamine component having an alkylene group and C 4-8 Homopolyamide with an aliphatic dicarboxylic acid component having an alkylene group, C 5-10 The proportion of homopolyamides of aliphatic aminocarboxylic acid components having alkylene groups and / or corresponding lactam components, and the total amount of copolyamides of monomer components forming these homopolyamides, may be selected from a range of, for example, 10% by mass or more (for example, 30 to 100% by mass), preferably in stages of 50% 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 more preferably substantially 100% by mass. The above proportions are the same not only for the resin composition (B), but also for the masterbatch (C) described later [i.e., the first resin (b1) described later] and the second resin (b2) described later, including preferred embodiments.

[0184] The number-average molecular weight (Mn) of polyamide resins (especially aliphatic polyamide resins) is, for example, 7,000 to 1,000,000, with preferred ranges being 10,000 to 750,000, 20,000 to 600,000, 30,000 to 500,000, and 50,000 to 500,000. The molecular weight can be evaluated as the molecular weight on a standard polystyrene basis using gel permeation chromatography (GPC).

[0185] In resin composition (B), the ratio of the total amount of fluorene compound (a1) and carboxylic acid component (a2) [or composition (A)] to resin (b) (especially polyamide resins such as aliphatic polyamide resins) is not particularly limited, but for example, the former / latter (mass ratio) may be around 0.01 / 99.99 to 90 / 10 (e.g., 0.05 / 99.95 to 85 / 15), preferably 0.1 / 99.9 to 80 / 20 (e.g., 0.2 / 99.8 to 60 / 40), and more preferably 0.3 / 99.7 to 50 / 50 (e.g., 0.4 / 99.6 to 40 / 60). When the resin composition (B) is molded into a predetermined shape (forms a molded body), the ratio of the total amount of fluorene compound (a1) and carboxylic acid component (a2) [or composition (A)] to the resin (b) (especially polyamide resins such as aliphatic polyamide resins) is such that it easily maintains its shape even in high-temperature environments and has excellent mechanical properties (strength, etc.). For example, the ratio of the former / latter (mass ratio) = 0.01 / 99.99~20 / 80, 0.05 / 99.95~15 / 85, 0.1 / 99.9~10 / 90, 0.2 / 99.8~5 / 95, 0.3 / 99.7~3 / 97, 0.4 / 99.6~2 / 98, 0.5 / 99.5~1.5 / 98.5, and 0.7 / 99.3~1.3 / 98.7. When the total amount of fluorene compound (a1) and carboxylic acid component (a2) [or composition (A)] is within a moderate range that is not too little, it tends to improve fluidity while suppressing a decrease in heat aging resistance. When it is within a moderate range that is not too much, it tends to maintain its shape and suppress a decrease in mechanical properties (such as strength) even when used in high-temperature environments.

[0186] In resin composition (B), the ratio of fluorene compound (a1) to carboxylic acid component (a2) is the same as, for example, the ratio (mass ratio) described in section [Composition (A)] above, including in preferred embodiments.

[0187] (Masterbatch(C)) The masterbatch (C) only needs to contain at least a fluorene compound (a1), a carboxylic acid component (a2), and a resin [also called the first resin (b1)], for example, it may contain at least composition (A) and the first resin (b1). Therefore, the masterbatch (C) is broadly encompassed by the resin composition (B).

[0188] More specifically, masterbatch (C) corresponds to a resin composition containing a fluorene compound (a1) and a carboxylic acid component (a2) [or composition (A)] in a high concentration relative to the resin. By further mixing this masterbatch (C) with a second resin (b2) [or diluting it with the second resin (b2)], a resin composition (B) containing a fluorene compound (a1) and a carboxylic acid component (a2) [or composition (A)] in a desired proportion at a lower concentration than that of masterbatch (C) can be prepared. That is, the first resin (b1) and the second resin (b2) may correspond to the aforementioned resin (b).

[0189] Since the masterbatch (C) is even easier to handle than composition (A), compared to directly preparing resin composition (B) by mixing the fluorene compound (a1) and carboxylic acid component (a2) [or composition (A)] with resin (b) in desired proportions, contamination of machinery (such as a kneader) is suppressed, workability is improved, and resin composition (B) can be produced easily, efficiently (or stably). Therefore, this disclosure also includes a method for producing resin composition (B) by mixing the masterbatch (C) with a second resin (b2).

[0190] Examples of the first resin (b1) include resins similar to those exemplified as resin (b), including preferred embodiments.

[0191] Furthermore, the second resin (b2) can be, for example, a resin similar to the resin exemplified as resin (b) above, including preferred embodiments.

[0192] Furthermore, it is preferable that the first resin (b1) and the second resin (b2) are of the same type or of the same type, and it is even more preferable that they are the same resin.

[0193] The proportion of the polyamide resin (PA) (especially the aliphatic polyamide resin mentioned above) to the total first resin (b1) may be selected from a range of, for example, 10% by mass or more (for example, 30 to 100% by mass), preferably in stages of 50% 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 more preferably substantially 100% by mass.

[0194] Furthermore, the proportion of the polyamide resin (PA) (especially the aliphatic polyamide resin mentioned above) to the total second resin (b2) may be selected from a range of, for example, 10% by mass or more (for example, 30 to 100% by mass), preferably in stages of 50% 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 more preferably substantially 100% by mass.

[0195] In the masterbatch (C), the ratio of the total amount of the fluorene compound (a1) and carboxylic acid component (a2) [or composition (A)] to the first resin (b1) may be, for example, about 5 / 95 to 90 / 10 (e.g., 10 / 90 to 85 / 15) in mass ratio, preferably 20 / 80 to 80 / 20 (e.g., 25 / 75 to 70 / 30), more preferably 30 / 70 to 60 / 40 (e.g., 35 / 65 to 55 / 45), and particularly 40 / 60 to 50 / 50. When the total amount of fluorene compound (a1) and carboxylic acid component (a2) [or composition (A)] is within a moderate range and not too high, the masterbatch (C) tends to be easier to mold into pellets. When it is within a moderate range and not too low, the amount of masterbatch (C) can be reduced when preparing the resin composition (B), which tends to improve work efficiency and reduce costs.

[0196] In addition, in the masterbatch (C), the ratio of the fluorene compound (a1) to the carboxylic acid component (a2) is the same as the ratio (mass ratio) described in the section [Composition (A)] above, including in preferred embodiments.

[0197] The method for producing the masterbatch (C) is not particularly limited, and for example, it may be prepared by mixing the fluorene compound (a1) and the carboxylic acid component (a2) [or composition (A)] with the first resin (b1) [and other components (b3) as described later, if necessary].

[0198] The mixing method used to prepare the masterbatch (C) is not particularly limited and can include, for example, dry mixing, wet mixing, or melt kneading. It may also be mixed using conventional mixers or kneaders such as extruders (single-screw, twin-screw, or multi-screw extruders), kneaders, mixers (Banbury mixers, Henschel mixers, etc.), plast mills, or rolls (mixing rolls). Alternatively, the masterbatch (C) may be formed into strands or pellets using the aforementioned extruders or conventional pelletizers.

[0199] (Other component (b3)) The resin composition (B) and the masterbatch (C) may or may not contain other components (b3) different from the fluorene compound (a1) and carboxylic acid component (a2) [or composition (A)] and resin (b) [first resin (b1) and second resin (b2)]. Examples of other components (b3) include other flow improvers, amides, sulfoxides, and conventional additives.

[0200] Other fluidity improvers include, for example, the fluidity improvers exemplified in section (a3) ​​of composition (A). These other fluidity improvers may be used alone or in combination of two or more.

[0201] The resin composition (B) and the masterbatch (C) may each contain amides. Combining the fluorene compound (a1) with amides appears to further improve fluidity while suppressing a decrease in heat aging resistance (heat resistance or thermal stability) and also suppressing discoloration or yellowing. Examples of amides include those exemplified in the section on other components (a3) ​​in composition (A). The amides may be used alone or in combination of two or more. The proportion of amides [the proportion of amides to the total amount of fluorene compound (a1) and amides, and the proportion of fluorene compound (a1) to amides] is similar to, for example, the proportions (mass ratios) exemplified in the section on other components (a3) ​​in composition (A), including preferred embodiments.

[0202] Furthermore, the resin composition (B) and the masterbatch (C) may each contain sulfoxides [such as dialkyl sulfoxides like dimethyl sulfoxide (DMSO)], but it is preferable that they do not contain sulfoxides in order to suppress the decrease in heat aging resistance, suppress discoloration or yellowing, suppress odor, and improve fluidity. The proportion of sulfoxides may be, for example, about 0 to 5% by mass relative to the total amount of fluorene compound (a1) and carboxylic acid component (a2) in the resin composition (B) or the masterbatch (C), and preferably in the following steps: 3% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.1% by mass or less (for example, 0.001 to 0.05% by mass), and in particular, substantially 0% by mass.

[0203] Commonly used additives include, for example, fillers or reinforcing agents (such as fibrous reinforcing agents), colorants such as dyes and pigments, conductive agents, flame retardants, flame retardant aids, plasticizers, lubricants, stabilizers (e.g., antioxidants, UV absorbers, heat stabilizers), mold release agents, antistatic agents, dispersants, compatibilizers, flow regulators, leveling agents, defoamers, surface modifiers, stress reducers, and carbon materials. Additives may be used individually or in combination of two or more.

[0204] Other components (b3) may be included alone or in combination of two or more. The proportion of other components (b3) may be, for example, 50% by mass or less, 0 to 30% by mass, 1 to 10% by mass, etc., relative to the entire resin composition (B). Alternatively, the proportion of other components (b3) may be, for example, 0 to 50% by mass, preferably in stages, 30% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less (for example, 0.1 to 3% by mass), relative to the entire masterbatch (C).

[0205] In resin composition (B), the total amount of fluorene compound (a1) and carboxylic acid component (a2) [or composition (A)] and resin (b) [first resin (b1) and second resin (b2)] may be the largest among the constituent components [may be a main component in a larger proportion than any other component in resin composition (B)], and may be, for example, 30 to 100% by mass of the entire resin composition (B), preferably in stages below, 50% 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 may be substantially 100% by mass.

[0206] In the masterbatch (C), the total proportion of the fluorene compound (a1) and the carboxylic acid component (a2) [or composition (A)] and the first resin (b1) may be the largest proportion among the constituent components [may be the main component, which may be a larger proportion than any other component in the masterbatch (C)], and may be, for example, 30 to 100% by mass of the entire masterbatch (C), preferably in stages below: 50% 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 may be substantially 100% by mass.

[0207] (Method for producing resin composition (B) and method for improving fluidity) The method for producing the resin composition (B) is not particularly limited. For example, it may be produced by mixing a fluorene compound (a1), a carboxylic acid component (a2), and resin (b); it may be produced by mixing composition (A) and resin (b); or, as described above, it may be produced by mixing (C) with the second resin (b2) [or diluting it with the second resin (b2)]. In these production methods, other components (b3), etc., may be mixed together as needed during the mixing process. The method of mixing the masterbatch (C) with the second resin (b2) is preferred because it can effectively improve productivity (or workability) and fluidity.

[0208] In these manufacturing methods, the mixing method is not particularly limited and examples include dry mixing, wet mixing, and melt kneading. For example, conventional mixers or kneaders such as extruders (single-screw, twin-screw, or multi-screw extruders), kneaders, mixers (Banbury mixers, Henschel mixers, etc.), plast mills, and rolls (mixing rolls) may be used for mixing. Alternatively, the resin composition (B) may be formed into strands or pellets using the aforementioned extruder or conventional pelletizer.

[0209] The disclosure also includes methods for improving fluidity by adding (mixing) a fluorene compound (a1) and a carboxylic acid component (a2) to a resin (b); methods for improving fluidity by adding (mixing) a composition (A) to a resin (b); and methods for improving fluidity by adding (mixing) a masterbatch (C) to a second resin (b2). These methods can improve the fluidity of the resin composition (B) after addition or mixing compared to the fluidity before addition or mixing [the fluidity of resin (b) or the second resin (b2)]. Furthermore, these methods may improve fluidity while suppressing a decrease in heat aging resistance.

[0210] (Properties of resin composition (B)) Resin composition (B) has high fluidity (melt fluidity). Therefore, the melt flow rate (MFR) [or melt flow index (MFI)] of resin composition (B) is, for example, 110 to 1000 (for example, 130 to 500), preferably 150 to 400, and more preferably 200 to 300, when the MFR of a resin composition that does not contain the fluorene compound (a1) and carboxylic acid component (a2) [or composition (A)] [a resin composition containing the same mass of resin (b) instead of the fluorene compound (a1) and carboxylic acid component (a2) [or composition (A)] in resin composition (B), hereinafter simply referred to as "blank"] is set to 100.

[0211] The MFR of the blank is, for example, 10-100 g / 10 min, preferably 20-50 g / 10 min, and more preferably 25-40 g / 10 min, under measurement conditions of a temperature of 265°C or 240°C, a test load of 1.20 kgf, and a holding time of 5 minutes.

[0212] In this specification and in the claims, MFR can be measured in accordance with JIS K 7210-1 B method, and specifically by the method described in the examples below.

[0213] The tensile strength (maximum tensile strength) of resin composition (B) is, for example, about 90 to 120, preferably 100 to 110, when the tensile strength of the blank (before thermal aging test) is set to 100.

[0214] The tensile strength of the blank (before thermal aging test) may be, for example, around 10 to 200 MPa, preferably 50 to 150 MPa, and more preferably 70 to 100 MPa (for example, 80 to 90 MPa).

[0215] Because resin composition (B) has high heat aging resistance (thermal stability), it tends to maintain high tensile strength even when exposed to high-temperature environments. Therefore, the tensile strength after a heat aging test (in air, 120°C, 250 hours) may be, for example, 50 to 99 (for example, 70 to 98), with the strength before the heat aging test set to 100, preferably 80 to 97, more preferably 85 to 96, and particularly 90 to 95.

[0216] In this specification and in the claims, tensile properties can be measured in accordance with JIS K 7161-1,-2, and specifically by the method described in the examples below.

[0217] [Molded body] This disclosure also includes molded articles comprising at least a resin composition (B). The shape of the molded article is not particularly limited and may be selected according to the application. For example, it may be pelletized, a one-dimensional structure such as linear (fibrous or thread-like), rod-like, a two-dimensional structure such as film-like, sheet-like, or plate-like, a three-dimensional structure such as block-like, lens-like (concave or convex lens-like), or hollow (tubular or tubular), or a composite or complex shape combining these shapes.

[0218] Molded articles can be manufactured using conventional molding methods depending on the type of resin, the shape and application of the molded article, and can be produced using methods such as injection molding, compression molding, transfer molding, lamination molding, FRP molding, casting, powder molding, extrusion molding, blow molding, lamination, casting, calendering, foam molding, and 3D printing.

[0219] Furthermore, the molded article may be a composite molded article comprising a resin composition (B) and other constituent members. The proportion of resin composition (B) in the molded article is not particularly limited and may be, for example, 10 to 100% by mass or 20 to 80% by mass. [Examples]

[0220] The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples. Various evaluation methods and raw materials used are also shown below.

[0221] [Evaluation Method] (HPLC) A Shimadzu LCMS-2020 HPLC (High Performance Liquid Chromatography) instrument was used, and a Shimadzu KINTEX XB-C18 column was used. The mobile phase (acetonitrile / water, volume ratio) was changed from 50 / 50 to 95 / 5 over 10 minutes, and then the cell was held at 95 / 5 for 5 minutes.

[0222] (Melt Flow Rate (MFR)) Using the "Meltflow Indexer IMC-1540C" manufactured by Imoto Seisakusho Co., Ltd., measurements were taken in accordance with JIS K 7210-1 Method B, with a holding time of 5 minutes, a temperature of 265°C (example including PA66) or 240°C (example including PA6), and a test load of 1.20 kgf.

[0223] (Tensile test) The tensile strength (maximum tensile strength) was measured using an Instron "Universal Testing Machine Model 5982" in accordance with JIS K 7161-1,-2, at a test speed of 5 mm / min. The test specimens were molded using an injection molding machine (Nissei Plastic Industrial Co., Ltd. "NEX50III").

[0224] (Thermal aging treatment) Using an ESPEC "Perfect Oven PH-302" manufactured by ESPEC Corporation, test specimens for tensile testing were left to stand in air at 120°C for 250 hours to undergo heat aging treatment. The tensile strength (maximum tensile strength) of the treated test specimens was measured in the same manner as described in the (Tensile Test) section above.

[0225] (Mixing and molding properties) The moldability of the obtained resin composition (or masterbatch) was evaluated according to the following criteria.

[0226] ○... Easily moldable into strands (easily moldable into pellets) ×...Difficult to mold into strands (difficult to mold into pellets)

[0227] (Color tone) The color of the obtained resin composition (or masterbatch) was visually inspected.

[0228] [Ingredients, etc.] (reagent) 9H-Fluorene: Manufactured by Tokyo Chemical Industry Co., Ltd. Acrylamide: Manufactured by Fujifilm Wako Pure Chemical Corporation DMF: N,N-dimethylformamide, manufactured by Kanto Chemical Co., Ltd., premium grade. KOH: Potassium hydroxide, manufactured by Kanto Chemical Co., Ltd. Methanol: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (Carboxylic acid component) Adipic acid: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade. Sebacic acid: Manufactured by Fujifilm Wako Pure Chemical Corporation, Wako Grade 1. Cyclohexanedicarboxylic acid: 1,4-cyclohexanedicarboxylic acid (cis- / trans mixture), manufactured by Tokyo Chemical Industry Co., Ltd. Terephthalic acid: Manufactured by Fujifilm Wako Pure Chemical Corporation, Wako Grade 1. (resin) PA6: Polyamide 6, manufactured by UBE Corporation, "UBENYLON(registered trademark) 1013B", good kneadability for molding, pale white. PA66: Polyamide 66, manufactured by Asahi Kasei Corporation as "Leona (registered trademark) 1300S", good kneadability and moldability, pale white. PA11: Polyamide 11, manufactured by ARKEMA, "Rilsan(registered trademark) BMNO", good kneadability, pale white.

[0229] [Synthesis Example 1] Preparation of AAD-FL 9H-fluorene (20.0 g; 0.12 mol) and DMF (41.2 mL) were charged into a reactor equipped with a magnetic stirrer and a three-way stopcock. After purging with nitrogen, the temperature was raised to 65°C, and the dissolution of 9H-fluorene was confirmed. Then, 48% by mass KOH aqueous solution (0.42 g; equivalent to 0.0036 mol (3.6 mmol) of KOH) was added. Furthermore, a mixed solution of DMF (16.5 mL) and acrylamide (17.05 g; 0.24 mol) was added dropwise over 0.5 to 1 hour, and the temperature was raised to 65°C and heated and stirred for 2 hours. The reaction was terminated when the disappearance of 9H-fluorene was confirmed by HPLC. The resulting reaction solution was cooled to 10°C and stirred, and white crystals gradually precipitated, becoming a white suspension. The crystals filtered from the suspension were washed with methanol to obtain the target product, 9,9-bis(2-carbamoylethyl)fluorene (AAD-FL, yield 32.6 g, 88.0%). Although the AAD-FL was dried under reduced pressure using a Tokyo Rikakikai Co., Ltd. "Diaphragm Vacuum Pump EVO-1100" at a temperature of 80°C, a pressure of 10 mmHg, and for 12 hours, trace amounts of DMF remained in the obtained AAD-FL.

[0230] [Examples 1-5] Preparation of fluidity improver (composition (A)) The AAD-FL obtained in Synthesis Example 1 and adipic acid were placed in an aluminum-coated bag (Lamizip, manufactured by Seisan Nippon Co., Ltd.) and sealed. The mixture was then mixed at room temperature and pressure (25°C, 1 atm) to prepare a fluidity improver [Composition (A)] in the mass ratios shown in Table 1 below.

[0231] [Table 1]

[0232] [Examples 6-14] Preparation of resin composition (B) Resin composition (B) was prepared by melt-kneading PA66 and the fluidity improver (A) obtained in Examples 1 to 5 at 280°C using a twin-screw extruder (Thermo Fisher "Process11 TwinScrewExtruder", L / D=40) in the mass ratio shown in Table 2 below, and various evaluations were performed.

[0233] [Reference example 1] Various evaluations were conducted on the PA66 alone.

[0234] [Reference example 2] The resin compositions were prepared in the same manner as in Examples 6-14, except that AAD-FL obtained in Synthesis Example 1 was used instead of the fluidity improver (A) obtained in Examples 1-5, and the mass ratio was as shown in Table 2 below. Various evaluations were then performed.

[0235] [Reference example 3] Resin compositions were prepared in the same manner as in Examples 6-14, except that adipic acid was used instead of the fluidity improver (A) obtained in Examples 1-5, and the mass ratio was as shown in Table 2 below. Various evaluations were then performed.

[0236] The evaluation results of the resin compositions obtained in Examples 6-14 and Reference Examples 1-3 are shown in Table 2 below.

[0237] [Table 2]

[0238] As is clear from the results in Table 2, in Reference Example 2, which had Synthesis Example 1 (AAD-FL) added, and in Reference Example 3, which had adipic acid added, fluidity improved compared to Reference Example 1 (PA66 alone), but tensile strength decreased after heat aging treatment (condition 2).

[0239] In contrast, Examples 6-14, despite containing a combination of Synthesis Example 1 (AAD-FL), which had reduced heat aging resistance in Reference Examples 2-3, and adipic acid, unexpectedly exhibited high heat aging resistance (or suppressed excessive reduction), demonstrating an excellent balance between fluidity and heat aging resistance. This is evident from a comparison between Example 7 and Reference Examples 2-3. Specifically, Example 7 corresponds to a configuration in which a portion of Synthesis Example 1 (AAD-FL) in Reference Example 2 is replaced with adipic acid, as in Reference Example 3. Therefore, it was expected that the MFR and tensile strength (condition 2) of Example 7 would be somewhere between those of Reference Examples 2 and 3, but both the MFR and tensile strength (condition 2) significantly exceeded those of Reference Examples 2 and 3, showing a surprising result.

[0240] In the examples, a lower proportion of adipic acid to Synthesis Example 1 (AAD-FL) was preferable in terms of heat aging resistance, and among them, Example 9 showed a particularly good balance between fluidity and heat aging resistance.

[0241] [Example 15] Preparation of resin composition (B) (or masterbatch (C)) PA66 and the fluidity improver obtained in Example 3 [Composition (A)] were melt-kneaded at 280°C using a twin-screw extruder [Parker Corporation's "Co-rotating Twin-Screw Compounding Extruder HK-25D", L / D=61] in the mass ratio shown in Table 3 below, and a resin composition (B) (or masterbatch (C)) was prepared using a granulator (ECON's Underwater Cutter EUP10). The evaluation results of the obtained resin composition (or masterbatch) are shown in Table 3 along with the results of Examples 13 and 8.

[0242] [Examples 16-19] Preparation of resin composition (B) (or masterbatch (C)) PA6 and the fluidity improver [Composition (A)] obtained in Example 3 were melt-kneaded at 230°C using a twin-screw extruder (Thermo Fisher "Process11 TwinScrewExtruder", L / D=40) in the mass ratio shown in Table 4 below to prepare resin composition (B) (or masterbatch (C)).

[0243] [Examples 20-23] Preparation of resin composition (B) (or masterbatch (C)) Resin composition (B) (or masterbatch (C)) was prepared in the same manner as in [Examples 16-19], except that PA11 was used instead of PA6.

[0244] Table 4 shows the evaluation results of the resin compositions (B) (or masterbatch (C)) obtained in Examples 16 to 23.

[0245] [Table 3]

[0246] [Table 4]

[0247] As is clear from the results in Tables 3-4, the resin compositions (B) (or masterbatch (C)) of the examples could all be molded into strands (pellets) even when they contained high concentrations of AAD-FL and adipic acid.

[0248] [Examples 24-35] Preparation of a fluidity improver (composition (A)) The AAD-FL obtained in Synthesis Example 1 was placed in an aluminum-coated bag (Lamizip, manufactured by Seisan Nippon Co., Ltd.) and sealed. The mixture was then mixed at room temperature and pressure (25°C, 1 atm) to prepare fluidity improvers [Composition (A)] in the mass proportions shown in Tables 5 to 7 below.

[0249] [Table 5]

[0250] [Table 6]

[0251] [Table 7]

[0252] [Examples 36-47] Preparation of resin composition (B) Resin composition (B) was prepared by melt-kneading PA66 and the fluidity improver (A) obtained in Examples 24-35 at 280°C using a twin-screw extruder (Thermo Fisher "Process11 TwinScrewExtruder", L / D=40) in the mass ratios shown in Tables 8-10 below, and various evaluations were performed.

[0253] [Reference examples 4~6] Resin compositions were prepared in the same manner as in Examples 36-47, except that sebacic acid (Reference Example 4), cyclohexanedicarboxylic acid (Reference Example 5), or terephthalic acid (Reference Example 6) were used instead of the fluidity improver (A) obtained in Examples 24-35, and the mass ratios were as shown in Tables 8-10 below. Various evaluations were then performed.

[0254] The evaluation results of the resin compositions obtained in Examples 36-47 and Reference Examples 4-6 are shown in Tables 8-10 below, along with the results for Reference Examples 1-2.

[0255] [Table 8]

[0256] [Table 9]

[0257] [Table 10]

[0258] As is clear from the results in Tables 8-10, Examples 36-47, which contain sebaciic acid, cyclohexanedicarboxylic acid, or terephthalic acid, also exhibited an excellent balance between fluidity and heat aging resistance, similar to Examples 6-14, which contain adipic acid. For example, Examples 36, 40, and 44 correspond to embodiments in which a portion of Synthesis Example 1 (AAD-FL) included in Reference Example 2 is replaced with sebaciic acid, cyclohexanedicarboxylic acid, or terephthalic acid, as in Reference Examples 4-6. Therefore, it was expected that the MFR and tensile strength (condition 2) of Examples 36, 40, and 44 would be somewhere between that of Reference Example 2 and Reference Examples 4-6, respectively. However, all of them significantly exceeded this expectation, demonstrating an excellent balance between fluidity and heat aging resistance.

[0259] [Example 48] Preparation of resin composition (B) (or masterbatch (C)) PA66 and the fluidity improver [composition (A)] obtained in Example 24 were melt-kneaded at 280°C using a twin-screw extruder (Thermo Fisher "Process11 TwinScrewExtruder", L / D=40) in the mass ratio shown in Table 11 below to prepare resin composition (B) (or masterbatch (C)).

[0260] [Examples 49-52] Preparation of resin composition (B) (or masterbatch (C)) PA6 and the fluidity improvers obtained in Examples 24-26 [Composition (A)] were melt-kneaded at 230°C using a twin-screw extruder [Thermo Fisher "Process11 TwinScrewExtruder", L / D=40] in the mass ratios shown in Table 11 below to prepare resin composition (B) (or masterbatch (C)).

[0261] Table 11 shows the evaluation results of the resin compositions (B) (or masterbatch (C)) obtained in Examples 48 to 52.

[0262] [Table 11]

[0263] As is clear from the results in Table 11, the resin compositions (B) (or masterbatch (C)) of the examples could be molded into strands (pellets) even when they contained high concentrations of AAD-FL and sebacic acid.

[0264] [Examples 53-54] Preparation of resin composition (B) PA6 and the fluidity improver [Composition (A)] obtained in Example 5 or 27 were melt-kneaded at 230°C using a twin-screw extruder (Thermo Fisher "Process11 TwinScrewExtruder", L / D=40) in the mass ratio shown in Table 12 below to prepare resin composition (B), and various evaluations were performed.

[0265] [Reference example 7] Various evaluations were conducted on PA6 alone.

[0266] [Reference example 8] The resin compositions were prepared in the same manner as in [Examples 53-54], except that AAD-FL obtained in Synthesis Example 1 was used instead of the fluidity improver (A) obtained in Example 5 or 27, and the mass ratio was as shown in Table 12 below. Various evaluations were then performed.

[0267] The evaluation results of the resin compositions obtained in Examples 53-54 and Reference Examples 7-8, along with the evaluation results for Examples 19 and 52, are shown in Table 12 below.

[0268] [Table 12]

[0269] As is clear from the results in Table 12, the resin composition (B) of the example containing PA6 also exhibited an excellent balance between fluidity and heat aging resistance. [Industrial applicability]

[0270] The compositions (A) and masterbatches (C) of this disclosure can be effectively used as resin modifiers for modifying resins, such as additives for improving the fluidity (melt fluidity or moldability) of resins (fluidity improvers) and / or additives for improving the heat aging resistance (heat resistance or thermal stability) of resins (heat aging resistance improvers), in particular as fluidity improvers.

[0271] The resin composition (B) of this disclosure can be used in a wide range of applications, from household goods to industrial products, depending on the type of resin, and can be used in a broad range of applications such as textile products [e.g., fibers, yarns, ropes, nets, fabrics (woven fabrics, knitted fabrics, nonwoven fabrics, etc.)], films, packaging materials, daily necessities, general merchandise, toys, sports and leisure-related products, vehicle-related parts, electrical and electronic-related parts, machine-related parts, building-related parts, and medical devices.

Claims

1. It comprises at least a fluorene compound (a1) represented by the following formula (1) and a carboxylic acid component (a2), 【Chemistry 1】 [In the formula, R １ represents a substituent, and m1 represents an integer from 0 to 8. R ２ａ , R ２ｂ , R ２ｃ and R ２ｄ These independently represent a hydrogen atom or a substituent. R ３ａ and R ３ｂ These independently represent a hydrogen atom or a substituent. X １ａ and X １ｂ are independently represented by the following formula (X1) 【Chemistry 2】 (In the formula, R ４ and R ５ This independently represents a hydrogen atom or a hydrocarbon group, or R ４ and R ５ (This shows a heterocycle formed by the bonding of these atoms with adjacent nitrogen atoms.) This indicates the group represented by [ ]. Composition (A), wherein the carboxylic acid component (a2) comprises a carboxylic acid having 5 or more carbon atoms or a salt thereof.

2. In equations (1) and (X1) above, R １ m1 represents an alkyl group, aryl group, or acyl group, and m1 represents an integer from 0 to 4. R ２ａ , R ２ｂ , R ２ｃ and R ２ｄ These independently represent a hydrogen atom or an alkyl group. R ３ａ and R ３ｂ These independently represent a hydrogen atom or an alkyl group. R ４ and R ５ This independently represents a hydrogen atom or an alkyl group; The composition (A) according to claim 1, wherein the carboxylic acid component (a2) is a polycarboxylic acid having 5 or more carbon atoms or a salt thereof.

3. In equations (1) and (X1) above, R １ is C １－６ Alkyl or C ６－１０ It represents an aryl group, and m1 represents an integer from 0 to 2. R ２ａ , R ２ｂ , R ２ｃ and R ２ｄ These are independently hydrogen atoms or C １－６ It shows an alkyl group, R ３ａ and R ３ｂ These are independently hydrogen atoms or C １－６ It shows an alkyl group, R ４ and R ５ These are independently hydrogen atoms or C １－６ The alkyl group was shown; The composition (A) according to claim 1, wherein the carboxylic acid component (a2) is a dicarboxylic acid having 5 to 12 carbon atoms or a salt thereof.

4. The composition (A) according to any one of claims 1 to 3, wherein the ratio of the fluorene compound (a1) to the carboxylic acid component (a2) is the former / latter (mass ratio) = 25 / 75 to 99 / 1.

5. A fluidity improver comprising the composition (A) described in any one of claims 1 to 3.

6. A method for improving fluidity by adding a fluorene compound (a1) and a carboxylic acid component (a2) according to any one of claims 1 to 3 to a resin (b).

7. The method according to claim 6, which improves fluidity while suppressing a decrease in heat aging resistance.

8. A resin composition (B) comprising a fluorene compound (a1) and a carboxylic acid component (a2) according to any one of claims 1 to 3, and a resin (b).

9. The resin composition (B) according to claim 8, wherein the resin (b) comprises at least one selected from polyester resins, polyamide resins, and polyurethane resins.

10. The resin composition (B) according to claim 8, wherein the ratio of the total amount of the fluorene compound (a1) and the carboxylic acid component (a2) to the resin (b) is the former / latter (mass ratio) = 0.01 / 99.99 to 10 / 90.

11. A method for producing a resin composition (B) by mixing a fluorene compound (a1) and a carboxylic acid component (a2) according to any one of claims 1 to 3 with a resin (b).

12. A molded article comprising the resin composition (B) according to claim 8.

13. A masterbatch (C) comprising a fluorene compound (a1) and a carboxylic acid component (a2) according to any one of claims 1 to 3, and a first resin (b1).

14. The masterbatch (C) according to claim 13, wherein the ratio of the total amount of the fluorene compound (a1) and the carboxylic acid component (a2) to the first resin (b1) is the former / latter (mass ratio) = 5 / 95 to 90 / 10.

15. A resin composition (B) comprising the masterbatch (C) according to claim 13 and a second resin (b2).

16. A method for producing a resin composition (B) by mixing the masterbatch (C) described in claim 13 with a second resin (b2).

17. A molded article comprising the resin composition (B) according to claim 15.

18. A method for improving fluidity by adding the masterbatch (C) described in claim 13 to a second resin (b2).

19. The method according to claim 18, which improves fluidity while suppressing a decrease in heat aging resistance.

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