Thermoplastic resin composition and molded article thereof

Abstract

To provide a thermoplastic composition (or thermoplastic elastomer composition) and its molded article, and a fluidity improving method and a fluidity improver, wherein the thermoplastic composition exhibits superior melt fluidity (moldability or processability) without unduly reducing mechanical properties, even in the absence of an additive having a 9,9-bisarylfluorene skeleton.SOLUTION: A thermoplastic composition is prepared which comprises at least a thermoplastic elastomer (A) and a fluorene compound (B) represented by the following formula (1), (in which R2a, R2b, R2c, and R2d denote H or a substituent, R3a and R3b denote H or a substituent, and X1a and X1b denote a group represented by formula (X1)).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a thermoplastic elastomer composition (or thermoplastic composition) containing a thermoplastic elastomer and a fluorene compound (or fluorene derivative) having a specific chemical structure, a molded product thereof, a method for improving flowability, and a flowability improver. [Background technology]

[0002] Thermoplastic elastomers are widely used as elastic materials with excellent mechanical, thermal, and electrical properties. Thermoplastic elastomers have the same elasticity as crosslinked rubber, but also exhibit melt fluidity (or thermoplasticity), making them moldable using standard plastic molding machines and easy to recycle. However, the melt fluidity of thermoplastic elastomers is sometimes insufficient, and improvements in moldability and recyclability are needed.

[0003] International Publication No. 2020 / 022356 (Patent Document 1) discloses a thermoplastic composition containing a thermoplastic elastomer and a compound having a 9,9-bisarylfluorene skeleton. It describes that this thermoplastic composition has excellent melt fluidity (moldability or processability) even when it contains a thermoplastic elastomer, and that even when the added component is a low-molecular-weight compound, it can suppress deterioration of physical properties such as mechanical and thermal properties (or improve physical properties).

[0004] In addition, International Publication No. 2021 / 172300 (Patent Document 2) discloses a novel fluorene derivative and a resin composition containing this fluorene derivative and a resin, and states that the fluorene compound can be used as a strength improver (mechanical property improver) for resin, a flowability improver, etc.

[0005] Furthermore, U.S. Pat. No. 2,299,948 (Patent Document 3) describes that 9,9-di-(β-carbamoyl-ethyl)fluorene represented by the following formula is useful as an intermediate for preparing synthetic resins.

[0006] [ka] [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2020 / 022356 [Patent Document 2] International Publication No. 2021 / 172300 [Patent Document 3] U.S. Patent No. 2,299,948 Summary of the Invention [Problem to be solved by the invention]

[0008] In the examples of Patent Document 1, it is described that by adding 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (hereinafter also referred to as BPEF), a compound having a 9,9-bisarylfluorene skeleton, to a thermoplastic urethane elastomer (TPU) or a thermoplastic ether ester elastomer (TEEE), it is possible to improve the melt fluidity without deteriorating the mechanical properties.

[0009] However, in applications where fine molding is required, even if the compound having a 9,9-bisarylfluorene skeleton described in Patent Document 1 is added, the fluidity may not be sufficient.

[0010] Furthermore, Patent Document 1 requires a 9,9-bisarylfluorene skeleton in the chemical structure, and does not disclose any fluorene compounds that do not have aryl groups at the 9,9-positions.

[0011] Furthermore, although Patent Document 2 describes thermoplastic elastomers, it only lists a number of resins, including thermosetting resins that are cured by heat (or do not exhibit melt fluidity), as examples, and does not specifically describe the preparation of a thermoplastic elastomer composition. In the examples, a specific fluorene derivative is added to plastics such as polyolefin resins and polyamide resins, and there is no description of the effect of adding the derivative to elastomers, which have properties completely different from those of plastics.

[0012] In the examples of Patent Document 3, 9,9-di-(β-carbamoyl-ethyl)fluorene is prepared by reacting 9,9-di-(β-cyanoethyl)fluorene with sulfuric acid under specific conditions.

[0013] However, there is no description or suggestion as to the use of 9,9-di-(β-carbamoyl-ethyl)fluorene as an additive for improving the melt flowability of thermoplastic elastomers.

[0014] Therefore, an object of the present disclosure is to provide a thermoplastic composition (or thermoplastic elastomer composition) and a molded product thereof that have excellent melt fluidity (moldability or processability) without excessively reducing mechanical properties, even without containing an additive having a 9,9-bisarylfluorene skeleton, as well as a method for improving fluidity and a flowability improver. [Means for solving the problem]

[0015] As a result of intensive research to achieve the above object, the present inventors have found that adding a fluorene compound having a specific chemical structure to a thermoplastic elastomer can effectively improve the fluidity of the thermoplastic elastomer, even though the thermoplastic elastomer does not have a 9,9-bisarylfluorene skeleton, and have completed the present invention (or the present disclosure). That is, the present disclosure may include the following aspects.

[0016] Aspect [1]: A thermoplastic composition (thermoplastic elastomer composition) containing at least a thermoplastic elastomer (A) and a fluorene compound (B) represented by the following formula (1):

[0017] [ka] [In the formula, R 1 represents a substituent, k represents an integer of 0 to 8, R 2a , R 2b , R 2c and R 2d each independently represents a hydrogen atom or a substituent, R 3a and R 3b each independently represents a hydrogen atom or a substituent, X 1a and X 1b are independently represented by the following formula (X1)

[0018] [ka] (In the formula, R 4 and R 5 each independently represents a hydrogen atom or a hydrocarbon group, or R 4 and R 5 and are bonded to each other to form a heterocycle together with the adjacent nitrogen atom. represents a group represented by the formula:

[0019] Aspect [2]: The thermoplastic composition according to aspect [1], wherein the thermoplastic elastomer (A) comprises at least one selected from a polyurethane-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, and a polyamide-based thermoplastic elastomer.

[0020] Aspect [3]: The thermoplastic composition according to aspect [1] or [2], wherein the thermoplastic elastomer (A) comprises a polyether-type polyurethane-based thermoplastic elastomer.

[0021] Aspect [4]: ​​In the formula (1), R 1represents a hydrocarbon group, k represents an integer of 0 to 4, R 2a , R 2b , R 2c and R 2d each independently represents a hydrogen atom or a hydrocarbon group; R 3a and R 3b each independently represents a hydrogen atom or a hydrocarbon group; In the formula (X1), R 4 and R 5 The thermoplastic composition according to any one of embodiments [1] to [3], wherein are independently a hydrogen atom or an alkyl group.

[0022] Aspect [5]: In the formula (X1), R 4 and R 5 The thermoplastic composition according to any one of aspects [1] to [4], wherein is a hydrogen atom.

[0023] Aspect [6]: The thermoplastic composition according to any one of aspects [1] to [5], wherein the proportion of the fluorene compound (B) is 0.01 to 30 parts by mass per 100 parts by mass of the total amount of the thermoplastic elastomer (A) and the fluorene compound (B).

[0024] Aspect [7]: A molded article comprising the thermoplastic composition according to any one of aspects [1] to [6].

[0025] Aspect [8]: A method for improving the flowability by adding the fluorene compound (B) represented by formula (1) according to any one of aspects [1] to [6] to the thermoplastic elastomer (A).

[0026] Aspect [9]: A flowability improver for a thermoplastic elastomer (A), comprising a fluorene compound (B) represented by formula (1) according to any one of aspects [1] to [6].

[0027] The present disclosure may also achieve the following secondary objectives (or solve secondary problems).

[0028] That is, another object of the present disclosure is to provide a thermoplastic composition (thermoplastic elastomer composition) having excellent melt fluidity even when a small amount of a fluorene compound is contained, a molded product thereof, a method for improving fluidity, and a fluidity improver.

[0029] Yet another object of the present disclosure is to provide a thermoplastic composition having an excellent balance of melt fluidity, mechanical properties, and handleability (or stability), a molded product thereof, a method for improving fluidity, and a flowability improver.

[0030] In addition, in this specification and claims, the number of carbon atoms in a substituent is not limited to C1, C6, C 10 For example, an alkyl group with 1 carbon atom is called a "C1 alkyl," and an aryl group with 6 to 10 carbon atoms is called a "C 6-10 It is indicated as "aryl" etc.

[0031] In the present specification and claims, "independently" means that two components are independent components, and the group R 2a and group R 2b In the case of R 2a and R 2b and do not necessarily have to be the same hydrogen atom or substituent, and may be different from each other.

[0032] In this specification and claims, a numerical range indicated as "X to Y" may include the numerical values ​​X and Y. [Effects of the Invention]

[0033] According to the present disclosure, it is possible to provide a thermoplastic composition (or a thermoplastic elastomer composition) and a molded product thereof that have excellent melt fluidity (moldability or processability) without excessively reducing mechanical properties, even without containing an additive having a 9,9-bisarylfluorene skeleton, as well as a flowability improving method and a flowability improving agent. DETAILED DESCRIPTION OF THE INVENTION

[0034] The thermoplastic composition (thermoplastic elastomer composition or TPE composition) of the present disclosure is a thermoplastic (or non-thermosetting) composition containing at least a thermoplastic elastomer (A) (hereinafter also simply referred to as TPE (A)) and a fluorene compound (B) (hereinafter also simply referred to as fluorene compound (B)) having a specific chemical structure represented by formula (1).

[0035] The thermoplastic composition of the present disclosure combines a thermoplastic elastomer (A) with a fluorene compound (B) having a specific chemical structure, even though the fluorene compound (B) does not have a 9,9-bisarylfluorene skeleton. Therefore, a high level of balance between mechanical properties such as tensile and flexural properties and melt fluidity can be achieved. Furthermore, even with a small amount of fluorene compound (B), the composition exhibits excellent melt fluidity and effectively suppresses bleed-out of the fluorene compound (B). Therefore, a high level of balance between melt fluidity, mechanical properties, and handleability (or stability) can be achieved. The present disclosure also encompasses a method of improving the fluidity (melt fluidity) of a thermoplastic elastomer (A) without impairing its mechanical properties by adding a fluorene compound (B).

[0036] [Thermoplastic elastomer (A)] Thermoplastic elastomers (TPEs) contain soft segments (soft phases, soft blocks, or rubber components) and hard segments (hard phases, hard blocks, or resin components).

[0037] Representative examples of thermoplastic elastomers include polystyrene-based thermoplastic elastomers, polyolefin-based thermoplastic elastomers (TPO), polydiene-based thermoplastic elastomers, chlorine-based thermoplastic elastomers, ionomers, fluorine-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers (TPU), polyester-based thermoplastic elastomers (TPEE), and polyamide-based thermoplastic elastomers (TPA).

[0038] These thermoplastic elastomers may be used alone or in combination.

[0039] (Polystyrene-based thermoplastic elastomer) Examples of polystyrene-based thermoplastic elastomers include elastomers having a hard segment formed of a styrene-based polymer such as polystyrene and a soft segment formed of a rubber component such as a polydiene such as polybutadiene or polyisopropylene or a hydrogenated product thereof.

[0040] Specific examples include styrene-diene-styrene block copolymers such as styrene-butadiene-styrene block copolymer (SBS) and styrene-isoprene-styrene block copolymer (SIS); hydrogenated styrene-diene-styrene block copolymers such as styrene-ethylene-butylene-styrene block copolymer (SEBS) and styrene-ethylene-propylene-styrene block copolymer (SEPS); and mixtures of hydrogenated random styrene-butadiene rubber (HSBR) with olefin resins such as polypropylene.

[0041] These polystyrene-based thermoplastic elastomers may be used alone or in combination.

[0042] (Polyolefin-based thermoplastic elastomer) Examples of polyolefin-based thermoplastic elastomers (TPOs) include elastomers having hard segments formed from polyolefins such as polyethylene and polypropylene, and soft segments formed from rubber components such as olefin-based rubber, diene-based rubber, acrylic rubber, butyl rubber, nitrile rubber, and natural rubber. Examples of the olefin-based rubbers include ethylene propylene rubber (EPM) and ethylene propylene diene rubber (EPDM).

[0043] The TPO may be a simple blend type TPO obtained by mechanically mixing a polyolefin with an uncrosslinked or partially crosslinked rubber component; an implanted TPO or reactor-made TPO (i-TPO or R-TPO) formed by stepwise polymerization of each segment; or a dynamically crosslinked TPO (dynamic vulcanization type TPO) formed by melt-kneading a polyolefin with an uncrosslinked rubber component, adding a crosslinking agent or crosslinking accelerator, and crosslinking while applying shear stress.

[0044] These TPOs may be used alone or in combination.

[0045] (Polydiene thermoplastic elastomer) Examples of polydiene-based thermoplastic elastomers include polybutadiene-based thermoplastic elastomers (RB) having hard segments formed from syndiotactic 1,2-polybutadiene and soft segments formed from atactic 1,2-polybutadiene; polyisoprene-based thermoplastic elastomers (TPI) having hard segments formed from crystalline trans-1,4-polyisoprene and soft segments formed from amorphous trans-1,4-polyisoprene; and natural rubber-based thermoplastic elastomers (TPNR) having hard segments formed from an olefin resin such as polypropylene and soft segments formed from natural rubber.

[0046] These polydiene-based thermoplastic elastomers may be used alone or in combination.

[0047] (Chlorine-based thermoplastic elastomer) Examples of chlorine-based thermoplastic elastomers include polyvinyl chloride-based thermoplastic elastomers (TPVC) having hard segments formed from rigid PVC such as high-molecular-weight polyvinyl chloride (PVC) or partially crosslinked PVC, and soft segments formed from flexible PVC such as plasticized PVC or rubber components such as partially crosslinked NBR; and chlorinated polyethylene-based thermoplastic elastomers having hard segments formed from crystalline polyethylene segments and soft segments formed from chlorinated polyethylene segments. The chlorinated polyethylene-based thermoplastic elastomer may form an alloy with other resins and / or rubber components, such as olefin-based resins such as polypropylene and polyamide-based resins such as aliphatic polyamide.

[0048] These chlorine-containing thermoplastic elastomers may be used alone or in combination.

[0049] (ionomer) Examples of ionomers include ion-crosslinked polyolefin resins having hard segments formed from carboxyl groups or the like introduced into the molecule by graft polymerization of (meth)acrylic acid or the like, and soft segments formed from polyolefin resins such as polyethylene.

[0050] These ionomers may be used alone or in combination.

[0051] (Fluorine-based thermoplastic elastomer) Examples of fluorine-based thermoplastic elastomers include elastomers having a hard segment formed from a crystalline fluororesin such as polyvinylidene fluoride (PVDF) or an ethylene-tetrafluoroethylene copolymer, and a soft segment formed from a fluororubber such as a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer.

[0052] These fluorine-containing thermoplastic elastomers may be used alone or in combination.

[0053] (Polyurethane-based thermoplastic elastomer) Thermoplastic polyurethane elastomers (TPUs) have hard segments formed from polyisocyanates (or diisocyanates) and chain extenders (or chain extenders) such as short-chain glycols, and soft segments formed from long-chain polyols (or long-chain glycols). They are preferably linear multi-block copolymers obtained by forming urethane bonds through a polyaddition reaction between polyisocyanates, long-chain polyols, and, if necessary, a chain extender.

[0054] Examples of polyisocyanates include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, and aromatic polyisocyanates.

[0055] Examples of aliphatic polyisocyanates include C tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI), etc. 2-16 Alkane diisocyanates and the like.

[0056] Examples of alicyclic polyisocyanates include 1,4-cyclohexane diisocyanate, isophorone diisocyanate (IPDI), 4,4'-methylenebis(cyclohexyl isocyanate), hydrogenated xylylene diisocyanate (hydrogenated XDI), hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), and norbornane diisocyanate.

[0057] Examples of the aralkyl polyisocyanate include xylylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI).

[0058] Examples of aromatic polyisocyanates include phenylene diisocyanate, tolylene diisocyanate (TDI), 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (MDI), tolidine diisocyanate (TODI), and diphenyl ether diisocyanate.

[0059] The polyisocyanates may be urethane prepolymers having free isocyanate groups, which are produced by reacting the above polyisocyanates with polyols described below.

[0060] Furthermore, the polyisocyanates may be, for example, polymers such as dimers (dimers or uretdione) and trimers (trimers or isocyanurates), or derivatives (or modified products) such as adducts, biurets, allophanates, and carbodiimides.

[0061] These polyisocyanates can be used alone or in combination of two or more. Among these polyisocyanates, bulky polyisocyanates such as MDI and TDI are often used.

[0062] As the long-chain polyols, polymer polyols are often used. Examples of polymer polyols include polyester polyols, polyether polyols, polyether ester polyols, polycarbonate polyols, (meth)acrylic polyols, polybutadiene polyols, and partially saponified ethylene-vinyl acetate copolymers. These polymer polyols can be used alone or in combination of two or more. Of these polymer polyols, polyester polyols, polyether polyols, polyether ester polyols, and polycarbonate polyols are often used.

[0063] The polyester polyol may be, for example, a homopolymer or copolymer of a polycarboxylic acid (or dicarboxylic acid) component and a polyol (short-chain polyol or diol) component; a homopolymer or copolymer of a lactone component (or a corresponding hydroxycarboxylic acid component); or a copolymer of a polycarboxylic acid component and / or a polyol component and a lactone component (or a corresponding hydroxycarboxylic acid component). The polycarboxylic acid component includes polycarboxylic acid and its ester-forming derivatives, for example, lower alkyl esters such as methyl esters and ethyl esters, acid halides such as acid chlorides, acid anhydrides, etc.

[0064] The polycarboxylic acid component is often a dicarboxylic acid component, and examples of the dicarboxylic acid component include aliphatic dicarboxylic acids such as succinic acid, adipic acid, and sebacic acid; alicyclic dicarboxylic acids such as tetrahydrophthalic (anhydride) and hexacarboxylic (anhydride); aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and phthalic anhydride, and ester-forming derivatives thereof. These polycarboxylic acid components can be used alone or in combination. Among these polycarboxylic acids, aliphatic dicarboxylic acid components are often used. Preferred aliphatic dicarboxylic acid components include C 2 dicarboxylic acids such as succinic acid, adipic acid, and sebacic acid. 4-20 Alkanedicarboxylic acids are preferred, and more preferably, C 4-16 Alkanedicarboxylic acids, C 4-12 Alkanedicarboxylic acids, C 4-8 Alkanedicarboxylic acids, especially C such as adipic acid 5-7 Examples of the aliphatic dicarboxylic acid component include alkanedicarboxylic acids and their ester-forming derivatives. These aliphatic dicarboxylic acid components can be used alone or in combination of two or more.

[0065] The polyol (or short-chain polyol) component is often a diol (or short-chain diol) component, and examples of the diol component include an aliphatic diol component, an alicyclic diol component, an aromatic diol component, and an alkylene oxide (alkylene carbonate or haloalkanol) adduct thereof.

[0066] Examples of the aliphatic diol component include alkanediols, specifically linear or branched C alkanediols such as ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol. 2-22 Alkanediols and the like.

[0067] Examples of the alicyclic diol component include cycloalkanediols such as 1,4-cyclohexanediol, cycloalkanedialkanols such as 1,4-cyclohexanedimethanol, and hydrogenated products of aromatic diol components described below, specifically hydrogenated bisphenols such as hydrogenated bisphenol A.

[0068] Examples of the aromatic diol component include aromatic aliphatic diols such as xylylene glycol, bisphenols such as bisphenol A, bisphenol S, and bisphenol F, and biphenol.

[0069] Examples of the alkylene oxide adducts of the diol components include C alkylene oxides such as ethylene oxide. 2-4 Examples include adducts of alkylene oxides (alkylene carbonates or haloalkanols).

[0070] These polyol components can be used alone or in combination. Among these polyols, aliphatic diol components are often used, and preferred are linear or branched C diols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol. 2-16Alkanediols, more preferably linear or branched C 2-12 Alkanediols, linear or branched C 2-8 Alkanediols, linear or branched C 2-6 These aliphatic diol components can be used alone or in combination of two or more.

[0071] Examples of lactone components include butyrolactone, valerolactone, caprolactone, and enantholactone. 3-18 These lactone components can be used alone or in combination of two or more. Among these lactone components, C lactones such as valerolactone and caprolactone are preferred. 4-12 Lactones, especially C 4-8 Lactones, especially C such as ε-caprolactone 5-7 Lactones are often used.

[0072] As a representative polyester polyol, an aliphatic polyester polyol, particularly an aliphatic polyester diol, is frequently used. Examples of the aliphatic polyester diol include a homopolymer or copolymer of an aliphatic dicarboxylic acid component and an aliphatic diol component, a homopolymer or copolymer of a lactone component (or a corresponding hydroxycarboxylic acid component), and a copolymer of an aliphatic dicarboxylic acid component and / or an aliphatic diol component and a lactone component (or a corresponding hydroxycarboxylic acid component).

[0073] Examples of the homopolymer or copolymer (or polyalkylene alkanoate) of an aliphatic dicarboxylic acid component and an aliphatic diol component include poly(mono- to penta-C) copolymers having hydroxyl groups at both ends, such as polyethylene adipate, polybutylene adipate, polyneopentylene adipate, polyhexamethylene adipate, polydiethylene glycol adipate, and copolymers thereof. 2-12 Alkylene glycol-C 4-12These polyalkylene alkanoates can be used alone or in combination of two or more. Preferred polyalkylene alkanoates include poly(mono- to tetra-C 2-10 Alkylene-C 4-10 Alkanoate), and more preferably poly(mono- to tri-C 2-8 Alkylene-C 4-8 Alkanoates), especially poly(mono or di C 2-6 Alkylene-C 5-7 alkanoates), or copolymers thereof. In the case of a copolymer, it is sufficient that the copolymer contains, as the main structural unit, structural units formed from an aliphatic dicarboxylic acid component and an aliphatic diol component, and may be modified by copolymerization with other components, such as the alicyclic diol component, the aromatic diol component, and their alkylene oxide adducts, as well as the alicyclic dicarboxylic acid component and the aromatic dicarboxylic acid component. The proportion of structural units derived from the aliphatic dicarboxylic acid component and the aliphatic diol component in the copolymer may be selected from a range of, for example, about 30 mol % or more, preferably 50 mol % or more, more preferably 70 mol % or more, and particularly preferably 90 mol % or more, based on the total structural units of the copolymer.

[0074] Examples of the homopolymer or copolymer (polylactone or polyhydroxyalkanoate) of the lactone component (or the corresponding hydroxycarboxylic acid component) include polyC having hydroxyl groups at both ends, such as polyβ-propiolactone, polyγ-butyrolactone, polyδ-valerolactone, polyβ-methyl-δ-valerolactone, polyε-caprolactone, and copolymers thereof. 3-12 Lactone (or polyC 3-12 These polylactones can be used alone or in combination of two or more. Preferred polylactones include polyC 4-10 Lactone, more preferably poly C 4-8 Lactones, especially poly C such as poly ε-caprolactone 5-7Lactones are included.

[0075] When ring-opening polymerizing a lactone component, a conventional initiator may be used. Examples of initiators for lactone components include water, alkylene oxide homopolymers or copolymers, low-molecular-weight polyols, and compounds having an amino group. Examples of alkylene oxide homopolymers or copolymers include polyalkylene glycols such as polyethylene glycol and polytetramethylene ether glycol. Examples of low-molecular-weight polyols include alkanediols such as ethylene glycol, trimethylolpropane, glycerin, diglycerin, pentaerythritol, sorbitol, and bisphenol A. Examples of compounds having an amino group include diamine compounds such as ethylenediamine, hexamethylenediamine, hydrazine, xylylenediamine, and isophoronediamine. These initiators can be used alone or in combination.

[0076] The copolymer of an aliphatic dicarboxylic acid component and / or an aliphatic diol component with a lactone component (or a corresponding hydroxycarboxylic acid component) may have hydroxyl groups at both ends, and may be, for example, 4-12 Alkanedicarboxylic acid component and / or linear or branched C 2-12 Alkanediol component and C 4-12 These copolymers may be used alone or in combination of two or more. Preferred copolymers include those listed below: 4-8 Alkanedicarboxylic acid component and / or linear or branched C 2-8 Alkanediol component and C 4-8 Copolymers with lactone components, more preferably C such as adipic acid 5-7 Alkanedicarboxylic acid components and / or linear or branched C such as ethylene glycol, 1,4-butanediol 2-6 Alkanediol components and C such as ε-caprolactone 5-7 Copolymers with lactone components are also included.

[0077] These aliphatic polyester diols may be used alone or in combination.

[0078] The polyether polyol (or polyether diol) may be a reaction product obtained by ring-opening an alkylene oxide and polymerizing it homopolymerically or copolymerically. A conventional initiator may be used for the ring-opening reaction, and examples of the initiator include the same initiators as those exemplified as initiators for the lactone component. Examples of alkylene oxide include C alkylene oxides such as ethylene oxide, propylene oxide, and tetrahydrofuran. 2-6 Alkylene oxide, preferably C 2-4 Alkylene oxides are exemplified.

[0079] Representative polyether polyols (or polyether diols) include alkylene oxide homopolymers or copolymers (polyalkylene glycols), alkylene oxide adducts of bisphenols or their hydrogenated derivatives, etc. Examples of polyalkylene glycols include C olefins such as polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol, ethylene oxide-propylene oxide copolymers, and tetrahydrofuran-ethylene oxide copolymers. 2-6 Alkylene oxide homo- or copolymer (or polyC 2-6 Examples of alkylene oxide adducts of bisphenols or their hydrogenated derivatives include alkylene oxide adducts of bisphenol A or hydrogenated bisphenol A. These polyether polyols can be used alone or in combination of two or more. Many of these polyether polyols are alkylene oxide homopolymers or copolymers, and among these, C 2-4 Alkylene oxide homo- or copolymers, especially C such as polytetramethylene ether glycol and polypropylene glycol 3-4Alkylene oxide homo- or copolymers are often used.

[0080] Examples of the polyetherester polyol (or polyetherester diol) include a polymer of the polycarboxylic acid (or dicarboxylic acid) or an ester-forming derivative thereof with the polyether polyol.

[0081] The polycarbonate polyol (or polycarbonate diol) can be prepared, for example, by reacting a polyol (or diol) component with phosgene, or by transesterification, in which a polyol component is reacted with a carbonate component. Examples of the carbonate component include di(alkyl or aryl) carbonates such as diethyl carbonate and diphenyl carbonate; and cyclic carbonates such as alkylene carbonates such as ethylene carbonate. Diol components are often used as the polyol component, and examples of the diol component include the polyol components exemplified in the polyester polyols (aliphatic diol components, alicyclic diol components, aromatic diol components, and alkylene oxide adducts thereof). These polyol components can be used alone or in combination.

[0082] Representative polycarbonate polyols include aliphatic polycarbonate polyols such as polyhexamethylene carbonate polyol, etc. These polycarbonate polyols can be used alone or in combination of two or more.

[0083] Of these polymer polyols, polyester polyols, polyether polyols, and polycarbonate polyols are commonly used, and among these, polyester polyols and polyether polyols such as polytetramethylene ether glycol are preferred, with polyether polyols being even more preferred because they can easily and effectively improve melt fluidity while maintaining or improving mechanical properties.

[0084] As the chain extender (chain extender), a conventional chain extender can be used, and examples thereof include polyols (short-chain polyols) such as short-chain glycols, polyamines, and the like.

[0085] Examples of polyols as chain extenders include diols (short-chain diols) such as alkanediols, cycloalkanediols, and aromatic diols; and polyols having three or more hydroxyl groups such as trimethylolpropane (TMP), glycerin, and sorbitol. Examples of the alkanediols include C alkanediols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, and 1,6-hexanediol. 2-6 Examples of the cycloalkanediol include cyclohexanediol and cyclohexanedimethanol. Examples of the aromatic diol include dihydroxyarenes such as hydroquinone diethylol ether (BHEB), dimethylolarenes such as 1,4-dimethylolbenzene, bisphenols such as bisphenol A, and C derivatives thereof. 2-4 alkylene oxide adducts.

[0086] Examples of polyamines as chain extenders include alkylenediamines such as ethylenediamine, tetramethylenediamine, and hexamethylenediamine, alkanolamines such as triethanolamine, and aromatic diamines such as 4,4'-diaminodiphenylmethane and 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA).

[0087] These chain extenders can be used alone or in combination. Among these chain extenders, polyols (short-chain polyols), particularly short-chain diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, hydroquinone diethylol ether (BHEB), 1,4-dimethylolbenzene, bisphenol A or its ethylene oxide adduct, and sugar alcohols are preferred, and 1,4-butanediol is particularly often used.

[0088] Such thermoplastic polyurethane elastomers (TPUs) can be used alone or in combination. Examples of commonly used TPUs include polyester-type TPUs containing polyester polyol in the soft segment, polyether-type TPUs containing polyether polyol in the soft segment, and polycarbonate-type TPUs containing polycarbonate polyol in the soft segment. Among these, polyester-type TPUs and polyether-type TPUs are preferred, with polyether-type TPUs being even more preferred because they can effectively improve melt fluidity while maintaining or improving mechanical properties.

[0089] (Polyester-based thermoplastic elastomer) The polyester-based thermoplastic elastomer (TPEE) has hard segments formed from aromatic crystalline polyester, liquid crystal molecules, etc., and soft segments formed from polyether or polyester with a low glass transition temperature, and is preferably a multi-block copolymer.

[0090] TPEE can be broadly classified into polyester-polyether type TPEE (or TEEE), polyester-polyester type TPEE, and liquid crystalline TPEE.

[0091] Polyester-polyether type TPEE (or TEEE) contains aromatic crystalline polyester as hard segments and polyether as soft segments.

[0092] Polyalkylene arylates are often used as aromatic crystalline polyesters for the hard segments. Diol components that form polyalkylene arylates include C 4 alkyl esters such as ethylene glycol and 1,4-butanediol. 2-6 Examples of the dicarboxylic acid component include C alkylene glycols, terephthalic acid, 2,6-naphthalenedicarboxylic acid, and ester-forming derivatives thereof. 6-12 arene-dicarboxylic acid components, etc. These diol components and / or dicarboxylic acid components can be used either alone or in combination of two or more.

[0093] Representative polyalkylene arylates include poly(C) such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polybutylene naphthalate. 2-6 Alkylene C 8-16 These polyalkylene arylates can be used alone or in combination of two or more. Among these polyalkylene arylates, poly C 2-5 Alkylene C 8-14 Arylate, especially poly C such as PBT 2-4 Alkylene C 8-12 Arylate is often used.

[0094] The soft segment polyether is usually introduced into the TEEE by copolymerizing it as a diol component with the diol component and dicarboxylic acid component that form the hard segment. Examples of such polyethers (or diol components that form the soft segment) include the same polyethers as the polyether polyols (polyether diols) described in the section on polyurethane-based thermoplastic elastomers (TPU). Representative polyethers include C polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. 2-6 Alkylene oxide homo- or copolymer (or polyC 2-6These polyethers can be used alone or in combination of two or more. Among these polyethers, C 2-4 They are often homopolymers or copolymers of alkylene oxides, among which C 3-4 Alkylene oxide homo- or copolymers are often used.

[0095] Polyester-polyester type TPEEs contain aromatic crystalline polyesters as hard segments and polyesters as soft segments. The aromatic crystalline polyesters are similar to the polyalkylene arylates exemplified in the polyester-polyether type TPEE (or TEEE) section, including preferred embodiments.

[0096] Examples of polyesters for the soft segment include polyesters similar to the polyester polyols described in the section on thermoplastic polyurethane elastomers (TPUs) above, except that they do not necessarily have hydroxyl groups at both ends. Among these, aliphatic polyesters similar to the polyesters exemplified as aliphatic polyester diols, including preferred embodiments, include homopolymers or copolymers of aliphatic dicarboxylic acid components and aliphatic diol components; homopolymers or copolymers of lactone components (or corresponding hydroxycarboxylic acid components); and copolymers of aliphatic dicarboxylic acid components and / or aliphatic diol components and lactone components (or corresponding hydroxycarboxylic acid components). These polyesters for the soft segment can be used alone or in combination of two or more.

[0097] The polyester-polyester type TPEE may contain a chain extender in its chemical structure as needed. Examples of the chain extender include those similar to those described in the section on thermoplastic polyurethane elastomers (TPUs). Among these, polyols (short-chain polyols) such as short-chain diols are preferred.

[0098] Liquid crystalline TPEEs contain liquid crystal molecules as hard segments and polyesters as soft segments. Examples of liquid crystal molecules include low-molecular-weight liquid crystal compounds, such as dihydroxy-ring-assembly arene compounds such as dihydroxy-para-quaterphenyl (DHQ). These liquid crystal molecules can be used alone or in combination. Examples of polyesters forming the soft segments include those described in the polyester-polyester TPEE section, with aliphatic polyesters being preferred. These polyesters as soft segments can be used alone or in combination.

[0099] These TPEEs can be used alone or in combination.

[0100] (Polyamide thermoplastic elastomer) The polyamide-based thermoplastic elastomer (TPA) has a hard segment formed of polyamide and a soft segment formed of a polyether, polyester, polycarbonate, or the like having a low glass transition temperature, and is preferably a multi-block copolymer.

[0101] Examples of polyamides for the hard segment include aliphatic polyamides such as polyamide 6, polyamide 66, polyamide 610, polyamide 11, and polyamide 12. These polyamides can be used alone or in combination. Among these polyamides, polyamide 6, polyamide 11, and polyamide 12 are often used.

[0102] Because soft segments are typically linked to the polyamide hard segments via ester bonds, long-chain polyol (or long-chain diol) components are often used as the polyether, polyester, or polycarbonate that forms the soft segments. Examples of such long-chain polyol (long-chain diol) components include the same long-chain polyol components as the polyether polyols, polyester polyols, polyether ester polyols, and polycarbonate polyols described in the section on thermoplastic polyurethane elastomers (TPU), including preferred embodiments. These long-chain polyol components can be used alone or in combination.

[0103] Furthermore, the thermoplastic polyamide elastomer (TPA) may contain a chain extender (chain extender) such as an aliphatic dicarboxylic acid such as adipic acid or an ester-forming derivative thereof in its chemical structure, if necessary.

[0104] These TPAs ​​can be used alone or in combination.

[0105] These thermoplastic elastomers (A) do not necessarily have a linear or straight-chain structure and may be partially crosslinked. The thermoplastic elastomer (A) may take the form of, for example, a block copolymer, a graft copolymer, a mixture of a rubber component and a resin, or an ionically crosslinked polymer, depending on its type. When it is a block copolymer, it may have various block structures such as a triblock structure, a multiblock structure, or a radial block (star) structure. Furthermore, these thermoplastic elastomers (A) may be modified by the introduction of functional groups, etc.

[0106] The molecular weight (or weight average molecular weight) of the hard segment of the thermoplastic elastomer (A) may be selected from the range of about 50 to 1,000, for example.

[0107] In the thermoplastic elastomer (A), the mass ratio between the hard segment and the soft segment may be, for example, the former / the latter = about 10 / 90 to 90 / 10.

[0108] The number average molecular weight Mn of the thermoplastic elastomer (A) may be, for example, about 10,000 to 1,000,000 in terms of polystyrene, as determined by GPC (gel permeation chromatography).

[0109] The glass transition temperature Tg of the thermoplastic elastomer (A) may be, for example, about −100 to 20° C., preferably about −50 to −10° C., and more preferably about −30 to −15° C. Tg can be measured by the temperature of E″max in a dynamic viscoelasticity test (10 Hz).

[0110] These thermoplastic elastomers (A) can be used alone or in combination. Among these thermoplastic elastomers (A), at least one engineering plastic (ERP) thermoplastic elastomer selected from polyurethane thermoplastic elastomers (TPU), polyester thermoplastic elastomers (TPEE), and polyamide thermoplastic elastomers (TPA) is preferred. TPU, TPEE, and TPA are obtained by polyaddition, polycondensation, transesterification, or other methods, and often have multiblock structures that effectively improve melt fluidity while maintaining or improving mechanical properties. Among these engineering plastic thermoplastic elastomers, TPU and TPEE are preferred, with TPU being particularly preferred due to its ability to more effectively improve melt fluidity. TPU is known for its particularly low fluidity, making it difficult to mold into fine or complex shapes. However, the thermoplastic composition of the present disclosure effectively improves melt fluidity even when it contains TPU, facilitating the easy and efficient molding or production of molded articles.

[0111] The proportion of the preferred thermoplastic elastomer (A) relative to the total thermoplastic elastomer (A) may be, for example, 50% by mass or more, specifically about 60 to 100% by mass, and preferably 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, and preferably substantially 100% by mass. The preferred proportion of the thermoplastic elastomer (A) may be the total proportion of polyurethane-based thermoplastic elastomer (TPU), polyester-based thermoplastic elastomer (TPEE), and polyamide-based thermoplastic elastomer (TPA); the total proportion of TPU and TPEE; or the proportion of TPU. When the proportion of the preferred thermoplastic elastomer (A) is within a moderate range that is not too small, it tends to be easier to achieve both strength and elongation.

[0112] The proportion of the thermoplastic elastomer (A) may be selected from a range of, for example, about 10% by mass or more, for example, 30% by mass or more, specifically about 50 to 99.99% by mass, based on the entire thermoplastic composition, and preferably in the following stepwise manner: 70 to 99.9% by mass, 80 to 99.7% by mass, 90 to 99.5% by mass, 95 to 99.3% by mass, 90 to 99% by mass, and 87 to 93% by mass. When the proportion of the thermoplastic elastomer (A) is within an appropriate range that is not too small, deterioration in moldability (thermoplasticity or melt fluidity) tends to be easily suppressed.

[0113] [Fluorene compound (B)] In the present disclosure, the fluorene compound (B) functioning as a flowability improver (melt flowability improver) is a compound represented by the following formula (1), and by combining it with the thermoplastic elastomer (A), it is possible to improve the melt flowability without impairing (maintaining or improving) the mechanical properties.

[0114] [ka] [In the formula, R 1 represents a substituent, k represents an integer of 0 to 8, R 2a , R 2b , R 2cand R 2d each independently represents a hydrogen atom or a substituent, R 3a and R 3b each independently represents a hydrogen atom or a substituent, X 1a and X 1b each independently represents a group represented by the following formula (X1):

[0115] [ka] (In the formula, R 4 and R 5 each independently represents a hydrogen atom or a hydrocarbon group, or R 4 and R 5 and bond to each other to form a heterocycle together with the adjacent nitrogen atom).

[0116] In the formula (1), the group R 1 The substituent may be a non-reactive substituent inert to the reaction, and examples thereof include a cyano group; a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; and a hydrocarbon group such as an alkyl group or an aryl group. The aryl group may be a C 6-10 Aryl groups are preferred. 1 is a cyano group, a halogen atom, or an alkyl group, particularly an alkyl group.

[0117] Examples of the alkyl group include C methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl groups. 1-12 Alkyl groups, preferably C 1-8 C alkyl groups, especially methyl groups 1-4 Examples of suitable alkyl groups include:

[0118] In addition, the group R 1 When the number of substitutions k is plural (2 or more), two or more groups R 1The types of groups may be the same or different, and two or more groups R 1 The types of groups R may be the same or different. 1 The bonding position (substitution position) of is not particularly limited as long as it is the 1st to 8th positions of the fluorene ring, and examples thereof include the 2nd, 7th, and 2,7th positions of the fluorene ring.

[0119] The number of substitutions k may be, for example, an integer of about 0 to 6, and preferred ranges are integers of 0 to 4, 0 to 3, and 0 to 2, stepwise, more preferably 0 or 1, and particularly preferably 0. In the two benzene rings constituting the fluorene ring, the group R 1 The number of substitutions in each of the above may be different from each other, but is preferably the same.

[0120] R 2a , R 2b , R 2c and R 2d The substituent represented by the formula (I) may be a non-reactive substituent that is inactive in the reaction, and examples thereof include hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups.

[0121] Examples of the alkyl group include linear or branched C alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, neopentyl, hexyl, octyl, and decyl groups. 1-12 alkyl groups, preferably straight-chain or branched-chain C 1-10 Alkyl groups, more preferably linear or branched C 1-6 It is an alkyl group.

[0122] Examples of the cycloalkyl group include C cyclopentyl and cyclohexyl groups. 5-10 Cycloalkyl groups are exemplified.

[0123] Examples of the aryl group include C phenyl, alkylphenyl, biphenylyl, and naphthyl groups. 6-12Examples of the alkylphenyl group include mono- to tri-C alkylphenyl groups such as methylphenyl (or tolyl) and dimethylphenyl (or xylyl). 1-4 Examples include alkyl-phenyl groups.

[0124] Examples of the aralkyl group include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl-C 1-4 Examples of suitable alkyl groups include:

[0125] R 2a , R 2b , R 2c and R 2d Preferred substituents represented by the formula: 1-6 Alkyl group, C 1-5 Alkyl group, C 1-4 Alkyl group, C 1-3 alkyl group, more preferably C 1-2 It is an alkyl group, in particular a methyl group.

[0126] Preferred R 2a , R 2b , R 2c , R 2d is a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom. 2c and R 2d is preferably a hydrogen atom, and in such an embodiment, the preferred R 2a and R 2b is a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom (i.e., R 2a , R 2b , R 2c and R 2d are preferably hydrogen atoms).

[0127] Also, R 2a , R 2b , R 2c , R 2dThe types of R may be different from each other, 2a and R 2b are identical and R 2c and R 2d are preferably the same.

[0128] R 3a and R 3b The substituent represented by may be a non-reactive substituent that is inert to the reaction, and examples thereof include hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. Examples of these hydrocarbon groups include the above-mentioned R 2a , R 2b , R 2c and R 2d Examples of the substituent represented by the formula (I) include the same groups as the hydrocarbon groups exemplified above.

[0129] R 3a and R 3b Among the substituents represented by the formula (I), preferred substituents are alkyl groups, and preferred alkyl groups are as follows, in the order of steps: 1-6 Alkyl group, C 1-5 Alkyl group, C 1-4 Alkyl group, C 1-3 alkyl group, more preferably C 1-2 It is an alkyl group, in particular a methyl group.

[0130] Also, the preferred R 3a and R 3b is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0131] X 1a and X 1b (or formula (X1)), R 4 and R 5 Examples of the hydrocarbon group in the formula include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and a group in which a plurality of these groups are combined. Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group, and a group in which a plurality of these groups are combined include, for example, the above-mentioned R 2a , R2b , R 2c and R 2d Examples of the substituent represented by the formula (I) include the same groups as the hydrocarbon groups exemplified above.

[0132] R 4 and R 5 Among the hydrocarbon groups in the formula (I), aliphatic hydrocarbon groups such as alkyl groups and cycloalkyl groups are preferred, and among these, alkyl groups (linear or branched alkyl groups) such as methyl groups, ethyl groups, and isopropyl groups are preferred. More preferred alkyl groups are those listed in the following order: 1-8 Alkyl group, C 1-6 Alkyl group, C 1-4 is an alkyl group, C 1-3 Alkyl group, C 1-2 R is an alkyl group or a methyl group. 4 and R 5 When both of R 4 and R 5 The types may be different from each other, but are preferably the same.

[0133] Also, R 4 and R 5 and may be bonded to each other to form a heterocycle (N-containing heterocycle) together with the adjacent nitrogen atom, the heteroatom being the nitrogen atom [i.e., R 4 , R 5and a nitrogen atom bonding with a carbonyl group to form an amide group (amide bond or carboxylic acid amide), and may further contain one or more heteroatoms in addition to the nitrogen atom, as necessary. Examples of the heteroatom that may further be contained include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocycle may contain at least one heteroatom selected from these, and preferably contains at least an oxygen atom. The number of heteroatoms constituting the heterocycle 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 is preferably non-aromatic.

[0134] Representative heterocycles include heterocycles containing one or more nitrogen atoms, such as a pyrrolidine ring, a piperidine ring, and a homopiperidine ring (an azepane ring, a hexahydroazepine ring, or a hexamethyleneimine ring), and heterocycles containing a nitrogen atom and a heteroatom of a different kind, such as a morpholine ring. Preferred are non-aromatic 5- to 7-membered heterocycles containing a nitrogen atom and a heteroatom of a different kind, particularly an oxygen atom, such as a morpholine ring.

[0135] R 4 ,R 5 is preferably a hydrogen atom or a hydrocarbon group such as an aliphatic hydrocarbon group, more preferably a hydrogen atom or an alkyl group (a linear or branched alkyl group), and even more preferably a hydrogen atom or a C 1-6 Alkyl group, hydrogen atom or C 1-5 Alkyl group, hydrogen atom or C 1-4 Alkyl group, hydrogen atom or C 1-3 Alkyl group, hydrogen atom or C 1-2 an alkyl group, a hydrogen atom or a methyl group, in particular a hydrogen atom; R 4 and R 5 Most preferably, both are hydrogen atoms.

[0136] X 1aand X 1b The types may be different from each other, but are preferably the same.

[0137] In formula (X1), R adjacent to the nitrogen atom 4 and R 5 may both be hydrogen atoms; one may be a hydrogen atom and the other may be a hydrocarbon group such as an aliphatic hydrocarbon group; R 4 and R 5 may both be hydrocarbon groups such as aliphatic hydrocarbon groups, or may be linked together to form a heterocyclic ring. 1a ] and / or [-C(=O)-X 1b ] may be an unsubstituted amide group (or a carbamoyl group [—C(═O)—NH]); a monosubstituted amide group (or an N-substituted amide group); or a disubstituted amide group (or an N,N-disubstituted amide group). When it is a disubstituted amide group, R 4 and R 5 Preferably, both of the groups are aliphatic hydrocarbon groups.

[0138] Preferred groups [—C(═O)—X 1a ] and / or [-C(=O)-X 1b ] is preferably an unsubstituted amide group or a monosubstituted amide group, and from the viewpoint of easily maintaining or improving mechanical properties such as flexural strength, flexural modulus, tensile strength, and tensile elongation, and effectively improving fluidity (melt fluidity), an unsubstituted amide group is more preferred, and the group [—C(═O)—X 1a ] and [-C(=O)-X 1b It is particularly preferred that both of the groups 1 and 2 are unsubstituted amide groups.

[0139] Representative fluorene compounds (B) include, for example, those represented by the formula (1) in which R 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, R 4 and R 5and a compound in which both are hydrogen atoms (unsubstituted amide compound), specifically, for example, 9,9-bis[(2-carbamoyl)C such as 9,9-bis(2-carbamoylethyl)fluorene and 9,9-bis(2-carbamoylpropyl)fluorene. 2-3 alkyl]fluorene, etc.; in formula (1), R 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, R 4 and R 5 and the other is an alkyl group (N-alkyl substituted compound), specifically, for example, 9,9-bis[2-(NC)-methylcarbamoylethyl]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, etc. 1-6 Alkyl-carbamoyl)C 2-3 alkyl]fluorene, etc.; in formula (1), R 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, R 4 and R 5is an alkyl group (N,N-dialkyl substituted compound), specifically, for example, 9,9-bis[2-(N,N-diC] such as 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, and 9,9-bis[2-(N,N-dibutylcarbamoyl)ethyl]fluorene. 1-6 Alkyl-carbamoyl)C 2-3 alkyl]fluorene, etc.; in formula (1), R 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, R 4 and R 5 and bond to each other to form a 5- to 7-membered heterocycle which may further contain at least one heteroatom selected from a nitrogen atom, an oxygen atom, and a sulfur atom in addition to the nitrogen atom constituting the amide group, specifically, for example, 9,9-bis[2-(N-containing heterocycle-N-yl-carbonyl)C such as 9,9-bis[2-(morpholin-4-yl-carbonyl)ethyl]fluorene, 9,9-bis[2-(morpholin-4-yl-carbonyl)propyl]fluorene, 9,9-bis[2-(pyrrolidin-1-yl-carbonyl)ethyl]fluorene, 9,9-bis[2-(piperidin-1-yl-carbonyl)ethyl]fluorene, and 9,9-bis[2-(homopiperidin-1-yl-carbonyl)ethyl]fluorene. 2-3 alkyl]fluorene and the like.

[0140] The molecular weight of the fluorene compound (B) may be, for example, about 308 to 2000, and preferably ranges in the following stepwise order: 308 to 1000, 308 to 800, 308 to 500, 308 to 450, 308 to 400, and 308 to 350. When the molecular weight is within an appropriate range that is not too large, fluidity tends to be easily improved.

[0141] The fluorene compound (B) may be in a crystalline or amorphous form, and the melting point of the crystalline form is determined by the group [—C(═O)—X 1a ] and [-C(=O)-X 1b When the group [—C(═O)—X 1a ] and [-C(=O)-X 1b When the group [—C(═O)—X 1a ] and [-C(=O)-X 1b When [Chemical Formula 1] is a disubstituted amide group, the temperature may be, for example, about 50 to 200°C, preferably 70 to 180°C, and more preferably 80 to 160°C.

[0142] In this specification and claims, the melting point can be measured using a melting point meter or the like, specifically, by the method described in the examples of WO 2021 / 172300.

[0143] The 5% weight loss temperature of the fluorene compound (B) may be, for example, about 200 to 400°C, and preferably the following stepwise temperatures: 230 to 380°C, 250 to 360°C, 280 to 350°C, 300 to 340°C, and 310 to 330°C. As described above, the fluorene compound (B) has high heat resistance. Therefore, it does not decompose even in a high-temperature environment and can be effectively used as a flow improver or strength improver.

[0144] In this specification and claims, the 5% weight loss temperature can be measured using thermogravimetry (TG), specifically, by the method described in the examples of WO 2021 / 172300.

[0145] These fluorene compounds (B) can be used alone or in combination of two or more. Among these fluorene compounds (B), the unsubstituted amide compounds, N-alkyl-substituted compounds or N,N-dialkyl-substituted compounds are preferred, and the unsubstituted amide compounds or N-alkyl-substituted compounds are more preferred. The unsubstituted amide compounds are particularly preferred from the viewpoint that they can easily maintain or improve mechanical properties such as bending strength, bending modulus, tensile strength, tensile elongation, and can effectively improve fluidity (melt fluidity).

[0146] The method for producing the fluorene compound (B) represented by the formula (1) is not particularly limited, and for example, the method described in WO 2021 / 172300, specifically, 1 and k, and 9H-fluorenes corresponding to R 2a ~R 2d , R 3a ~R 3b and X 1a ~X 1b (or R 4 ~R 5 ) with a corresponding acryloyl group-containing compound (Michael addition reaction).

[0147] The proportion of the fluorene compound (B) can be selected from a range of, for example, about 0.01 to 80 parts by mass relative to 100 parts by mass of the total amount of the thermoplastic elastomer (A) and the fluorene compound (B), preferably in the following stepwise manner: 0.01 to 50 parts by mass, 0.01 to 30 parts by mass, 0.01 to 15 parts by mass, 0.03 to 10 parts by mass, 0.04 to 8 parts by mass, 0.05 to 5 parts by mass, 0.06 to 4 parts by mass, 0.07 to 3.5 parts by mass, 0.08 to 3 parts by mass, and 0.1 to 2 parts by mass. When the proportion of the fluorene compound (B) is within a moderate range, it tends to improve fluidity without significantly impairing (maintaining or improving) mechanical properties, and it also tends to suppress bleed-out of the fluorene compound (B). When the proportion of the fluorene compound (B) is within a moderate range, it tends to improve mechanical properties such as fluidity and bending properties. However, in the present disclosure, even if the proportion of the fluorene compound (B) is relatively small, it is possible to effectively improve the flowability and improve the mechanical properties such as bending properties in some cases.

[0148] [Other ingredients] The thermoplastic composition may or may not contain other components different from the thermoplastic elastomer (A) and the fluorene compound (B), as needed, such as other flow improvers, thermoplastic resins, fibrous reinforcing materials, and conventional additives.

[0149] (Other flow improvers) The thermoplastic composition may or may not contain a second fluidity improver different from the fluorene compound (B) (first fluidity improver) represented by formula (1). Examples of the second fluidity improver include compounds having a 9,9-bisarylfluorene skeleton, such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF), specifically compounds described in International Publication No. 2020 / 022356. The second fluidity improver may be used alone or in combination. The proportion of the second fluidity improver is, for example, approximately 0 to 100 parts by mass, preferably 50 parts by mass or less, 30 parts by mass or less, 10 parts by mass or less, 5 parts by mass or less, and 1 part by mass or less, per 100 parts by mass of the fluorene compound (B) (first fluidity improver).

[0150] The flowability improver for the thermoplastic elastomer (A) of the present disclosure only needs to contain the fluorene compound (B) (first flowability improver) represented by the formula (1), and may also contain the second flowability improver, if necessary. In the flowability improver of the present disclosure, the fluorene compound (B) (first flowability improver) represented by the formula (1) may be used alone or in combination of two or more, and the second flowability improver may be used alone or in combination of two or more. In the flowability improver of the present disclosure, the ratio of the second flowability improver to 100 parts by mass of the fluorene compound (B) (first flowability improver) represented by the formula (1) may be the same as described above, including preferred embodiments. In the flow improver of the present disclosure, the proportion of the fluorene compound (B) (first flow improver) represented by the formula (1) may be, for example, about 10% by mass or more relative to the total amount of the flow improver, and is preferably 30% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, and substantially 100% by mass is more preferred. When the proportion of the fluorene compound (B) represented by the formula (1) is in an appropriate range that is not too small, it tends to be easier to achieve a good balance between flowability and mechanical properties.

[0151] (thermoplastic resin)Examples of thermoplastic resins include polyolefin resins, specifically, linear olefin resins such as polyethylene resins and polypropylene resins, and cyclic polyolefin resins; styrene resins, specifically, polystyrene (PS) such as general-purpose polystyrene (GPPS) and syndiotactic polystyrene (SPS), and styrene copolymers, such as MS resin, AS resin, high impact polystyrene (HIPS), ABS resin, AAS resin, ACS resin, AES resin, and MBS resin, and rubber component-containing styrene resins (or rubber graphite resins). (meth)acrylic resins, specifically, homopolymers or copolymers of (meth)acrylic monomers such as polymethyl methacrylate (PMMA); vinyl acetate resins, specifically, polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), polyvinyl formal (PVF), polyvinyl butyral (PVB), and other polyvinyl acetals; vinyl chloride resins, specifically, polyvinyl chloride (PVC), vinyl chloride-vinyl acetate copolymers, vinylidene chloride-vinyl chloride copolymers, vinylidene chloride-acrylic copolymers, Vinyl chloride and / or vinylidene chloride homo- or copolymers such as thiazolinone nitrile copolymers; fluororesins, specifically, polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE); polyester resins, specifically, polyalkylene arylate resins such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), poly 1,4-cyclohexyldimethylene terephthalate (PCT), and polyethylene naphthalate, polyarylate resins, liquid crystalline polyesters; polycarbonate resins (PC), specifically, bisphenol-type polycarbonate resins such as bisphenol A;Polyamide resins (PA), specifically aliphatic polyamide resins such as polyamide 6 and polyamide 66, and aromatic polyamide resins (aramid resins) such as polyphenylene isophthalamide; polyacetal resins (POM); polyphenylene ether resins (PPE); polyphenylene sulfide resins (PPS); polysulfone resins, specifically polysulfone resins (PSF) and polyethersulfone (PES); polyetherketone resins, specifically polyetherketone resins (PEK), polyetheretherketone resins (PEEK), polyetherketoneetherketoneketone (PEKEKK), and the like; phenoxy resins; polyketone resins such as aliphatic polyketone resins; cellulose derivatives, specifically cellulose esters such as nitrocellulose, cellulose acetate, and cellulose acetate propionate, and cellulose ethers such as ethyl cellulose; thermoplastic polyimide resins, specifically polyetherimide (PEI), polyamideimide, and the like; polyethernitrile resins;

[0152] These thermoplastic resins may be contained alone or in combination of two or more. The thermoplastic composition may be substantially free of polyolefin resins such as polypropylene resins and / or polyamide resins (PA), or may be completely free of such resins.

[0153] If necessary, the thermoplastic elastomer (A) may form a polymer alloy with the thermoplastic resin, and the polymer alloy may contain a compatibilizer.

[0154] The proportion of the thermoplastic elastomer (A) relative to the total amount of the thermoplastic elastomer (A) and thermoplastic resin in the thermoplastic composition may be, for example, about 10% by mass or more, and preferably is 30% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, and 100% by mass in the following stepwise manner. When the proportion of the thermoplastic elastomer (A) is within an appropriate range that is not too small, there is a tendency for the flowability and / or mechanical properties to be effectively improved.

[0155] (fibrous reinforcing material) The thermoplastic composition may or may not contain a fibrous reinforcing material (fibrous reinforcing material or fibrous filler) as needed. Generally, fibrous reinforcing materials can significantly improve the mechanical properties of a composition, but they also significantly increase viscosity, making it difficult to achieve both mechanical properties and fluidity (moldability or processability). In particular, in applications where mechanical properties are important, a high proportion of fibrous reinforcing material must be added, and the significant increase in viscosity associated with an increase in the amount of fibrous reinforcing material may require the sacrifice of fluidity (moldability or processability). However, in the present disclosure, fluidity can be effectively improved even when a fibrous reinforcing material is included, making it easy to achieve both mechanical properties and fluidity.

[0156] Examples of fibrous reinforcing materials include organic fibers and inorganic fibers. Examples of organic fibers include modified or unmodified cellulose fibers (fibers of cellulose or its derivatives), such as cellulose fibers and cellulose acetate fibers; polyester fibers, such as polyalkylene arylate fibers; and polyamide fibers, such as aliphatic polyamide fibers and aramid fibers. Examples of inorganic fibers include glass fibers, carbon fibers, boron fibers, and wollastonite, as well as metal fibers, such as whiskers. Examples of carbon fibers include polyacrylonitrile (PAN)-based carbon fibers, pitch-based carbon fibers, such as isotropic pitch-based carbon fibers and mesophase pitch-based carbon fibers, and vapor-grown carbon fibers.

[0157] These fibrous reinforcing materials can be used alone or in combination. Preferred fibrous reinforcing materials are inorganic fibers such as modified or unmodified cellulose fibers, glass fibers, and carbon fibers.

[0158] Examples of glass components that form glass fibers include E-glass (alkali-free electrical insulating glass), S-glass (high-strength glass), C-glass (chemical glass), A-glass (general-use alkali-containing glass), and YM-31-A-glass (high-elasticity glass). Among these, E-glass, C-glass, and S-glass are preferred from the standpoint of mechanical properties, and E-glass is particularly preferred. Glass fibers formed from these glass components can be used alone or in combination of two or more.

[0159] The form of the fibrous reinforcing material may be short fiber or long fiber, or may be fabric such as woven fabric, knitted fabric, or nonwoven fabric, depending on the application. These fibrous reinforcing materials may be used alone or in combination of two or more. Short fiber is preferred because it is easy to improve flowability.

[0160] The average fiber length of the fibrous reinforcing material (when in the form of a fabric, the average fiber length of the fibers constituting the fabric) may be selected, for example, from a range of about 0.1 to 10 mm, preferably in the following stepwise order: 0.2 to 8 mm, 0.5 to 6 mm, and 1 to 4 mm. The average fiber length of the fibrous reinforcing material in the composition or molded article may be shorter than that before mixing due to the influence of mixing (kneading) when preparing the composition or shear force during molding, and is, for example, 0.05 to 5 mm, preferably 0.1 to 3 mm, and more preferably 0.2 to 1 mm.

[0161] The average fiber diameter (filament diameter) of the fibrous reinforcing material may be on the order of nanometers, and examples of such fibrous reinforcing materials include modified or unmodified cellulose nanofibers, carbon nanotubes, carbon nanocoils, carbon nanofibers, etc. From the standpoint of mechanical strength, the average fiber diameter (filament diameter) may be on the order of microns, for example, selected from the range of about 1 to 200 μm, preferably 3 to 100 μm, more preferably 4 to 30 μm, and particularly 5 to 15 μm.

[0162] The cross-sectional shape of the fibrous reinforcing material may be, for example, circular, elliptical, polygonal, etc. The fibrous reinforcing material may be subjected to a conventional surface treatment, for example, may be treated with a surface treatment agent such as a bundling agent or a silane coupling agent.

[0163] The proportion of the fibrous reinforcing material may be, for example, 50% by mass or less, 0 to 30% by mass, or 1 to 10% by mass, based on the total amount of the thermoplastic elastomer (A), the fluorene compound (B), and the fibrous reinforcing material.

[0164] (Conventional additives) The thermoplastic composition may optionally contain various additives, such as fillers or reinforcing agents (excluding the fibrous reinforcing materials), colorants such as dyes and pigments, conductive agents, flame retardants, flame retardant assistants, plasticizers, lubricants, stabilizers, release agents, antistatic agents, dispersants, compatibilizers, flow control agents, leveling agents, antifoaming agents, surface modifiers, stress reducing agents, and carbon materials (excluding the fibrous reinforcing materials). Examples of the stabilizers include antioxidants, ultraviolet absorbers, and heat stabilizers. These additives may be used alone or in combination.

[0165] The proportion of the additive may be, for example, 50% by mass or less, 0 to 30% by mass, or 1 to 10% by mass, relative to the entire thermoplastic composition.

[0166] The thermoplastic composition can be prepared by mixing the thermoplastic elastomer (A), the fluorene compound (B) (flow improver), and, if necessary, other components, by a conventional method such as dry mixing or melt kneading, and the thermoplastic composition may be in the form of pellets or the like.

[0167] [Characteristics of thermoplastic composition and molded product] The thermoplastic composition of the present disclosure has high melt fluidity, although its properties vary depending on the types and proportions of the thermoplastic elastomer (A) and fluorene compound (B). Therefore, the melt flow rate (MFR) [or melt flow index (MFI)] of the thermoplastic composition may be, for example, about 110 to 6000, preferably 150 to 5000, 200 to 4500, 250 to 4000, 300 to 3000, and 350 to 2000, when the MFR of a composition not containing the fluorene compound (B) [a composition containing the same mass of thermoplastic elastomer (A) instead of the fluorene compound (B) in the composition, hereinafter simply referred to as blank] is taken as 100.

[0168] The MFR of the blank varies depending on the type and proportion of the thermoplastic elastomer (A), but is, for example, 0.1 to 30 g / min, preferably 0.5 to 20 g / min, 1 to 15 g / min, and 2 to 10 g / min in the following stepwise manner, under measurement conditions of a temperature of 230°C and a test load of 2.16 kgf.

[0169] In this specification and claims, MFR can be measured in accordance with JIS K 7210-1 Method B, and specifically, can be measured by the method described in the examples below.

[0170] Furthermore, the thermoplastic composition of the present disclosure may be able to improve mechanical properties such as bending properties and tensile properties without excessively deteriorating them, despite containing the fluorene compound (B), which is a low molecular weight compound.

[0171] The flexural strength of the thermoplastic composition may be, for example, about 80 to 140, and preferably 90 to 135, 100 to 130, and 105 to 125, where the flexural strength of the blank is taken as 100.

[0172] The flexural strength of the blank varies depending on the type and proportion of the thermoplastic elastomer (A), but is, for example, 0.1 to 100 MPa, preferably 10 to 30 MPa, 2 to 10 MPa, and 3 to 5 MPa in the following stepwise manner.

[0173] The flexural modulus of the thermoplastic composition may be, for example, about 70 to 130, and preferably 80 to 125, 90 to 120, and 95 to 115, where the flexural modulus of the blank is 100.

[0174] The flexural modulus of the blank varies depending on the type and proportion of the thermoplastic elastomer (A), but is, for example, 10 to 300 MPa, preferably 20 to 100 MPa, 30 to 80 MPa, 40 to 70 MPa, and 45 to 65 MPa in the following stepwise manner.

[0175] In this specification and claims, the bending properties can be measured in accordance with JIS K 7171, and specifically, can be measured by the method described in the examples below.

[0176] The tensile strength (maximum tensile strength) of the thermoplastic composition may be, for example, about 70 to 120, and preferably 75 to 115, 80 to 110, 85 to 105, and 90 to 100, where the tensile strength of the blank is 100.

[0177] The tensile strength of the blank varies depending on the type and proportion of the thermoplastic elastomer (A), but is, for example, 1 to 100 MPa, preferably 5 to 50 MPa, 10 to 40 MPa, and 15 to 35 MPa in the following stepwise manner.

[0178] The tensile elongation of the thermoplastic composition may be, for example, 100 or more, and preferably 110 or more, relative to the tensile elongation of the blank, which is 100.

[0179] The tensile elongation of the blank varies depending on the type and proportion of the thermoplastic elastomer (A), but is, for example, 150% or more, preferably 200% or more.

[0180] In this specification and claims, the tensile properties can be measured in accordance with JIS K 7161-1, -2, and specifically, can be measured by the method described in the examples below.

[0181] (Molded body) The present disclosure also encompasses molded articles formed from the thermoplastic composition. The shape of the molded article is not particularly limited and can be selected depending on the application, and may be, for example, a pellet-like shape, a linear (or filamentous) one-dimensional structure, a film-like, sheet-like, or plate-like two-dimensional structure, a block-like, rod-like, or hollow (tubular or tubular) three-dimensional structure, or a composite or complex shape that combines these shapes.

[0182] The molded article can be produced by utilizing a conventional molding method such as compression molding, injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, pressure molding, casting molding, calendering, or foam molding.

[0183] The molded article may also be a composite molded article containing a thermoplastic composition part formed from the thermoplastic composition and other constituent members. The proportion of the thermoplastic composition (thermoplastic composition part) in the molded article is not particularly limited and may be, for example, about 10 to 100 mass %, or about 20 to 80 mass %. [Example]

[0184] 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.

[0185] [Evaluation method] (Tensile properties) The tensile strength (maximum tensile strength) and tensile elongation were measured at a test speed of 5 mm / min in accordance with JIS K 7161-1, -2.

[0186] (bending properties) The bending strength and bending modulus were measured at a support distance of 64 mm and a test speed of 2 mm / min in accordance with JIS K 7171. The bending modulus was calculated by the tangent method.

[0187] (MFR) Measurement was performed in accordance with JIS K 7210-1 Method B. Specifically, in Examples 1 to 15 and Comparative Examples 1 to 4, which used a thermoplastic elastomer (TPE) as the base, the measurement was performed under conditions of a holding time of 5 minutes, a temperature of 230°C, and a test load of 2.16 kgf, while in Reference Examples 1 to 7, which used PP as the base, the measurement was performed under conditions of a holding time of 5 minutes, a temperature of 190°C, and a test load of 2.16 kgf.

[0188] [Raw materials] (thermoplastic elastomer or base resin) Polyether-based TPU: BASF "Elastollan (registered trademark) 1198A50S" Polyester-based TPU: BASF "Elastollan (registered trademark) ET195-50" PP: Polypropylene resin, Prime Polypro (registered trademark) J105G manufactured by Prime Polymer Co., Ltd. (Additive (fluorene compound)) BPEF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, "BPEF" manufactured by Osaka Gas Chemicals Co., Ltd. AAD-FL: 9,9-bis(2-carbamoylethyl)fluorene represented by the following formula (1-1), prepared in accordance with Comparative Example 1 of WO 2021 / 172300, melting point 254 to 259°C, 5% weight loss temperature 320°C

[0189] [ka]

[0190] DMAA-FL: 9,9-bis[2-(N,N-dimethylcarbamoyl)ethyl]fluorene represented by the following formula (1-2), prepared in accordance with Example 2 of WO 2021 / 172300, melting point 158 ​​to 159°C, 5% weight loss temperature 318°C

[0191] [ka]

[0192] DEAA-FL: 9,9-bis[2-(N,N-diethylcarbamoyl)ethyl]fluorene represented by the following formula (1-3), prepared in accordance with Example 1 of WO 2021 / 172300, melting point 87 to 89°C, 5% weight loss temperature 294°C

[0193] [ka]

[0194] (Examples 1 to 8, Comparative Example 2) A thermoplastic elastomer (TPE) and an additive (fluorene compound) were dry-blended in the proportions shown in Table 1 below. The resulting mixture was melt-kneaded using a twin-screw extruder ("MAX30" manufactured by Nippon Placon Co., Ltd., L / D = 42, screw diameter 30 mm) at a temperature of 190 to 220°C, a screw rotation speed of 250 rpm, and a discharge rate of 20 kg / hour to prepare a pellet-shaped thermoplastic composition, and the tensile properties, flexural properties, and MFR were measured. Test pieces for the tensile properties and flexural properties were prepared by injection molding the resulting thermoplastic composition.

[0195] (Comparative Example 1) Each evaluation was carried out in the same manner as in Examples 1 to 8 and Comparative Example 2, except that no additive (fluorene compound) was added.

[0196] The evaluation results of Comparative Examples 1 and 2 and Examples 1 to 8 are shown in Table 1 below, along with the blending ratios.

[0197] [Table 1]

[0198] As is clear from Table 1, in the Examples, the MFR was significantly improved without significantly decreasing (maintaining or improving) mechanical properties such as tensile properties and flexural properties compared to Comparative Example 1 (without additives), and both mechanical properties and melt fluidity were achieved. For example, in Example 1, even with the addition of only 0.1 parts by mass, the MFR was improved by 3.5 times compared to Comparative Example 1 while maintaining or improving mechanical properties.

[0199] Although Comparative Example 2, which contains the conventional additive BPEF, is able to achieve a certain level of compatibility between mechanical properties and melt fluidity, Example 4, which contains the additive of the present disclosure in the same proportion as Comparative Example 2, exhibits mechanical properties superior to those of Comparative Example 2 while having an MFR that is more than three times that of Comparative Example 2 (42.5 times that of Comparative Example 1). Furthermore, Example 3, despite containing half the amount of additive as Comparative Example 2, exhibits an MFR similar to that of Comparative Example 2 and also has mechanical properties superior to those of Comparative Example 2. Therefore, the additive of the present disclosure is able to achieve a higher level of compatibility between mechanical properties and melt fluidity than conventional products.

[0200] Among Examples 1 to 8, it was found that Examples 1 to 4 (AAD-FL) had a superior fluidity improving effect compared to Examples 5 to 8 (DMAA-FL), and were also more likely to maintain or improve mechanical properties even when the amount of additive was increased.

[0201] In Example 8, which contained a larger amount of additive than the other Examples, the surfaces of the test pieces felt sticky, possibly due to the tendency for bleeding out to occur.

[0202] (Examples 9 to 15, Comparative Example 4) A thermoplastic elastomer (TPE) and an additive (fluorene compound) were dry-blended in the proportions shown in Table 2 below. The resulting mixture was melt-kneaded using a twin-screw extruder ("MAX30" manufactured by Nippon Placon Co., Ltd., L / D = 42, screw diameter 30 mm) at a temperature of 190 to 220°C, a screw rotation speed of 250 rpm, and a discharge rate of 20 kg / hour to prepare a pellet-shaped thermoplastic composition, and the tensile properties, flexural properties, and MFR were measured. Test pieces for the tensile properties and flexural properties were prepared by injection molding the resulting thermoplastic composition.

[0203] (Comparative Example 3) Each evaluation was carried out in the same manner as in Examples 9 to 15, except that no additive (fluorene compound) was added.

[0204] The evaluation results of Comparative Examples 3 to 4 and Examples 9 to 15 are shown in Table 2 below, along with the blending ratios.

[0205] [Table 2]

[0206] As is clear from Table 2, Examples 9 to 15 are examples in which a polyester-based TPU was used instead of the polyether-based TPU used in Examples 1 to 8. The fluidity improving effect of Examples 1 to 8 (polyether-based TPU) appears to be greater than that of examples without additives (Comparative Examples 1 and 3). However, a similar trend was also observed in Examples 9 to 15 (polyester-based TPU), and compared to Comparative Example 3 (without additives), the MFR was significantly improved without significantly decreasing (maintaining or improving) mechanical properties such as tensile properties and flexural properties, thereby achieving both mechanical properties and melt fluidity.

[0207] Although Comparative Example 4, which contains the conventional additive BPEF, is able to achieve a certain degree of compatibility between mechanical properties and melt fluidity, Example 12, which contains the additive of the present disclosure in the same proportion as Comparative Example 4, exhibits better mechanical properties than Comparative Example 4, while having an MFR that is about 1.8 times that of Comparative Example 4 (17.5 times that of Comparative Example 3). Therefore, the additive of the present disclosure was able to achieve a higher level of compatibility between mechanical properties and melt fluidity than conventional products.

[0208] Among Examples 9 to 15, it was found that Examples 9 to 12 (AAD-FL) had a superior fluidity improving effect compared to Examples 13 to 15 (DMAA-FL), and were also more likely to maintain or improve mechanical properties even when the amount of additive was increased.

[0209] (Reference examples 2~7) PP and an additive (fluorene compound) were dry-blended in the ratios shown in Table 3. The resulting mixture was melt-kneaded using a twin-screw extruder (Thermo Fisher "Process 11 Twin Screw Extruder", L / D = 40) at a temperature of 190 to 230°C, a screw rotation speed of 200 rpm, and a discharge rate of 1 kg / hour to prepare a pellet-shaped resin composition, and the MFR was measured.

[0210] (Reference example 1) Evaluation was carried out in the same manner as in Reference Examples 2 to 7, except that no additive (fluorene compound) was added.

[0211] The evaluation results of Reference Examples 1 to 7 are shown in Table 3 below, along with the blending ratios.

[0212] [Table 3]

[0213] As is clear from Table 3, in Reference Examples 3 to 5, in which AAD-FL was added to PP as a base, no improvement in MFR was observed, and rather, a decrease in MFR was observed as the addition ratio increased. On the other hand, in Reference Examples 6 and 7, in which DEAA-FL was added, an improvement in MFR was observed. Furthermore, in Reference Example 2, in which BPEF was added, the MFR was improved compared to Reference Examples 4 and 7, in which the additive was added at the same ratio. Therefore, the trends in Reference Examples 1 to 7, which used PP as a base, and Examples 1 to 15 and Comparative Examples 1 to 4, which used a thermoplastic elastomer (TPE), were completely different. [Industrial Applicability]

[0214] The thermoplastic composition (thermoplastic elastomer composition) of the present disclosure has good melt fluidity and excellent moldability without compromising mechanical properties, and therefore has a wide range of uses, from household products to industrial products.

[0215] Examples of household goods include footwear, miscellaneous goods, sporting goods, and components forming these. Examples of footwear include shoes, sandals, slippers, and the like, and the material can be used as the sole material for these footwear. Examples of miscellaneous goods or components thereof include toothbrush handles, stationery, toys, artificial flowers, and the like. Examples of sporting goods or components thereof include soles and uppers for sports shoes, shells and cuffs for ski boots and hiking boots, ski pole grips, skis, frames and end grips for tennis rackets, baseball bases, soccer balls, golf balls, golf club grips, and training machines.

[0216] Examples of industrial products include automotive parts; hoses or tubes; belts; mechanical parts such as gears, bearings, rollers, and casters; sealing materials such as packings, gaskets, and O-rings; lining materials such as interior pipe linings and water pipe repair linings; sheet materials such as flexible containers, diaphragms, keyboard sheets, gasoline tank sheets, and waterproof sheets; packaging materials; food packaging films; vibration-damping materials such as flex hammers, cushion grips, sound-absorbing gears, and vibration-proof and sound-proofing parts; wire, cable, and insulating materials such as wiring for office equipment and audio equipment, optical fiber coating materials, curl cords, and robot cables; foam materials such as sponges; shape-memory materials; medical devices such as medical tubing, bags, and medical shielded wires; adhesives or pressure-sensitive adhesives such as hot-melt adhesives; and modifiers.

[0217] Automotive parts include, for example, body parts such as bumpers, steering wheels, door latches, door strikers, seat belt parts, emblems, control cable covers, and trunk linings; chassis and steering parts such as constant velocity joint boots, rack and pinion boots, strut suspension, bushings, gear cover caps, bumper rubbers, and lower arm ball seats; engine peripheral parts such as air duct hoses and fuel line covers; and interior components such as soundproofing materials and interior covering materials.

[0218] Examples of hoses or tubes include hydraulic hoses, high-pressure hoses, ultra-high-pressure hoses, duct hoses, fire hoses, agricultural chemical hoses, painting hoses, washing machine hoses, fuel tubes, pneumatic tubes, coil tubes, gas pipes, and hose exteriors.

[0219] Examples of belts include power transmission belts such as flat belts, V-belts and toothed belts; and conveyor belts.

[0220] Examples of modifiers include resin or rubber modifiers such as impact resistance modifiers, low shrinkage agents and compatibilizers; asphalt modifiers such as roofing modifiers and road paving modifiers; and the like.

[0221] The thermoplastic composition (thermoplastic elastomer composition) of the present disclosure can also be formed into textile products that can be used as household goods, industrial products, etc. Examples of textile products include fibers, threads, ropes, nets, and fabrics (woven fabrics, knitted fabrics, nonwoven fabrics, etc.).

Claims

1. A thermoplastic elastomer (A) and a copolymer represented by the following formula (1): 【Chemical 1】 [In the formula, R １ represents a substituent, k represents an integer of 0 to 8, R ２ａ , R ２ｂ , R ２ｃ and R ２ｄ each independently represents a hydrogen atom or a substituent, R ３ａ and R ３ｂ each independently represents 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 each independently represents a hydrogen atom or a hydrocarbon group, or R ４ and R ５ and are bonded to each other to form a heterocycle together with the adjacent nitrogen atom. represents a group represented by the following formula: and a fluorene compound (B) represented by the following formula:

2. 2. The thermoplastic composition according to claim 1, wherein the thermoplastic elastomer (A) comprises at least one selected from the group consisting of a polyurethane-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, and a polyamide-based thermoplastic elastomer.

3. The thermoplastic composition according to claim 1, wherein the thermoplastic elastomer (A) comprises a polyether-type polyurethane-based thermoplastic elastomer.

4. In the formula (1), R １ represents a hydrocarbon group, k represents an integer of 0 to 4, R ２ａ , R ２ｂ , R ２ｃ and R ２ｄ each independently represents a hydrogen atom or a hydrocarbon group; R ３ａ and R ３ｂ each independently represents a hydrogen atom or a hydrocarbon group; In the formula (X1), R ４ and R ５ The thermoplastic composition according to any one of claims 1 to 3, wherein each of is independently a hydrogen atom or an alkyl group.

5. In the formula (X1), R ４ and R ５ The thermoplastic composition according to any one of claims 1 to 3, wherein is a hydrogen atom.

6. The thermoplastic composition according to any one of claims 1 to 3, wherein the proportion of the fluorene compound (B) is 0.01 to 30 parts by mass relative to 100 parts by mass of the total amount of the thermoplastic elastomer (A) and the fluorene compound (B).

7. A molded article comprising the thermoplastic composition according to any one of claims 1 to 3.

8. A method for improving the flowability of a thermoplastic elastomer (A) by adding a fluorene compound (B) represented by formula (1) according to claim 1 to the thermoplastic elastomer (A).

9. A flowability improver for a thermoplastic elastomer (A), comprising a fluorene compound (B) represented by formula (1) according to claim 1.

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