Composition containing a fluorene compound

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) comprising a fluorene compound (a1) represented by formula (1) and an amide compound (a2) represented by formula (2), wherein the proportion of the amide compound (a2) is less than 10% by mass relative to the total amount of the fluorene compound (a1) and the amide compound (a2). TIFF2026068709000023.tif51154

Description

[Technical Field]

[0001] This disclosure relates to compositions (or flow improvers) comprising specific proportions of a particular fluorene compound (or fluorene derivative) and a particular amide compound, resin compositions and masterbatches comprising this composition (or the particular fluorene compound and the particular amide compound), 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 Initiative] [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] Furthermore, in the examples described in Patent Documents 2 and 3, which describe the use of specific fluorene derivatives as resin additives, it is stated that the fluorene derivatives were synthesized by reacting them in a reaction solvent containing dimethyl sulfoxide (DMSO), and the obtained fluorene derivatives were added to the resin.

[0009] However, as detailed in the Examples section, the inventors discovered that a small amount of DMSO remains in the fluorene derivative, and that this may significantly reduce the heat aging resistance of the resin composition.

[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 amide compound, it is possible to effectively improve fluidity while suppressing a 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 contains at least a fluorene compound (a1) represented by the following formula (1) and an amide compound (a2) represented by the following formula (2). A composition (A) in which the proportion of the amide compound (a2) is less than 10% by mass based on the total amount of the fluorene compound (a1) and the amide compound (a2).

[0013]

Chemical formula

[0014] [In the formula, R 1 represents a substituent, m1 represents an integer from 0 to 8. R 2a , R 2b , R 2c and R 2d independently represent a hydrogen atom or a substituent. R 3a and R 3b independently represent a hydrogen atom or a substituent. X 1a and X 1b independently represent the following formula (X1)

[0015]

Chemical formula

[0016] (In the formula, R 4 and R 5 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]

Chemical formula

[0018] (In the formula, R 6 represents a hydrogen atom or a hydrocarbon group. R 7and R 8 (Each represents either a hydrogen atom or a hydrocarbon group.)

[0019] Appearance [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; In equation (2) above, R 6 This represents a hydrogen atom or an alkyl group. R 7 and R 8 A composition (A) according to embodiment [1], wherein is independently a hydrogen atom or an alkyl group.

[0020] 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; In equation (2) above, R 6 is a hydrogen atom or C 1-6It shows an alkyl group, R 7 and R 8 These are independently hydrogen atoms or C 1-6 A composition (A) according to embodiment [1] or [2], which exhibits an alkyl group.

[0021] Appearance [4]: A composition (A) according to any one of embodiments [1] to [3], wherein the ratio of the fluorene compound (a1) to the amide compound (a2) is the former / latter (mass ratio) = 91 / 9 to 99.995 / 0.005.

[0022] Appearance [5]: A method for producing composition (A) according to any one of embodiments [1] to [4], comprising a reaction step of reacting a compound represented by the following formula (3) with a compound represented by the following formulas (4a) and (4b) in a reaction solvent containing at least the amide compound (a2).

[0023] [ka]

[0024] (In the formula, R 1 And m1 are the same as in equation (1) above.

[0025] [ka]

[0026] (In the formula, R 2a , R 2b , R 2c and R 2d , R 3a and R 3b , X 1a and X 1b These are the same as equations (1) and (X1) above, respectively.

[0027] Appearance [6]: A fluidity improver comprising composition (A) as described in any of embodiments [1] to [4].

[0028] Appearance [7]: A method for improving fluidity by adding a fluorene compound (a1) and an amide compound (a2) [or composition (A)] described in any of embodiments [1] to [4] to a resin (b).

[0029] Appearance [8]: The method according to embodiment [7], which improves fluidity while suppressing a decrease in heat aging resistance and / or discoloration or yellowing.

[0030] Appearance [9]: A resin composition (B) comprising a fluorene compound (a1) and an amide compound (a2) [or composition (A)] described in any of embodiments [1] to [4], and a resin (b).

[0031] Appearance

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

[0032] Appearance

[11] : A resin composition (B) according to embodiment [9] or

[10] , wherein the ratio of the total amount of the fluorene compound (a1) and the amide compound (a2) [or composition (A)] to the resin (b) is the former / latter (mass ratio) = 0.01 / 99.99 to 10 / 90.

[0033] Appearance

[12] : A molded article comprising the resin composition (B) described in any of embodiments [9] to

[11] .

[0034] Appearance

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

[0035] Appearance

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

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

[0036] Appearance

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

[13] or

[14] and a second resin (b2).

[0037] 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).

[0038] Appearance

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

[15] .

[0039] Appearance

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

[13] or

[14] to a second resin (b2).

[0040] Appearance

[19] : The method according to embodiment

[18] , which improves fluidity while suppressing a decrease in heat aging resistance and / or discoloration or yellowing.

[0041] Furthermore, this disclosure may achieve the following secondary objectives (or solve the following secondary problems):

[0042] In other words, another object of this disclosure is to provide compositions (or flow improvers) that are easy to handle and can easily or efficiently (or stably) form resin compositions, resin compositions and masterbatches containing such compositions, and methods for producing and using these.

[0043] Another 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) while suppressing discoloration or yellowing, a resin composition and masterbatch containing this composition, and methods for producing and using these.

[0044] Another object of this disclosure is to provide a composition (or fluidity improver) capable of forming a resin composition with excellent fluidity even when added in small amounts, a resin composition and masterbatch containing this composition, and methods for producing and using these.

[0045] 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.

[0046] 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.

[0047] 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]

[0048] 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]

[0049] Composition (A) of the present disclosure can be effectively used as a fluidity improver because it 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). 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 an amide compound (a2) described later].

[0050] Furthermore, composition (A) of this disclosure has excellent handling properties, making it easy to prepare resin compositions (B) and masterbatches (C) easily, efficiently, or stably. In addition, composition (A) of this disclosure [or the fluorene compound (a1) and amide compound (a2) described later] can effectively suppress discoloration or yellowing in resin compositions (B) and masterbatches (C). Moreover, composition (A) of this disclosure [or the fluorene compound (a1) and amide compound (a2) described later] can effectively improve fluidity even with small amounts added. In particular, when resin composition (B) is prepared using masterbatches (C), fluidity can be further improved.

[0051] [Composition (A)] Composition (A) (flow improver) contains at least a fluorene compound (a1) represented by the following formula (1) and an amide compound (a2) represented by the formula (2) described later.

[0052] (Fluorene compound (a1))

[0053] [ka]

[0054] [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 2dThese 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

[0055] [ka]

[0056] (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 [ ].

[0057] 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 [-SR h ](where R h Examples include hydrocarbon groups, acyl groups, nitro groups, cyano groups, and substituted amino groups (mono or disubstituted amino groups).

[0058] 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.

[0059] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0060] Hydrocarbon group (or R hmay be a saturated or unsaturated hydrocarbon group, which may be an aliphatic (including alicyclic) or aromatic hydrocarbon group, and may be a hydrocarbon group having a chain (linear or branched) or cyclic structure, or a structure combining a chain and a ring. Note that the number of carbon atoms constituting the hydrocarbon group (or R h ) is not particularly limited, and may be, for example, about 20 or less, preferably, stepwise, 1 to 16, 1 to 12, 1 to 10, 1 to 8, 1 to 6. Representative hydrocarbon groups (or R h ) include, for example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and the like.

[0061] Examples of the alkyl group (linear or branched alkyl group) include C 1-10 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and the like, preferably a C 1-6 alkyl group, more preferably a C 1-4 alkyl group such as a methyl group.

[0062] Examples of the cycloalkyl group include C 5-10 cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and the like.

[0063] Examples of the aryl group include C 6-12 aryl groups such as a phenyl group, an alkylphenyl group, a biphenylyl group, a naphthyl group, and the like. Examples of the alkylphenyl group include mono- to tri-C 1-4 alkyl-phenyl groups such as a methylphenyl group (or tolyl group), a dimethylphenyl group (or xylyl group), and the like.

[0064] Examples of the aralkyl group include C 6-10 aryl-C 1-4 alkyl groups such as a benzyl group, a phenethyl group, and the like.

[0065] The group [-OR h and the group [-SRh In, R h Examples of the hydrocarbon group represented by include the same hydrocarbon groups as those exemplified above for R 1 including preferred embodiments, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and the like. The group [-OR h and the group [-SR h include, for example, groups corresponding to the examples of the hydrocarbon group (or R h ). Representative examples of the group [-OR h include, for example, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, and the like; representative examples of the group [-SR h include, for example, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, and the like.

[0066] Examples of the alkoxy group (linear or branched alkoxy group) include C 1-10 alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a t-butoxy group, and the like. Examples of the cycloalkyloxy group include C 5-10 cycloalkyloxy groups such as a cyclohexyloxy group. Examples of the aryloxy group include C 6-10 aryloxy groups such as a phenoxy group. Examples of the aralkyloxy group include C 6-10 aryl-C 1-4 alkyloxy groups such as a benzyloxy group.

[0067] Examples of the alkylthio group include C 1-10 alkylthio groups such as a methylthio group, an ethylthio group, a propylthio group, an n-butylthio group, a t-butylthio group, and the like. Examples of the cycloalkylthio group include C 5-10 cycloalkylthio groups such as a cyclohexylthio group. Examples of the arylthio group include C 6-10Examples of arylthio groups include the benzylthio group. 6-10 Aryl-C 1-4 Alkylthio groups are one example.

[0068] Examples of acyl groups include C 1-12 Examples include acyl groups, specifically C groups such as acetyl groups. 1-6 Examples include alkyl-carbonyl groups.

[0069] Examples of mono- or disubstituted amino groups include mono- or dialkylamino groups and mono- or diacylamino groups. Examples of mono- or dialkylamino groups include mono- or diC such as mono- or dimethylamino groups. 1-4 Examples include alkylamino groups. Mono or diacylamino groups include mono or diacetylamino groups, for example. 1-5 Examples include acylamino groups.

[0070] Typical R 1 Examples include halogen atoms, hydrocarbon groups (e.g., alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, etc.), and groups [-OR h Examples 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.

[0071] 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 1The 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 If substitution occurs, then 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.

[0072] 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 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.

[0073] 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 2dPreferably, 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.

[0074] 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.

[0075] 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. 3a or 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.

[0076] Preferred R 3a and R 3bThe 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.

[0077] 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.).

[0078] Also, R 4 and R 5 and bond to each other, and adjacent nitrogen atoms [the first heteroatom, i.e., R 4 , R 5When 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.

[0079] 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.

[0080] 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 C 1-4 Alkyl alkyl group, hydrogen atom or C1-3 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.

[0081] X 1a and X 1b The types may be different from each other, but it is preferable that they be the same.

[0082] 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);

[0083] 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 3b These are independently hydrogen atoms or C 1-6Alkyl 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:

[0084] 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:

[0085] 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).

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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).

[0095] 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.

[0096] 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.

[0097] (Amide compound (a2)) In this disclosure, it appears that by combining the amide compound (a2) represented by the following formula (2) with the fluorene compound (a1), when mixed with the resin, it is possible to further improve fluidity while suppressing a decrease in heat aging resistance (heat resistance or thermal stability), as well as suppressing discoloration or yellowing. Furthermore, even if the amide compound (a2) is present, odor is less likely to occur.

[0098] [ka]

[0099] (In the formula, R 6 This represents a hydrogen atom or a hydrocarbon group. R 7 and R 8 (Each represents either a hydrogen atom or a hydrocarbon group.)

[0100] In equation (2) above, R 6 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 1-4 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.

[0101] Preferred R 6 Examples include hydrogen atoms or alkyl groups (for example, hydrogen atoms or C 1-6 Alkyl alkyl group), more preferably a hydrogen atom or C 1-4 Alkyl (e.g., hydrogen atom or C) 1-3 Alkyl alkyl groups), more preferably hydrogen atoms or C 1-2 It is an alkyl group (for example, a hydrogen atom or a methyl group), and in particular, a hydrogen atom.

[0102] R 7 or R 8 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 1-4 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.

[0103] Preferred R 7 and R8 This includes a hydrogen atom or an alkyl group (preferably an alkyl group), and more preferably a hydrogen atom or C 1-6 Alkyl (e.g., hydrogen atom or C) 1-4 Alkyl alkyl groups), more preferably hydrogen atoms or C 1-3 Alkyl (e.g., hydrogen atom or C) 1-2 (Alkyl group), and in particular, C such as a methyl group. 1-2 It is an alkyl group. 7 and R 8 The types may be different from each other, but it is preferable that they be the same.

[0104] A typical amide compound (a2) is, for example, in formula (2) above, R 6 This represents a hydrogen atom or an alkyl group. R 7 and R 8 Examples include compounds that independently exhibit a hydrogen atom or an alkyl group (preferably an alkyl group);

[0105] Preferably R 6 is a hydrogen atom or C 1-6 Alkyl (e.g., hydrogen atom or C) 1-4 (Alkyl alkyl group) R 7 and R 8 These are independently hydrogen atoms or C 1-6 Alkyl (e.g., hydrogen atom or C) 1-4 Examples of compounds exhibiting alkyl groups include:

[0106] More preferably R 6 is a hydrogen atom or C 1-3 Alkyl (e.g., hydrogen atom or C) 1-2 (Alkyl alkyl group) R 7 and R 8 These are independently hydrogen atoms or C 1-3 Alkyl(hydrogen atom or C) 1-2 Examples of compounds exhibiting alkyl groups include:

[0107] Particularly preferred R 6 This represents a hydrogen atom or a methyl group (preferably a hydrogen atom), R 7 and R 8 C is independent 1-3 Alkyl group (preferably a C such as a methyl group) 1-2 Examples include compounds exhibiting alkyl groups.

[0108] Specific amide compounds (a2) include, for example, 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. The amide compound (a2) may be included alone or in combination of two or more.

[0109] The proportion of amide compound (a2) may be 10% by mass or more (for example, 10 to 30% by mass) relative to the total amount of fluorene compound (a1) and amide compound (a2). However, from the viewpoint of suppressing the stickiness of composition (A) and effectively improving handling, the proportion of amide compound (a2) 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 amide compound (a2). More preferably, it is 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) in stages, 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 amide compound (a2) is within a moderate range, not too low, it tends to improve fluidity, and when it is within a moderate range, not too high, it tends to improve handling and heat aging resistance (heat resistance or thermal stability).

[0110] The ratio of fluorene compound (a1) to amide compound (a2) may be, for example, approximately 91 / 9 to 99.995 / 0.005 in mass ratio, and 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, and 95 / 5 to 99.96 / 0.04. The ratios are 96 / 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 the amide compound (a2) 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.

[0111] (Other components (a3)) Composition (A) may or may not contain other components (a3) ​​different from the fluorene compound (a1) and the amide compound (a2), as needed. Examples of other components (a3) ​​include other flow improvers, sulfoxides, and conventional additives.

[0112] 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.

[0113] Furthermore, composition (A) may contain sulfoxides [such as dialkyl sulfoxides like dimethyl sulfoxide (DMSO)], but it is preferable that it does not contain sulfoxides, as this suppresses a decrease in heat aging resistance, inhibits discoloration or yellowing, and suppresses odor, while also improving fluidity when mixed with the resin. The proportion of sulfoxides may be, for example, about 0 to 5% by mass of the entire composition (A), and preferably in stages below, 3% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, and 0.1% by mass or less (for example, 0.001 to 0.05% by mass), and in particular, substantially 0% by mass.

[0114] 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.

[0115] Although composition (A) may contain a resin, it is preferable that it be a composition that is substantially free of resin (a non-resin composition).

[0116] 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 of the whole composition (A), preferably in stages of 30% by mass or less, 20% by mass or less, and 10% by mass or less (for example, 0.1 to 5% by mass), and in particular, substantially 0% by mass.

[0117] The total amount of fluorene compound (a1) and amide compound (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, 90% by mass or more (for example, about 95 to 99.9% by mass), and in particular, substantially 100% by mass. When the total amount of fluorene compound (a1) and amide compound (a2) is within a moderate range that is not too small, it tends to improve fluidity.

[0118] 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.

[0119] (Method for manufacturing composition (A)) The method for producing composition (A) is not particularly limited, and for example, it may be prepared by mixing a fluorene compound (a1), an amide compound (a2), and [other components (a3) ​​as needed]. A preferred production method includes a reaction step in which a compound represented by the following formula (3) [also called compound (3)] and a compound represented by the following formulas (4a) and (4b) [also called compounds (4a) and (4b)] are reacted (Michael addition reaction) in a reaction solvent containing at least an amide compound (a2).

[0120] [ka]

[0121] (In the formula, R 1 And m1 are the same as in formula (1), including preferred embodiments.

[0122] [ka]

[0123] (In the formula, R 2a , R 2b , R 2c and R 2d , R 3a and R 3b , X 1a and X 1b These are the same as formulas (1) and (X1) above, including preferred embodiments.

[0124] Representative compounds (3) include 9H-fluorene.

[0125] Furthermore, compounds (4a) and (4b) are R 2a , R 2b , R 2c and R 2d , R 3a and R 3b , and X 1a and X 1b Depending on the type, either the E-form or the Z-form may be used.

[0126] As typical compounds (4a) and (4b), compounds corresponding to the compounds exemplified as the fluorene compound (a1) represented by the above formula (1) can be mentioned. For example, (meth)acrylamide; N-C such as N-isopropyl(meth)acrylamide 1-6 N-alkyl-(meth)acrylamide; N,N-dialkyl-(meth)acrylamide such as N,N-dimethyl(meth)acrylamide and N,N-diethyl(meth)acrylamide 1-6 N-(meth)acryloyl N-containing heterocycles such as N-(meth)acryloylmorpholine can be mentioned. It is preferable that the compounds (4a) and (4b) are the same compound as each other.

[0127] The ratio of the amount of the compound (3) to the total amount of the compounds (4a) and (4b) may be, for example, about the former / latter (molar ratio) = 1 / 2 to 1 / 10. The preferable ranges are, step by step, 1 / 2 to 1 / 5, 1 / 2 to 1 / 3, and 1 / 2 to 1 / 2.5.

[0128] The reaction may usually be carried out in the presence of a base. Examples of the base include metal hydroxides, metal carbonates or bicarbonates, and metal alkoxides.

[0129] Examples of the metal hydroxide include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides such as barium hydroxide.

[0130] Examples of the metal carbonate or bicarbonate include alkali metal carbonates or bicarbonates such as sodium carbonate, potassium carbonate, and sodium bicarbonate.

[0131] Examples of the metal alkoxide include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide.

[0132] These bases can be used individually or in combination of two or more. Of these bases, metal hydroxides are preferred, and alkali metal hydroxides such as potassium hydroxide are more preferred. The proportion of the base may be, for example, about 0.001 to 0.1 moles per mole of compound (3), and preferably 0.01 to 0.05 moles.

[0133] The reaction is carried out in a reaction solvent containing at least the amide compound (a2). The reaction solvent may or may not contain other solvents (solvents inert to the reaction) different from the amide compound (a2). Examples of other solvents include water; alcohols such as methanol and ethanol; ethers such as cyclic ethers and chain ethers; sulfoxides such as dimethyl sulfoxide (DMSO); and hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

[0134] Examples of cyclic ethers include 1,4-dioxane and tetrahydrofuran. Examples of linear ethers include dialkyl ethers such as diethyl ether and diisopropyl ether, and glycol ethers. Examples of the glycol ethers include (poly)alkylene glycol monoalkyl ethers such as methyl cellosolve and methyl carbitol, and (poly)alkylene glycol dialkyl ethers such as dimethoxyethane.

[0135] Examples of aliphatic hydrocarbons include hexane and dodecane. Examples of alicyclic hydrocarbons include cyclohexane. Examples of aromatic hydrocarbons include toluene and xylene.

[0136] Other solvents may be used alone or in combination of two or more. A preferred other solvent is water. Water may be added in the form of an aqueous solution of the base mentioned above. The proportion of amide compound (a2) may be the largest in the reaction solvent (it may also be the main component), and is, for example, 50 to 100% by mass of the total reaction solvent, preferably in stages below 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 99% by mass or more, and may be substantially 100% by mass. The amount of reaction solvent used is not particularly limited as long as it does not hinder the progress of the reaction, and may be, for example, about 10 to 1000 parts by mass per 100 parts by mass of the total amount of compound (3) and compounds (4a) and (4b), preferably 50 to 500 parts by mass, and more preferably 100 to 200 parts by mass.

[0137] The reaction may be carried out under an inert gas atmosphere, such as nitrogen gas or a noble gas such as helium or argon. The reaction temperature is, for example, 30 to 100°C, preferably 50 to 80°C, and more preferably 60 to 70°C. The reaction time is not particularly limited and may be, for example, about 0.5 to 10 hours, preferably 1 to 3 hours.

[0138] After the reaction is complete, the reaction mixture may be separated and purified as needed by conventional separation and purification methods, such as neutralization, washing, extraction, filtration, decantation, concentration, dehydration, drying, crystallization or recrystallization, reprecipitation, chromatography, or a combination thereof.

[0139] Since a small amount of amide compound (a2) tends to remain in the fluorene compound (a1) obtained through the reaction steps described above, composition (A) can be easily or efficiently produced.

[0140] If necessary, the content of amide compound (a2) in composition (A) may be adjusted by partially removing the amide compound (a2) from composition (A) [fluorene compound (a1) with a small amount of amide compound (a2) remaining] obtained in the reaction step (for example, by vacuum drying) or by adding (mixing) the amide compound (a2) to the obtained composition (A).

[0141] Furthermore, other components (a3) ​​may be mixed with the obtained composition (A) as needed.

[0142] The mixing method used to prepare composition (A) is not particularly limited. Examples include dry mixing, wet mixing, and melt kneading. Specifically, the mixture may 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, and rolls (mixing rolls). Alternatively, the mixture may be placed in a designated container (or bag), sealed, and mixed by shaking.

[0143] [Resin composition (B) and masterbatch (C)] The resin composition (B) may contain at least a fluorene compound (a1), an amide compound (a2), and a resin [also known as resin (b)], for example, it may contain at least composition (A) and resin (b).

[0144] (Resin (b)) The resin (b) is not particularly limited, but examples include curable resins (thermo- or photo-curable resins) and thermoplastic resins.

[0145] 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.

[0146] 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.

[0147] Resin (b) may be included alone or in combination of two or more. From the viewpoint of improving melt fluidity, preferred resin (b) is a thermoplastic resin. More preferred resin (b) is a resin containing at least one structure selected from an ester bond [-C(=O)-O-], an amide bond [-C(=O)-NH-], and a urethane bond [-O-C(=O)-NH-] in its chemical structure (particularly, a resin containing as a chemical structure forming the main chain), and it is more preferred to contain at least one selected from polyester resins, polyamide resins (PA), and polyurethane resins (thermoplastic polyurethane resins). Among them, polyamide resin (PA) or polyurethane resin, particularly polyamide resin (PA) is preferred.

[0148] The proportion of polyamide resin (PA) (particularly, aliphatic polyamide resin described later) with respect to the whole 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, about 30 to 100% by mass), preferably in the following steps: 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.

[0149] (Polyamide resin (PA)) As the polyamide resin (PA), conventional polyamide resins can be used. For example, it may be formed from an aliphatic monomer component, an alicyclic monomer component, and / or an aromatic monomer component.

[0150] In addition, in this specification and the claims, monomer components having a carboxyl group such as dicarboxylic acid described later may be amide-forming derivatives, such as acid halides such as acid chlorides, acid anhydrides, etc.

[0151] Examples of the aliphatic monomer component include aliphatic diamine components, aliphatic dicarboxylic acid components, aliphatic aminocarboxylic acid components, lactam components, and the like.

[0152] 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.

[0153] Examples of aliphatic dicarboxylic acid components include saturated aliphatic dicarboxylic acids (alkanedicarboxylic acids) and unsaturated aliphatic dicarboxylic acids.

[0154] 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.

[0155] Examples of unsaturated aliphatic dicarboxylic acids include maleic acid, fumaric acid, and itaconic acid. 2-10 Examples include alkene-dicarboxylic acids.

[0156] 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.

[0157] The lactam component may be a lactam corresponding to the aliphatic aminocarboxylic acid, for example, a lactam with a 4- to 13 member ring such as ε-caprolactam or ω-laurolactam, and preferably a lactam with a 7- to 13 member ring.

[0158] Alicyclic monomer components only need to have an alicyclic skeleton (or aliphatic hydrocarbon ring skeleton), and examples include alicyclic diamine components, alicyclic dicarboxylic acid components, and alicyclic aminocarboxylic acid components.

[0159] Examples of alicyclic diamine components include diaminocycloalkanes, bis(aminoalkyl)cycloalkanes, and bis(aminocyclohexyl)alkanes.

[0160] Examples of diaminocycloalkanes include diaminocyclohexane and other diaminoC 5-10 Examples include cycloalkanes.

[0161] Examples of bis(aminoalkyl)cycloalkanes include bis(aminomethyl)cyclohexane and other bis(aminoC 1-4 Alkyl)C 5-10 Examples include cycloalkanes.

[0162] Examples of bis(aminocyclohexyl)alkanes include bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, and other bis(aminocyclohexyl)C 1-6 Alkanes; such as bis(4-amino-3-methylcyclohexyl)methane, bis(4-amino-3,5-dimethylcyclohexyl)methane, 2,2-bis(4-amino-3-methylcyclohexyl)propane, etc. (bis(amino-mono or tri-C)) 1-6 Alkyl-C 5-10 Cycloalkyl)C 1-6 Alkanes are one example.

[0163] Examples of alicyclic dicarboxylic acid components include cycloalkanedicarboxylic acids, crosslinked cyclic cycloalkanedicarboxylic acids, cycloalkenedicarboxylic acids, and crosslinked cyclic cycloalkenedicarboxylic acids.

[0164] Examples of cycloalkanedicarboxylic acids include C1,4-cyclohexanedicarboxylic acid. 5-10 Examples include cycloalkane-dicarboxylic acids.

[0165] Examples of crosslinked cyclic cycloalkanedicarboxylic acids include decalindicarboxylic acid, norbornanedicarboxylic acid, adamantanedicarboxylic acid, tricyclodecanedicarboxylic acid, and other bi or tricycloalkanedicarboxylic acids.

[0166] Examples of cycloalkenedicarboxylic acids include C15, such as cyclohexenedicarboxylic acid. 5-10 Examples include cycloalkene-dicarboxylic acids.

[0167] Examples of cross-linked cyclic cycloalkenedicarboxylic acids include bi- or tricycloalkenedicarboxylic acids such as norbornenedicarboxylic acid.

[0168] Examples of alicyclic aminocarboxylic acid components include aminocycloalkanecarboxylic acids, specifically aminoC, such as aminocyclohexanecarboxylic acid. 5-10 Examples include cycloalkane-carboxylic acids.

[0169] 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.

[0170] 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.

[0171] 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.

[0172] 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.

[0173] Examples of polycyclic arenedicarboxylic acids include condensed polycyclic arenedicarboxylic acids and ring-assembled arenedicarboxylic acids.

[0174] 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.

[0175] Examples of ring-assembled allene dicarboxylic acids include 2,2'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, and other biphenyldicarboxylic acids. 6-10 Examples include arene-dicarboxylic acids.

[0176] Examples of diarylalkanedicarboxylic acids include diC such as 4,4'-diphenylmethanedicarboxylic acid. 6-10 Aryl C 1-6 Examples include alkane-dicarboxylic acids.

[0177] Examples of diarylketone dicarboxylic acids include di(C) such as 4,4'-diphenylketone dicarboxylic acid. 6-10 Examples include aryl)ketone-dicarboxylic acids.

[0178] Examples of diaryl ether dicarboxylic acids include di(C) such as 4,4'-diphenyl ether dicarboxylic acid. 6-10 Examples include aryl) ether-dicarboxylic acids.

[0179] Examples of diarylsulfide dicarboxylic acids include di(C) such as 4,4'-diphenylsulfide dicarboxylic acid. 6-10 Examples include aryl sulfide dicarboxylic acids.

[0180] Examples of diarylsulfonedicarboxylic acids include di(C) such as 4,4'-diphenylsulfonedicarboxylic acid. 6-10 Examples include aryl)sulfone-dicarboxylic acids.

[0181] Examples of aromatic aminocarboxylic acid components include aminoarenecarboxylic acids. Examples of aminoarenecarboxylic acids include aminobenzoic acid and other amino C 6-12 Examples include arene-carboxylic acids.

[0182] 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.

[0183] 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.

[0184] 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.

[0185] 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.

[0186] 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.

[0187] 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.

[0188] 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.

[0189] 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.

[0190] 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, and copolyamides of monomer components that form these homopolyamides; 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.

[0191] 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.

[0192] 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).

[0193] In resin composition (B), the ratio of the total amount of fluorene compound (a1) and amide compound (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 amide compound (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) is 0.01 / 99.99 to 20 / 80, 0.05 / 99.95 to 15 / 85, 0.1 / 99.9 to 10 / 90, 0.2 / 99.8 to 5 / 95, 0.3 / 99.7 to 3 / 97, 0.4 / 99.6 to 2 / 98, and 0.5 / 99.5 to 1 / 99. When the total amount of fluorene compound (a1) and amide compound (a2) [or composition (A)] is within a moderate range that is not too little, it tends to improve fluidity, and when it is within a moderate range that is not too much, it tends to maintain its shape and suppress the deterioration of mechanical properties (such as strength) even when used in high-temperature environments.

[0194] In resin composition (B), the ratio of fluorene compound (a1) to amide compound (a2) is the same as the ratio (mass ratio) described in section [Composition (A)] above, including in preferred embodiments.

[0195] (Masterbatch(C)) The masterbatch (C) only needs to contain at least a fluorene compound (a1), an amide compound (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 within the resin composition (B).

[0196] More specifically, masterbatch (C) corresponds to a resin composition containing a fluorene compound (a1) and an amide compound (a2) [or composition (A)] in high concentrations 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 an amide compound (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).

[0197] Since the masterbatch (C) is even easier to handle than composition (A), compared to directly preparing resin composition (B) by mixing composition (A) [or fluorene compound (a1) and amide compound (a2)] and resin (b) in a desired proportion, contamination of machinery (such as a kneader) is suppressed, workability is improved, and resin composition (B) can be produced easily, efficiently (or stably). Moreover, in this disclosure, it appears that the fluidity can be further improved by preparing resin composition (B) via (diluting) the masterbatch (C) as described above. Therefore, this disclosure also includes a method for producing resin composition (B) by mixing the masterbatch (C) with a second resin (b2).

[0198] Examples of the first resin (b1) include resins similar to those exemplified as resin (b), including preferred embodiments.

[0199] Furthermore, the second resin (b2) can be, for example, a resin similar to the resin exemplified as resin (b) above, including preferred embodiments.

[0200] 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 even more preferable that they are the same resin.

[0201] 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.

[0202] 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.

[0203] In the masterbatch (C), the ratio of the total amount of fluorene compound (a1) and amide compound (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 amide compound (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.

[0204] In addition, in the masterbatch (C), the ratio of fluorene compound (a1) to amide compound (a2) is the same as the ratio (mass ratio) described in the section [Composition (A)] above, including in preferred embodiments.

[0205] The method for producing the masterbatch (C) is not particularly limited, and for example, it may be prepared by mixing a fluorene compound (a1) and an amide compound (a2) [or composition (A)] with a first resin (b1) [and other components (b3) as described later, if necessary].

[0206] 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.

[0207] (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 the amide compound (a2) [or composition (A)] and the resin (b) [first resin (b1) and second resin (b2)]. Examples of other components (b3) include other flow improvers, sulfoxides, and conventional additives.

[0208] 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.

[0209] 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 amide compound (a2) in the resin composition (B) or the masterbatch (C), and preferably in stages below, 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.

[0210] 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.

[0211] 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).

[0212] In resin composition (B), the total proportion of the fluorene compound (a1) and the amide compound (a2) [or composition (A)] and the resin (b) [first resin (b1) and second resin (b2)] may be the largest proportion among the constituent components [may be a main component that is larger than the proportion of 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.

[0213] In the masterbatch (C), the total proportion of the fluorene compound (a1) and the amide compound (a2) [or composition (A)] and the first resin (b1) may be the largest proportion among the constituent components [may be a main component in a proportion greater than the proportion of 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 substantially 100% by mass.

[0214] (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), an amide compound (a2), and a resin (b); it may be produced by mixing composition (A) and a resin (b); or, as described above, it may be produced by mixing (C) with a second resin (b2) [or diluting it with the second resin (b2)]. In these production methods, other components (b3) 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.

[0215] 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.

[0216] The disclosure also includes methods for improving fluidity by adding (mixing) a fluorene compound (a1) and an amide compound (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 and / or suppressing discoloration or yellowing.

[0217] (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, 103 to 200, preferably 105 to 150, and more preferably 108 to 130, when the MFR of a resin composition that does not contain fluorene compound (a1) and amide compound (a2) [or composition (A)] [a resin composition containing the same mass of resin (b) instead of fluorene compound (a1) and amide compound (a2) [or composition (A)] in resin composition (B), hereinafter simply referred to as "blank"] is set to 100.

[0218] The blank's MFR may be, for example, 10-100 g / 10 min, preferably 30-50 g / 10 min or 20-50 g / 10 min, more preferably 35-40 g / 10 min or 25-35 g / 10 min, under measurement conditions of a temperature of 265°C, a test load of 1.20 kgf, and a holding time of 5 minutes, and for example, 10-100 g / 10 min, preferably 20-50 g / 10 min, more preferably 25-35 g / 10 min, under measurement conditions of a temperature of 240°C, a test load of 1.20 kgf, and a holding time of 5 minutes.

[0219] 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.

[0220] The tensile strength (maximum tensile strength) of resin composition (B) may be, for example, around 90 to 110, when the tensile strength of the blank (before thermal aging test) is set to 100.

[0221] 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).

[0222] 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, around 65 to 80, and preferably 70 to 75, when the strength before the heat aging test is set to 100.

[0223] 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.

[0224] [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.

[0225] 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.

[0226] 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]

[0227] 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.

[0228] [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.

[0229] (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.

[0230] (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").

[0231] (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.

[0232] (Mixing and molding properties) The moldability of the obtained resin composition (or masterbatch) was evaluated according to the following criteria.

[0233] ○... Easily moldable into strands (easily moldable into pellets) ×...Difficult to mold into strands (difficult to mold into pellets)

[0234] (Color tone) The color of the obtained resin composition (or masterbatch) was visually inspected.

[0235] [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. DMSO: Dimethyl sulfoxide, manufactured by Kanto Chemical Co., Ltd., premium grade. Toluene: Manufactured by Kanto Chemical Co., Ltd. TBAB: Tetrabutylammonium bromide, manufactured by Tokyo Chemical Industry Co., Ltd. KOH: Potassium hydroxide, manufactured by Kanto Chemical Co., Ltd. Methanol: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Isopropanol: Manufactured by Kanto Chemical Co., Ltd. (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.

[0236] [Synthesis Example 1] Preparation of AAD-FL (DMF-containing product) 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.

[0237] [Synthesis Example 2] Preparation of AAD-FL (DMSO-containing product) AAD-FL was synthesized according to Synthesis Example 4 of International Publication No. 2021 / 171756. 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 DMSO remained in the obtained AAD-FL.

[0238] [Examples 1-5, Reference Example 1] Preparation of a fluidity improver (Composition (A)) Using the AAD-FL (DMF-containing product) obtained in Synthesis Example 1, a fluidity improver (composition (A)) was prepared such that the mass ratio of AAD-FL and DMF was as shown in Table 1 below. When mixing the AAD-FL (DMF-containing product) obtained in Synthesis Example 1 with DMF, both were placed in an aluminum-metallized bag ("Lamizip" manufactured by Seisan Nippon Co., Ltd.) and sealed, and mixed at room temperature and pressure (25°C, 1 atm).

[0239] [Reference Examples 2-6] Preparation of Flowability Improvers Using the AAD-FL (DMSO-containing product) obtained in Synthesis Example 2, a fluidity improver was prepared so that the mass ratio of AAD-FL and DMSO was as shown in Table 1 below. When mixing the AAD-FL (DMSO-containing product) obtained in Synthesis Example 2 with DMSO, both were placed in an aluminum-metallized bag ("Lamizip" manufactured by Seisan Nippon Co., Ltd.) and sealed, and mixed at room temperature and pressure (25°C, 1 atm).

[0240] [Table 1]

[0241] [Examples 6-10, Reference Examples 7-12] Preparation of resin compositions The fluidity improvers obtained in Examples 1-5 and Reference Examples 1-6 were melt-kneaded with PA66 at 280°C using a twin-screw extruder (Thermo Fisher "Process11 TwinScrewExtruder", L / D=40) in the mass ratios shown in Table 2 below to prepare resin compositions. The evaluation results of the obtained resin compositions are shown in Table 2 below.

[0242] [Table 2]

[0243] As is clear from the results in Table 2, in Reference Examples 7 and 12, the amount of DMF or DMSO in the fluidity improver was too high, resulting in poor handling (severe stickiness) and difficulty in feeding, making it impossible to stably (easily or efficiently) prepare a homogeneous resin composition. On the other hand, in Examples 6-10 and Reference Examples 8-11, in which resin compositions were successfully prepared, fluidity improved compared to PA66 alone (MFR: 33g / 10min), but the examples containing DMF tended to show a greater improvement.

[0244] Furthermore, regarding tensile strength, before heat aging treatment (Condition 1), all of Examples 6-10 and Reference Examples 8-11 maintained the strength of PA66 alone (tensile strength: 84 MPa). However, in Reference Examples 8-11, which included DMSO, the strength decreased significantly after heat aging treatment (Condition 2). In contrast, in Examples 6-10, which included DMF, the decrease in strength was suppressed even after heat aging treatment (Condition 2), indicating high heat aging resistance (or thermal stability).

[0245] In addition, in the resin compositions (B) obtained in Examples 6 to 10, as the amount of DMF increased, the MFR improved, and the tensile strength after heat aging treatment (condition 2) tended to decrease. Of Examples 6 to 10, Examples 6 to 8 were preferred from the viewpoint of having better heat aging resistance, and Examples 7 to 8 were preferred in that they had a particularly good balance between heat aging resistance and fluidity.

[0246] [Examples 11-15, Reference Example 13] Preparation of resin composition (B) (or masterbatch (C)) PA66, AAD-FL (DMF-containing product) obtained in Synthesis Example 1, and DMF were melt-kneaded at 280°C using a twin-screw extruder (Thermo Fisher "Process11 TwinScrewExtruder", L / D=40) to prepare a resin composition (B) (or masterbatch (C)) such that PA66, AAD-FL, and DMF were in the mass ratios shown in Table 3 below.

[0247] [Reference Examples 14-15] Preparation of resin composition (or masterbatch) PA66, AAD-FL (DMSO-containing product) obtained in Synthesis Example 2, and DMSO were melt-kneaded at 280°C using a twin-screw extruder (Thermo Fisher "Process11 TwinScrewExtruder", L / D=40) to prepare a resin composition (or masterbatch) in which PA66, AAD-FL, and DMSO were in the mass ratios shown in Table 3 below.

[0248] [Examples 16-18] Preparation of resin composition (B) (or masterbatch (C)) Resin composition (B) (or masterbatch (C)) was prepared in the same manner as in [Examples 11-15, Reference Example 13], except that PA6 was used instead of PA66, and the mixture was melt-kneaded at 230°C to obtain the mass ratios shown in Table 4 below.

[0249] [Reference Example 16] Preparation of resin composition (or masterbatch) The resin composition (or masterbatch) was prepared in the same manner as in [Reference Examples 14-15], except that PA6 was used instead of PA66, and the mixture was melt-kneaded at 230°C to achieve the mass ratios shown in Table 4 below.

[0250] [Examples 19-21] Preparation of resin composition (B) (or masterbatch (C)) Resin composition (B) (or masterbatch (C)) was prepared in the same manner as in [Examples 11-15, Reference Example 13], except that PA11 was used instead of PA66 and the mixture was melt-kneaded at 230°C to obtain the mass ratios shown in Table 4 below.

[0251] [Reference Example 17] Preparation of resin composition (or masterbatch) The resin composition (or masterbatch) was prepared in the same manner as in [Reference Examples 14-15], except that PA11 was used instead of PA66, and the mixture was melt-kneaded at 230°C to achieve the mass ratios shown in Table 4 below.

[0252] The evaluation results of the resin compositions (or masterbatches) obtained in Examples 11-21 and Reference Examples 13-17 are shown in Tables 3-4 below. In the DMF and DMSO columns in Tables 3-4, the numbers in parentheses indicate the percentage [mass%] of DMF or DMSO relative to the total amount of AAD-FL.

[0253] [Table 3]

[0254] [Table 4]

[0255] As is clear from the results in Tables 3-4, the resin compositions (or masterbatches) of Examples 11-21 and Reference Examples 14-17 could all be molded into strands (pellets) even when they contained high concentrations of AAD-FL and DMF, or AAD-FL and DMSO.

[0256] Furthermore, as is clear from the comparison of Example 12 and Reference Example 14, Example 13 and Reference Example 15, Example 18 and Reference Example 16, and Example 21 and Reference Example 17, in the examples containing DMF, not only was discoloration (or yellowing) suppressed, but no odor was detected, which was unexpected compared to the reference example containing DMSO.

[0257] [Example 22] Preparation of resin composition (B) The pelletized masterbatch (C) obtained in Example 12 and PA66 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 5 below to prepare resin composition (B). The evaluation results of the obtained resin composition (B) are shown in Table 5 below, along with those of Example 14.

[0258] [Table 5]

[0259] As is clear from the results in Table 5, although the resin compositions (B) of Example 22 and Example 14 were prepared to have substantially the same constituent components and composition ratios, unexpectedly, Example 22, prepared using the masterbatch (C), showed even greater fluidity of resin composition (B) compared to Example 14, prepared without the use of the masterbatch (C).

[0260] [Example 23] Preparation of resin composition (B) PA6, AAD-FL (DMF-containing product) obtained in Synthesis Example 1, and DMF were melt-kneaded at 230°C using a twin-screw extruder (Thermo Fisher "Process11 TwinScrewExtruder", L / D=40) to prepare resin composition (B) such that PA6, AAD-FL, and DMF were in the mass ratios shown in Table 6 below.

[0261] [Example 24] Preparation of resin composition (B) The pelletized masterbatch (C) obtained in Example 18 and PA6 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 6 below to prepare resin composition (B).

[0262] The evaluation results of the resin compositions (B) obtained in Examples 23-24 are shown in Table 6 below.

[0263] [Table 6]

[0264] As is clear from the results in Table 6, similar to the case of PA66, in Examples 23 and 24 using PA6, the fluidity was improved compared to PA6 alone (MFR: 29 g / 10 min) while maintaining the strength of PA6 alone (tensile strength: 80 MPa). Furthermore, although the resin compositions (B) of Examples 23 and 24 were prepared to have substantially the same constituent components and composition ratios, unexpectedly, in Example 24, which was prepared using the masterbatch (C), the fluidity of the resin composition (B) was further improved compared to Example 23, which was prepared without the use of the masterbatch (C), and the tensile strength was also improved. [Industrial applicability]

[0265] The composition (A) and masterbatch (C) of this disclosure can be effectively used as resin modifiers for modifying resins, for example, as additives (or flow improvers) for improving the fluidity (melt fluidity or moldability) of resins.

[0266] 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 an amide compound (a2) represented by the following formula (2), 【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 [ ]. 【Transformation 3】 (In the formula, R ６ This represents a hydrogen atom or a hydrocarbon group. R ７ and R ８ (Each represents either a hydrogen atom or a hydrocarbon group.) Composition (A), wherein the proportion of the amide compound (a2) is less than 10% by mass relative to the total amount of the fluorene compound (a1) and the amide compound (a2).

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; In the above formula (2), R ６ This represents a hydrogen atom or an alkyl group. R ７ and R ８ The composition (A) according to claim 1, wherein is independently a hydrogen atom or an alkyl group.

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; In the above formula (2), R ６ is a hydrogen atom or C １－６ It shows an alkyl group, R ７ and R ８ These are independently hydrogen atoms or C １－６ A composition (A) according to claim 1, which represents an alkyl group.

4. The composition (A) according to any one of claims 1 to 3, wherein the ratio of the fluorene compound (a1) to the amide compound (a2) is the former / latter (mass ratio) = 91 / 9 to 99.995 / 0.

005.

5. A method for producing composition (A) according to any one of claims 1 to 3, comprising a reaction step of reacting a compound represented by the following formula (3) with a compound represented by the following formulas (4a) and (4b) in a reaction solvent containing at least the amide compound (a2). 【Chemistry 4】 (In the formula, R １ (And m1 are the same as in formula (1) above.) 【Transformation 5】 (In the formula, R ２ａ , R ２ｂ , R ２ｃ and R ２ｄ , R ３ａ and R ３ｂ , X １ａ and X １ｂ These are the same as equations (1) and (X1) above.

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

7. A method for improving fluidity by adding a fluorene compound (a1) and an amide compound (a2) according to any one of claims 1 to 3 to a resin (b).

8. The method according to claim 7, which improves fluidity while suppressing a decrease in heat aging resistance and / or discoloration or yellowing.

9. A resin composition (B) comprising a fluorene compound (a1) and an amide compound (a2) according to any one of claims 1 to 3, and a resin (b).

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

11. The resin composition (B) according to claim 9, wherein the ratio of the total amount of the fluorene compound (a1) and the amide compound (a2) to the resin (b) is the former / latter (mass ratio) = 0.01 / 99.99 to 10 / 90.

12. A molded article comprising the resin composition (B) according to claim 9.

13. A masterbatch (C) comprising a fluorene compound (a1) and an amide compound (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 amide compound (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 and / or discoloration or yellowing.

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