WO2024122349A1 - 樹脂組成物及び成形体 - Google Patents

樹脂組成物及び成形体 Download PDF

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Publication number
WO2024122349A1
WO2024122349A1 PCT/JP2023/042047 JP2023042047W WO2024122349A1 WO 2024122349 A1 WO2024122349 A1 WO 2024122349A1 JP 2023042047 W JP2023042047 W JP 2023042047W WO 2024122349 A1 WO2024122349 A1 WO 2024122349A1
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group
resin composition
carbon atoms
resin
formula
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English (en)
French (fr)
Japanese (ja)
Inventor
敦史 酒井
良輔 藤井
勇希 佐藤
卓弥 福島
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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Priority to JP2024562675A priority Critical patent/JPWO2024122349A1/ja
Priority to EP23900468.2A priority patent/EP4632008A4/en
Priority to CN202380081832.8A priority patent/CN120283015A/zh
Priority to KR1020257017265A priority patent/KR20250116645A/ko
Publication of WO2024122349A1 publication Critical patent/WO2024122349A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
    • C08G73/1017—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)amine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a resin composition and a molded article.
  • Polyimide resins are useful engineering plastics that have high thermal stability, high strength, and high solvent resistance due to the rigidity of their molecular chains, resonance stabilization, and strong chemical bonds, and are used in a wide range of fields.
  • polyimide resins have high heat resistance, they do not exhibit thermoplasticity and have the problem of low moldability.
  • polyimide resins with thermoplasticity have been reported.
  • Thermoplastic polyimide resins have excellent moldability in addition to the heat resistance that polyimide resins inherently have. Therefore, thermoplastic polyimide resins can be used for molded products used in harsh environments, which is not possible with general-purpose thermoplastic resins such as nylon and polyester.
  • thermoplasticity to polyimide resins is the incorporation of a flexible structure, such as an aliphatic structure, into the main chain.
  • the aliphatic structure has the advantages of being relatively easy to impart thermoplasticity to polyimides and of being prone to exhibiting low dielectric properties due to its bulkiness, but it has the problem of being inferior in oxidation resistance compared to aromatic structures, which ultimately reduces the high flame retardancy inherent to polyimides. Therefore, in order to apply such thermoplastic polyimide resins to applications requiring high flame retardancy, studies are also being conducted on adding flame retardants to improve flame retardancy.
  • Patent Document 1 discloses that a resin composition containing a polyimide resin having a specific structure and a metal phosphinate-based flame retardant has excellent moldability and can achieve both high flame retardancy and good appearance.
  • Patent Document 2 discloses that a resin composition containing specific polyimide resin particles and at least one resin selected from the group consisting of thermoplastic resins and thermosetting resins can improve various properties such as heat resistance and mechanical properties while maintaining the light weight inherent to the resin.
  • Patent Document 2 is a technology for improving heat resistance, mechanical properties, etc. by incorporating a polyimide resin into a thermoplastic resin or a thermosetting resin while maintaining the particulate state without thermally melting the polyimide resin, but does not improve the flame retardancy of the resin composition.
  • An object of the present invention is to provide a resin composition and a molded article that can exhibit high flame retardancy even when a small amount of a flame retardant is used or when no flame retardant is used at all.
  • the present inventors have found that the above-mentioned problems can be solved by a resin composition containing a polyimide resin in which specific different polyimide structural units are combined in a specific ratio, and an aromatic resin having a specific structure, in a predetermined ratio. That is, the present invention relates to the following.
  • a resin composition comprising: a polyimide resin (A) containing a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2), in which the content ratio of the repeating structural unit of the formula (1) to the total content of the repeating structural units of the formula (1) and the repeating structural units of the formula (2) is 20 to 70 mol %, and a resin represented by the following formula (5) or an acid-modified product thereof (B), in which the ratio of the content of the mass of the component (B) to the total content of the components (A) and (B) [(B)/ ⁇ (A)+(B) ⁇ ] is greater than 0.50.
  • R1 is a divalent group having 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure.
  • R2 is a divalent chain aliphatic group having 5 to 16 carbon atoms.
  • X1 and X2 are each independently a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring.
  • R 51 to R 55 and R 61 to R 64 are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms, and R 65 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • n is the number of repeating structural units and is a number of 10 or more.
  • the present invention provides a resin composition and molded article that can exhibit high flame retardancy even when using little or no flame retardant.
  • FIG. 1 is a schematic diagram showing a method for preparing a sample (ultrathin section) used for observation with a field emission scanning transmission electron microscope (FE-STEM).
  • FE-STEM field emission scanning transmission electron microscope
  • 1 is a micrograph of a cross section of the resin composition (pellet) of Example 1 cut in a direction perpendicular to the machine direction (MD), observed by FE-STEM.
  • FIG. 2 is a schematic diagram for explaining a method for preparing a test piece used for evaluating adhesion between a film and a copper foil.
  • FIG. 2 is a schematic diagram for explaining a method for evaluating the adhesion between a film and a copper foil and the tensile adhesive strength.
  • the resin composition of the present invention contains a polyimide resin (A) that contains a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2), and the content ratio of the repeating structural unit of the formula (1) to the total content of the repeating structural units of the formula (1) and the repeating structural units of the formula (2) is 20 to 70 mol %; and a resin represented by the following formula (5) or an acid-modified product thereof (B), in which the ratio of the content of the component (B) to the total content of the components (A) and (B) [(B)/ ⁇ (A)+(B) ⁇ ] is greater than 0.50.
  • R1 is a divalent group having 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure.
  • R2 is a divalent chain aliphatic group having 5 to 16 carbon atoms.
  • X1 and X2 are each independently a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring.
  • R 51 to R 55 and R 61 to R 64 are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms, and R 65 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • n is the number of repeating structural units and is a number of 10 or more.
  • the resin composition of the present invention contains the polyimide resin (A) obtained by combining specific different polyimide structural units in the above-mentioned specific ratio, and the resin represented by the formula (5) or an acid-modified product thereof (B) in a predetermined ratio, and thus can exhibit high flame retardancy even when a small amount of a flame retardant is used or no flame retardant is used at all.
  • the reason why the above-mentioned effects are obtained in the present invention is not clear, but is thought to be as follows.
  • the resin composition of the present invention is a resin composition in which the mass ratio [(B)/ ⁇ (A)+(B) ⁇ ] is more than 0.50 and the content ratio of aromatic rings is high.
  • component (A) and component (B) form a microphase separation structure in the resin composition or the molded body, and at the phase separation interface between component (A) and component (B), the aromatic ring in component (A) and the aromatic structure in component (B) partially form a charge transfer complex, which is thermally stabilized.
  • the resin composition of the present invention can achieve an extremely low dielectric constant and dielectric tangent (hereinafter, these are also collectively referred to as "low dielectric properties") for a resin material, and furthermore, it has good adhesion to metal foils such as copper foil.
  • the polyimide resin (A) used in the present invention contains a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2), and the content of the repeating structural unit of the formula (1) relative to the total of the repeating structural units of the formula (1) and the repeating structural units of the formula (2) is 20 to 70 mol %.
  • R1 is a divalent group having 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure.
  • R2 is a divalent chain aliphatic group having 5 to 16 carbon atoms.
  • X1 and X2 are each independently a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring.
  • the polyimide resin (A) used in the present invention is a thermoplastic resin, and is preferably in the form of a powder or pellets.
  • Thermoplastic polyimide resins are formed, for example, by molding a polyimide precursor such as polyamic acid and then closing the imide rings, and are distinguished from polyimide resins that do not have a glass transition temperature (Tg) or polyimide resins that decompose at a temperature lower than the glass transition temperature.
  • Tg glass transition temperature
  • R1 is a divalent group containing at least one alicyclic hydrocarbon structure and having 6 to 22 carbon atoms.
  • the alicyclic hydrocarbon structure means a ring derived from an alicyclic hydrocarbon compound, and the alicyclic hydrocarbon compound may be saturated or unsaturated, and may be monocyclic or polycyclic.
  • alicyclic hydrocarbon structure examples include, but are not limited to, a cycloalkane ring such as a cyclohexane ring, a cycloalkene ring such as a cyclohexene ring, a bicycloalkane ring such as a norbornane ring, and a bicycloalkene ring such as norbornene.
  • a cycloalkane ring is preferred, a cycloalkane ring having 4 to 7 carbon atoms is more preferred, and a cyclohexane ring is even more preferred.
  • R1 has 6 to 22 carbon atoms, and preferably 8 to 17 carbon atoms.
  • R1 contains at least one alicyclic hydrocarbon structure, and preferably contains 1 to 3 alicyclic hydrocarbon structures.
  • R 1 is preferably a divalent group represented by the following formula (R1-1) or (R1-2).
  • ( m11 and m12 each independently represent an integer of 0 to 2, preferably 0 or 1.
  • m13 to m15 each independently represent an integer of 0 to 2, preferably 0 or 1.)
  • R 1 is particularly preferably a divalent group represented by the following formula (R1-3).
  • R1-3 the positional relationship of the two methylene groups to the cyclohexane ring may be either cis or trans, and the ratio of cis to trans may be any value.
  • X1 is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.
  • the aromatic ring may be a single ring or a condensed ring, and examples thereof include, but are not limited to, a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring. Among these, a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred.
  • X1 has 6 to 22 carbon atoms, and preferably 6 to 18 carbon atoms.
  • X1 contains at least one aromatic ring, and preferably contains 1 to 3 aromatic rings.
  • X1 is preferably a tetravalent group represented by any one of the following formulae (X-1) to (X-4).
  • R 11 to R 18 are each independently an alkyl group having 1 to 4 carbon atoms.
  • p 11 to p 13 are each independently an integer of 0 to 2, preferably 0.
  • p 14 , p 15 , p 16 and p 18 are each independently an integer of 0 to 3, preferably 0.
  • p 17 is an integer of 0 to 4, preferably 0.
  • L 11 to L 13 are each independently a single bond, an ether group, a carbonyl group or an alkylene group having 1 to 4 carbon atoms.) Since X1 is a tetravalent group containing at least one aromatic ring and having 6 to 22 carbon atoms, R12 , R13 , p12 , and p13 in formula (X-2) are selected so that the number of carbon atoms of the tetravalent group represented by formula (X-2) is in the range of 10 to 22.
  • L 11 , R 14 , R 15 , p 14 and p 15 in formula (X-3) are selected so that the number of carbon atoms in the tetravalent group represented by formula (X-3) falls within the range of 12 to 22, and L 12 , L 13 , R 16 , R 17 , R 18 , p 16 , p 17 and p 18 in formula (X-4) are selected so that the number of carbon atoms in the tetravalent group represented by formula (X-4) falls within the range of 18 to 22.
  • X1 is particularly preferably a tetravalent group represented by the following formula (X-5) or (X-6).
  • R2 is a divalent chain aliphatic group having 5 to 16 carbon atoms, preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and even more preferably 8 to 10 carbon atoms.
  • the chain aliphatic group means a group derived from a chain aliphatic compound, and the chain aliphatic compound may be saturated or unsaturated, may be linear or branched, and may contain a heteroatom such as an oxygen atom.
  • R2 is preferably an alkylene group having 5 to 16 carbon atoms, more preferably an alkylene group having 6 to 14 carbon atoms, even more preferably an alkylene group having 7 to 12 carbon atoms, and particularly preferably an alkylene group having 8 to 10 carbon atoms.
  • the alkylene group may be a linear alkylene group or a branched alkylene group, but is preferably a linear alkylene group.
  • R2 is preferably at least one selected from the group consisting of an octamethylene group and a decamethylene group, and particularly preferably an octamethylene group.
  • R2 is a divalent chain aliphatic group containing an ether group and having 5 to 16 carbon atoms.
  • the number of carbon atoms is preferably 6 to 14, more preferably 7 to 12, and even more preferably 8 to 10.
  • a divalent group represented by the following formula (R2-1) or (R2-2) is preferred.
  • ( m21 and m22 each independently represent an integer of 1 to 15, preferably 1 to 13, more preferably 1 to 11, and even more preferably 1 to 9.
  • m23 to m25 each independently represent an integer of 1 to 14, preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 8.
  • R 2 is a divalent chain aliphatic group having 5 to 16 carbon atoms (preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and even more preferably 8 to 10 carbon atoms)
  • m 21 and m 22 in formula (R2-1) are selected so that the number of carbon atoms in the divalent group represented by formula (R2-1) is in the range of 5 to 16 (preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and even more preferably 8 to 10 carbon atoms).
  • m 21 +m 22 is 5 to 16 (preferably 6 to 14, more preferably 7 to 12, and even more preferably 8 to 10).
  • m 23 to m 25 in formula (R2-2) are selected so that the carbon number of the divalent group represented by formula (R2-2) is in the range of 5 to 16 (preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and even more preferably 8 to 10 carbon atoms).
  • m 23 + m 24 + m 25 is 5 to 16 (preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and even more preferably 8 to 10 carbon atoms).
  • X2 is defined in the same manner as X1 in formula (1), and the preferred embodiments are also the same.
  • the content ratio of the repeating structural unit of formula (1) to the total of the repeating structural unit of formula (1) and the repeating structural unit of formula (2) is 20 to 70 mol %.
  • the content ratio of the repeating structural unit of formula (1) is within the above range, it becomes possible to sufficiently crystallize the polyimide resin even in a general injection molding cycle. If the content ratio is less than 20 mol %, the moldability decreases, and if it exceeds 70 mol %, the crystallinity decreases, and therefore the heat resistance decreases.
  • the content ratio of the repeating structural unit of formula (1) to the total of the repeating structural units of formula (1) and formula (2) is preferably 65 mol % or less, more preferably 60 mol % or less, and even more preferably 50 mol % or less.
  • the content ratio of the repeating structural unit of formula (1) to the total of the repeating structural units of formula (1) and formula (2) is preferably 20 mol % or more and less than 40 mol %.
  • the above content is preferably 25 mol% or more, more preferably 30 mol% or more, and even more preferably 32 mol% or more, and from the viewpoint of expressing high crystallinity, it is even more preferably 35 mol% or less.
  • the total content ratio of the repeating units of formula (1) and the repeating units of formula (2) to all repeating units constituting polyimide resin (A) is preferably 50 to 100 mol%, more preferably 75 to 100 mol%, even more preferably 80 to 100 mol%, and even more preferably 85 to 100 mol%.
  • the polyimide resin (A) may further contain a repeating unit of the following formula (3).
  • the content ratio of the repeating unit of the formula (3) to the total of the repeating unit of the formula (1) and the repeating unit of the formula (2) is preferably 25 mol% or less.
  • the lower limit is not particularly limited, and it is sufficient that it is more than 0 mol%.
  • the content ratio is preferably 5 mol % or more, more preferably 10 mol % or more, while from the viewpoint of maintaining crystallinity, the content ratio is preferably 20 mol % or less, more preferably 15 mol % or less.
  • R3 is a divalent group having 6 to 22 carbon atoms containing at least one aromatic ring.
  • X3 is a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring.
  • R3 is a divalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.
  • the aromatic ring may be a single ring or a condensed ring, and examples thereof include, but are not limited to, a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring. Among these, a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred.
  • R3 has 6 to 22 carbon atoms, and preferably 6 to 18 carbon atoms.
  • R3 contains at least one aromatic ring, and preferably contains 1 to 3 aromatic rings.
  • a monovalent or divalent electron-withdrawing group may be bonded to the aromatic ring.
  • the monovalent electron-withdrawing group include a nitro group, a cyano group, a p-toluenesulfonyl group, a halogen, a halogenated alkyl group, a phenyl group, and an acyl group.
  • divalent electron-withdrawing group examples include a halogenated alkylene group such as a fluorinated alkylene group (e.g., -C(CF 3 ) 2 -, -(CF 2 ) p - (wherein p is an integer of 1 to 10)), -CO-, -SO 2 -, -SO-, -CONH-, -COO-, and the like.
  • a fluorinated alkylene group e.g., -C(CF 3 ) 2 -, -(CF 2 ) p - (wherein p is an integer of 1 to 10)
  • R3 is preferably a divalent group represented by the following formula (R3-1) or (R3-2).
  • ( m31 and m32 each independently represent an integer of 0 to 2, preferably 0 or 1.
  • m33 and m34 each independently represent an integer of 0 to 2, preferably 0 or 1.
  • R21 , R22 , and R23 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms.
  • p21 , p22 , and p23 each independently represent an integer of 0 to 4, preferably 0.
  • L21 represents a single bond, an ether group, a carbonyl group, or an alkylene group having 1 to 4 carbon atoms.
  • R 3 is a divalent group containing at least one aromatic ring and having 6 to 22 carbon atoms
  • m 31 , m 32 , R 21 and p 21 in formula (R3-1) are selected so that the number of carbon atoms of the divalent group represented by formula (R3-1) falls within the range of 6 to 22.
  • L 21 , m 33 , m 34 , R 22 , R 23 , p 22 and p 23 in formula (R3-2) are selected so that the divalent group represented by formula (R3-2) has 12 to 22 carbon atoms.
  • X3 is defined in the same manner as X1 in formula (1), and the preferred embodiments are also the same.
  • the polyimide resin (A) may further contain a repeating unit represented by the following formula (4).
  • R 4 is a divalent group containing -SO 2 - or -Si(R x )(R y )O-, and R x and R y each independently represent a chain aliphatic group having 1 to 3 carbon atoms or a phenyl group.
  • X 4 is a tetravalent group containing at least one aromatic ring and having 6 to 22 carbon atoms.
  • X4 is defined in the same manner as X1 in formula (1), and the preferred embodiments are also the same.
  • the terminal structure of the polyimide resin (A) is not particularly limited, but it is preferable that the polyimide resin (A) has a chain aliphatic group having 5 to 14 carbon atoms at the terminal.
  • the chain aliphatic group may be saturated or unsaturated, and may be linear or branched.
  • Examples of the saturated chain aliphatic group having 5 to 14 carbon atoms include an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, a lauryl group, an n-tridecyl group, an n-tetradecyl group, an isopentyl group, a neopentyl group, a 2-methylpentyl group, a 2-methylhexyl group, a 2-ethylpentyl group, a 3-ethylpentyl group, an isooctyl group, a 2-ethylhexyl group, a 3-ethylhexyl group, an isononyl group, a 2-ethyloctyl group, an isodecyl group, an iso
  • Examples of the unsaturated linear aliphatic group having 5 to 14 carbon atoms include a 1-pentenyl group, a 2-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 1-heptenyl group, a 2-heptenyl group, a 1-octenyl group, a 2-octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, a tridecenyl group, and a tetradecenyl group.
  • the chain aliphatic group is preferably a saturated chain aliphatic group, more preferably a saturated linear chain aliphatic group.
  • the chain aliphatic group preferably has 6 or more carbon atoms, more preferably 7 or more carbon atoms, even more preferably 8 or more carbon atoms, and preferably has 12 or less carbon atoms, more preferably 10 or less carbon atoms, even more preferably 9 or less carbon atoms.
  • the chain aliphatic group may be of only one kind or of two or more kinds.
  • the chain aliphatic group is particularly preferably at least one selected from the group consisting of an n-octyl group, an isooctyl group, a 2-ethylhexyl group, an n-nonyl group, an isononyl group, an n-decyl group, and an isodecyl group, further preferably at least one selected from the group consisting of an n-octyl group, an isooctyl group, a 2-ethylhexyl group, an n-nonyl group, and an isononyl group, and most preferably at least one selected from the group consisting of an n-octyl group, an isooctyl group, and a 2-ethylhexyl group.
  • the polyimide resin (A) preferably has, at its terminal, other than a terminal amino group and a terminal carboxy group, only a chain aliphatic group having 5 to 14 carbon atoms.
  • the content thereof is preferably 10 mol % or less, more preferably 5 mol % or less, based on the chain aliphatic group having 5 to 14 carbon atoms.
  • the content of the chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (A) is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, and even more preferably 0.2 mol% or more, based on 100 mol% of the total of all repeating units constituting the polyimide resin (A).
  • the content of the chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (A) is preferably 10 mol% or less, more preferably 6 mol% or less, and even more preferably 3.5 mol% or less, based on 100 mol% of the total of all repeating units constituting the polyimide resin (A).
  • the content of the chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (A) can be determined by depolymerizing the polyimide resin (A).
  • the polyimide resin (A) preferably has a melting point of 360° C. or less and a glass transition temperature of 150° C. or more.
  • the melting point of the polyimide resin (A) is more preferably 280° C. or more, and even more preferably 290° C. or more from the viewpoint of heat resistance, and is preferably 345° C. or less, more preferably 340° C. or less, and even more preferably 335° C. or less from the viewpoint of high moldability.
  • the glass transition temperature of the polyimide resin (A) is more preferably 160° C. or more, and even more preferably 170° C. or more from the viewpoint of heat resistance, and is preferably 250° C. or less, more preferably 230° C.
  • the polyimide resin (A) preferably has a heat quantity of the crystallization heat peak observed when the polyimide resin is melted and then cooled at a temperature drop rate of 20° C./min by differential scanning calorimetry (hereinafter, also simply referred to as "crystallization heat quantity") of 5.0 mJ/mg or more, more preferably 10.0 mJ/mg or more, and even more preferably 17.0 mJ/mg or more.
  • the upper limit of the crystallization heat quantity is not particularly limited, but is usually 45.0 mJ/mg or less.
  • the melting point, glass transition temperature and heat of crystallization of the polyimide resin (A) can be specifically measured by the method described in the Examples.
  • the logarithmic viscosity of a 0.5% by mass solution of polyimide resin (A) in concentrated sulfuric acid at 30° C. is preferably in the range of 0.2 to 2.0 dL/g, more preferably 0.3 to 1.8 dL/g. If the logarithmic viscosity is 0.2 dL/g or more, sufficient mechanical strength is obtained when the resulting resin composition is molded into a molded article, and if it is 2.0 dL/g or less, moldability and handleability are good.
  • the weight average molecular weight Mw of the polyimide resin (A) is preferably in the range of 10,000 to 150,000, more preferably 15,000 to 100,000, even more preferably 20,000 to 80,000, still more preferably 30,000 to 70,000, and even more preferably 35,000 to 65,000. If the weight average molecular weight Mw of the polyimide resin (A) is 10,000 or more, the mechanical strength of the obtained molded article becomes good, if it is 40,000 or more, the stability of the mechanical strength becomes good, and if it is 150,000 or less, the moldability becomes good.
  • the weight average molecular weight Mw of the polyimide resin (A) can be measured by gel permeation chromatography (GPC) using polymethyl methacrylate (PMMA) as a standard sample.
  • the polyimide resin (A) can be produced by reacting a tetracarboxylic acid component containing at least one aromatic ring-containing tetracarboxylic acid and/or a derivative thereof with a diamine component containing at least one alicyclic hydrocarbon structure and a chain aliphatic diamine.
  • the tetracarboxylic acid containing at least one aromatic ring is preferably a compound in which four carboxy groups are directly bonded to the aromatic ring, and may contain an alkyl group in the structure.
  • the tetracarboxylic acid preferably has 6 to 26 carbon atoms.
  • pyromellitic acid, 2,3,5,6-toluenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, etc. are preferred. Among these, pyromellitic acid is more preferred.
  • Examples of derivatives of tetracarboxylic acids containing at least one aromatic ring include anhydrides or alkyl esters of tetracarboxylic acids containing at least one aromatic ring.
  • the tetracarboxylic acid derivatives preferably have 6 to 38 carbon atoms.
  • anhydrides of tetracarboxylic acids include pyromellitic monoanhydride, pyromellitic dianhydride, 2,3,5,6-toluenetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 1,4,5,8-naphthalenetetracarboxylic dianhydride.
  • alkyl esters of tetracarboxylic acids include dimethyl pyromelliticate, diethyl pyromelliticate, dipropyl pyromelliticate, diisopropyl pyromelliticate, dimethyl 2,3,5,6-toluenetetracarboxylate, dimethyl 3,3',4,4'-diphenylsulfonetetracarboxylate, dimethyl 3,3',4,4'-benzophenonetetracarboxylate, dimethyl 3,3',4,4'-biphenyltetracarboxylate, and dimethyl 1,4,5,8-naphthalenetetracarboxylate.
  • the alkyl group preferably has 1 to 3 carbon atoms.
  • the tetracarboxylic acid and/or its derivative containing at least one aromatic ring may be at least one compound selected from the above, or two or more compounds may be used in combination.
  • the carbon number of the diamine containing at least one alicyclic hydrocarbon structure is preferably 6 to 22, and examples thereof include 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-diaminodicyclohexylmethane, 4,4'-methylenebis(2-methylcyclohexylamine), carvonediamine, limonenediamine, isophoronediamine, norbornanediamine, bis(aminomethyl)tricyclo[5.2.1.0 2,6 ]decane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, and 4,4'-diaminodicyclohexylpropane.
  • Diamines containing an alicyclic hydrocarbon structure generally have structural isomers, but the ratio of cis/trans isomers is not limited.
  • the chain aliphatic diamine may be linear or branched, and has a carbon number of preferably 5 to 16, more preferably 6 to 14, and even more preferably 7 to 12. In addition, if the carbon number of the chain portion is 5 to 16, an ether bond may be contained therebetween.
  • chain aliphatic diamine for example, 1,5-pentamethylenediamine, 2-methylpentane-1,5-diamine, 3-methylpentane-1,5-diamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine, 2,2'-(ethylenedioxy)bis(ethyleneamine), and the like are preferable.
  • the chain aliphatic diamine may be used alone or in combination of two or more.
  • a chain aliphatic diamine having 8 to 10 carbon atoms is preferably used, and in particular, at least one selected from the group consisting of 1,8-octamethylenediamine and 1,10-decamethylenediamine is preferably used.
  • the molar ratio of the amount of diamine containing at least one alicyclic hydrocarbon structure charged to the total amount of diamine containing at least one alicyclic hydrocarbon structure and chain aliphatic diamine is preferably 20 to 70 mol%.
  • the molar amount is preferably 25 mol% or more, more preferably 30 mol% or more, and even more preferably 32 mol% or more, and from the viewpoint of expressing high crystallinity, it is preferably 60 mol% or less, more preferably 50 mol% or less, even more preferably less than 40 mol%, and even more preferably 35 mol% or less.
  • the diamine component may also contain a diamine containing at least one aromatic ring.
  • the diamine containing at least one aromatic ring preferably has 6 to 22 carbon atoms, and examples thereof include orthoxylylenediamine, metaxylylenediamine, paraxylylenediamine, 1,2-diethynylbenzenediamine, 1,3-diethynylbenzenediamine, 1,4-diethynylbenzenediamine, 1,2-diaminobenzene, 1,3-diaminobenzene, 1,4-diaminobenzene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, ⁇ , ⁇ '-bis(4-aminophenyl)1,4-diisopropylbenzene, ⁇ , ⁇ '-bis(3-aminophenyl)-1,4-di
  • the molar ratio of the amount of the diamine containing at least one aromatic ring to the total amount of the diamine containing at least one alicyclic hydrocarbon structure and the chain aliphatic diamine is preferably 25 mol% or less.
  • the lower limit is not particularly limited as long as it is more than 0 mol%.
  • the molar ratio is preferably 5 mol % or more, more preferably 10 mol % or more, while from the viewpoint of maintaining crystallinity, the molar ratio is preferably 20 mol % or less, more preferably 15 mol % or less.
  • the molar ratio is preferably 12 mol % or less, more preferably 10 mol % or less, even more preferably 5 mol % or less, and still more preferably 0 mol %.
  • the ratio of the amount of the tetracarboxylic acid component to the amount of the diamine component is preferably 0.9 to 1.1 moles of the diamine component per mole of the tetracarboxylic acid component.
  • a terminal blocking agent may be mixed in addition to the tetracarboxylic acid component and the diamine component.
  • the terminal blocking agent is preferably at least one selected from the group consisting of monoamines and dicarboxylic acids.
  • the amount of the terminal blocking agent used may be any amount that allows a desired amount of terminal groups to be introduced into the polyimide resin (A), and is preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.06 mol, and even more preferably 0.002 to 0.035 mol, per mol of the tetracarboxylic acid and/or its derivative.
  • a monoamine end-capping agent is preferable, and from the viewpoint of improving heat aging resistance by introducing the above-mentioned chain aliphatic group having 5 to 14 carbon atoms into the end of the polyimide resin (A), a monoamine having a chain aliphatic group having 5 to 14 carbon atoms is more preferable, and a monoamine having a saturated linear aliphatic group having 5 to 14 carbon atoms is even more preferable.
  • the end-capping agent is particularly preferably at least one selected from the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, isononylamine, n-decylamine, and isodecylamine, further preferably at least one selected from the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, and isononylamine, and most preferably at least one selected from the group consisting of n-octylamine, isooctylamine, and 2-ethylhexylamine.
  • a known polymerization method can be applied as the polymerization method for producing polyimide resin (A), and the method described in WO 2016/147996 can be used.
  • the resin composition of the present invention contains a polyimide resin (A) and a resin represented by the following formula (5) or an acid-modified product thereof (B).
  • R 51 to R 55 and R 61 to R 64 are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms, and R 65 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • n is the number of repeating structural units and is a number of 10 or more.
  • the alkyl group having 1 to 4 carbon atoms in R 51 to R 55 and R 61 to R 65 may be either linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is preferred, and a methyl group is more preferred.
  • R 51 , R 53 , R 61 and R 63 are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
  • R 52 , R 54 , R 62 and R 64 are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a methyl group.
  • R 65 is preferably a hydrogen atom.
  • n is a number of 10 or more, and more preferably 20 or more.
  • the resin represented by the formula (5) is preferably poly(2,6-dimethyl-1,4-phenylene ether), which is a resin represented by the following formula (5-1). (In the formula, n is the same as above.)
  • the acid-modified product of the resin represented by the formula (5) includes a resin obtained by modifying the resin represented by the formula (5) with a carboxylic acid or a carboxylic acid derivative.
  • a carboxylic acid or the carboxylic acid derivative an unsaturated carboxylic acid or its derivative is preferable from the viewpoint of reactivity with the resin represented by the formula (5).
  • the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, angelic acid, etc.
  • the derivatives of the unsaturated carboxylic acid include acid anhydrides, esters, amides, imides, and metal salts, and among these, acid anhydrides are preferred.
  • the acid-modified product of the resin represented by the formula (5) is preferably a resin obtained by modifying the resin represented by the formula (5) with maleic acid or a maleic acid derivative (a maleic acid-modified product of the resin represented by the formula (5)), from the viewpoints of exhibiting high flame retardancy and availability, and more preferably a resin obtained by modifying the resin represented by the formula (5) with maleic anhydride.
  • Examples of the maleic acid modified resin represented by the formula (5) include resins having structures represented by the following formula (5-2) and/or formula (5-3). (In the formula, R 51 to R 55 , R 61 , R 63 , R 64 , R 65 and n are the same as defined above.)
  • the acid modification rate of the acid modified product of the resin represented by formula (5) is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 3.0 mass%, even more preferably 0.1 to 2.0 mass%, and even more preferably 0.2 to 1.0 mass%, from the viewpoints of obtaining low dielectric properties, improving film formability, and availability.
  • the acid modification rate here refers to the content (mass%) of structures derived from acid in the acid modified product.
  • the acid modification rate refers to the content (mass%) of structures derived from maleic anhydride in the acid modified product.
  • component (B) is preferably a resin represented by formula (5) or a maleic acid modified product thereof, more preferably a resin represented by formula (5), and even more preferably poly(2,6-dimethyl-1,4-phenylene ether), which is a resin represented by formula (5-1).
  • the intrinsic viscosity of component (B) measured in chloroform at 30°C is preferably 0.20 to 0.60 dL/g, more preferably 0.30 to 0.50 dL/g, and even more preferably 0.30 to 0.45 dL/g, from the viewpoints of achieving high flame retardancy and improving moldability.
  • the ratio of the mass content of component (B) to the total mass content of components (A) and (B) in the resin composition [(B)/ ⁇ (A)+(B) ⁇ ] is more than 0.50, preferably 0.60 or more, more preferably 0.65 or more, even more preferably 0.70 or more, still more preferably 0.75 or more, and even more preferably 0.80 or more, from the viewpoint of expressing high flame retardancy and obtaining low dielectric properties.
  • the upper limit is less than 1.00, and from the viewpoint of expressing high flame retardancy, it is preferably 0.99 or less, more preferably 0.98 or less, and even more preferably 0.95 or less.
  • the content of component (A) in the resin composition is not particularly limited as long as the above-mentioned [(B)/ ⁇ (A)+(B) ⁇ ] is in the range of more than 0.50, but from the viewpoint of achieving high flame retardancy and low dielectric properties, it is preferably 1 to 45 mass%, more preferably 2 to 40 mass%, even more preferably 5 to 30 mass%, and even more preferably 5 to 25 mass%.
  • the content of component (B) in the resin composition is not particularly limited as long as the above-mentioned [(B)/ ⁇ (A)+(B) ⁇ ] is in the range of more than 0.50, but from the viewpoint of achieving high flame retardancy and low dielectric properties, it is preferably 30 to 99.5 mass%, more preferably 40 to 99.5 mass%, even more preferably 50 to 99.5 mass%, even more preferably 60 to 98 mass%, even more preferably 70 to 95 mass%, and even more preferably 75 to 95 mass%.
  • the resin composition of the present invention may contain additives such as fillers, reinforcing fibers, matting agents, plasticizers, antistatic agents, coloring inhibitors, antigelling agents, colorants, sliding property improvers, antioxidants, conductive agents, resin modifiers, and compatibilizers, as necessary.
  • additives such as fillers, reinforcing fibers, matting agents, plasticizers, antistatic agents, coloring inhibitors, antigelling agents, colorants, sliding property improvers, antioxidants, conductive agents, resin modifiers, and compatibilizers, as necessary.
  • the amount of the additives used in the resin composition is usually 50% by mass or less, preferably 0.0001 to 30% by mass, more preferably 0.001 to 15% by mass, and even more preferably 0.01 to 10% by mass.
  • the resin composition of the present invention can be blended with resins other than component (A) and component (B) to the extent that the properties are not impaired.
  • the resin is preferably a highly heat-resistant thermoplastic resin, and examples thereof include polyamide resin, polyester resin, polyimide resin other than polyimide resin (A), polycarbonate resin, polyetherimide resin, polyamideimide resin, polyphenylene etherimide resin, polyphenylene sulfide resin, polysulfone resin, polyethersulfone resin, polyarylate resin, liquid crystal polymer, polyetheretherketone resin, polyetherketone resin, polyetherketoneketone resin, polyetheretherketoneketone resin, polybenzimidazole resin, and fluorine-based resin.
  • the fluorine-based resin includes polytetrafluoroethylene, perfluoroalkylvinylether copolymer, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, and polychlorotrifluoroethylene
  • one or more selected from the group consisting of polyetherimide resins, polyphenylene sulfide resins, and polyether ether ketone resins are preferred, from the viewpoint of low water absorption, liquid crystal polymers are preferred, and from the viewpoint of obtaining high flame retardancy, one or more selected from the group consisting of polyphenylene sulfide resins, polytetrafluoroethylene, and perfluoroalkyl vinyl ether copolymers are preferred.
  • resins other than the components (A) and (B) are used in combination, there are no particular limitations on the amount of such resins added, so long as the properties of the resin composition are not impaired.
  • the total content of component (A) and component (B) in the resin composition of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and is 100% by mass or less.
  • the resin composition of the present invention can exhibit high flame retardancy even if the content of the flame retardant is small.
  • the content of the flame retardant in the resin composition is preferably 5% by mass or less, more preferably 2% by mass or less, even more preferably 1% by mass or less, still more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less, still more preferably 0.1% by mass or less, still more preferably 0.05% by mass or less, still more preferably 0.02% by mass or less, still more preferably less than 0.01% by mass, and still more preferably 0% by mass.
  • the flame retardant examples include existing flame retardants such as halogen-based flame retardants, phenol-based flame retardants, phosphorus-based flame retardants, metal oxide-based flame retardants, metal hydroxide-based flame retardants, metal salt-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, and boron compound-based flame retardants.
  • existing flame retardants such as halogen-based flame retardants, phenol-based flame retardants, phosphorus-based flame retardants, metal oxide-based flame retardants, metal hydroxide-based flame retardants, metal salt-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, and boron compound-based flame retardants.
  • the resin composition of the present invention preferably does not contain a solvent from the viewpoint of forming a pellet.
  • the content of the solvent in the resin composition is preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less.
  • the resin composition of the present invention may take any form, but from the viewpoint of expressing high flame retardancy by forming a microphase separation structure described later and from the viewpoint of obtaining low dielectric properties, it is preferably one obtained by melt kneading at a temperature exceeding the melting point of component (A), and more preferably a pellet obtained by melt kneading at a temperature exceeding the melting point of component (A). That is, it is preferable that component (A) in the resin composition of the present invention has been subjected to a heat history, and the resin composition is distinguished from a resin composition containing component (A) in a powder state.
  • the resin composition of the present invention has thermoplasticity, for example, after component (A), component (B), and various optional components as required are added and dry blended, or after component (B) and optional components are separately fed from a location other than the feeding of component (A) to the extruder, the mixture is melt-kneaded in the extruder to extrude strands, and the strands are cut to form pellets.
  • the pellets can be introduced into various molding machines and thermoformed by the method described below to easily produce molded articles having desired shapes.
  • the flame retardant is usually prone to bleeding out or thermal decomposition, coloring, whitening, etc. during the pellet production process and the thermoforming process.
  • the resin composition of the present invention has the advantage that these problems do not occur.
  • pellets made of the resin composition of the present invention and molded articles obtained by molding the resin composition preferably have a microphase-separated structure.
  • the microphase-separated structure is a phase-separated structure at the micro to nano level formed by phase separation between component (A) and component (B), and may be either a sea-island structure or a co-continuous structure, but a sea-island structure is preferred. In the sea-island structure, either component may form the "sea" depending on the mass ratio of component (A) and component (B) in the pellet.
  • Whether or not the pellet or molded article has a microphase-separated structure can be determined by observing the surface or cross section of the pellet or molded article with a scanning transmission electron microscope (STEM).
  • STEM scanning transmission electron microscope
  • the present invention provides a molded article comprising the resin composition.
  • the shape of the molded article is not particularly limited, and examples thereof include a sheet, a film, a strand, a filament, etc. These may be intermediate parts of industrial products or final products.
  • the molded article of the present invention can be easily produced by thermoforming.
  • Thermoforming methods include injection molding, extrusion molding, inflation molding, blow molding, hot press molding, vacuum molding, compressed air molding, laser molding, welding, and adhesion, and any molding method that involves a thermal melting step can be used.
  • the molded article of the present invention is preferably an injection molded article.
  • the resin composition is injection molded, it is preferable because it can be molded without setting the molding temperature and the mold temperature during molding to a high temperature.
  • molding can be performed with a molding temperature of preferably 400° C. or less, more preferably 360° C. or less, and a mold temperature of preferably 260° C. or less, more preferably 220° C. or less.
  • the pellets produced by the above method are dried, and then the pellets are introduced into various molding machines and thermoformed to produce a molded body having the desired shape.
  • the resin composition and molded article of the present invention have high flame retardancy.
  • the oxygen index of the molded article having a thickness of 4 mm, measured in accordance with JIS K 7201:1995, is preferably 28 or more, more preferably 28.5 or more, even more preferably 29 or more, still more preferably 30 or more, and still more preferably 32 or more.
  • the degree of flame retardancy can be confirmed by measuring the oxygen index.
  • the oxygen index indicates the concentration of oxygen required to continue combustion, and if it exceeds 21, combustion will not continue in air under normal conditions.
  • an oxygen index of 27 or more is generally considered to indicate high flame retardancy.
  • the oxygen index can be measured by the method described in the Examples.
  • the resin composition and molded article of the present invention have low dielectric properties, and can achieve, for example, a dielectric constant of 3.0 or less and a dielectric loss tangent of 0.005 or less at a measurement frequency of 10 GHz.
  • the dielectric constant is preferably 2.90 or less, more preferably 2.85 or less, even more preferably 2.70 or less, and even more preferably 2.50 or less, and the dielectric loss tangent is preferably 0.004 or less, more preferably 0.003 or less.
  • the dielectric constant and dielectric loss tangent can be specifically measured by the method described in the Examples.
  • the resin composition and molded article of the present invention also have good adhesion to metal foils such as copper foils. Therefore, the resin composition and molded article of the present invention can also be used for metal foil laminates such as copper-clad laminates.
  • the adhesion of the molded article made of the resin composition of the present invention to copper foil can be evaluated by the method described in the Examples.
  • the resin composition and molded article of the present invention are useful in applications requiring high flame retardancy, low dielectric constant and low dielectric dissipation factor, such as 5G or 6th generation mobile communication system (6G) related members using a frequency band of 70 G to 300 GHz (smartphones, flexible printed circuit boards, metal foil laminates such as copper-clad laminates, antennas, antenna substrates, etc.), various antennas other than those mentioned above (microwave antennas, millimeter wave antennas, waveguide slot antennas, horn antennas, lens antennas, printed antennas, triplate antennas, microstrip antennas, patch antennas, etc.), various antenna substrates (antenna substrates for 77 GHz vehicle-mounted millimeter wave radar, antenna substrates for terahertz wave radar, antenna substrates for aircraft radar, antenna substrates for caterpillar-type special vehicles, antenna substrates for WiGig, etc.), wire coating materials (low dielectric wire coating materials, etc.), bonding sheets, insulating films, raw materials
  • 6G 6th
  • IR measurement ⁇ Infrared spectroscopic analysis (IR measurement)>
  • the IR measurement of the polyimide resin was carried out using a JIR-WINSPEC50 manufactured by JEOL Ltd.
  • ⁇ Logarithmic Viscosity ⁇ > The polyimide resin was dried at 190 to 200° C. for 2 hours, and then 0.100 g of the polyimide resin was dissolved in 20 mL of concentrated sulfuric acid (96%, manufactured by Kanto Chemical Co., Ltd.) to prepare a polyimide resin solution for measurement, and measurement was performed at 30° C. using a Cannon-Fenske viscometer.
  • the measurement sample was subjected to the following thermal history under a nitrogen atmosphere: first heating (heating rate 10° C./min), then cooling (cooling rate 20° C./min), then second heating (heating rate 10° C./min).
  • the melting point Tm was determined by reading the peak top value of the endothermic peak observed during the second heating.
  • the glass transition temperature Tg was determined by reading the value observed during the second heating.
  • the crystallization temperature Tc was determined by reading the peak top value of the exothermic peak observed during cooling. For Tm, Tg, and Tc, when multiple peaks were observed, the peak top value of each peak was read.
  • the heat of fusion Hm was calculated from the area of the heat of fusion peak (endothermic peak) observed near the melting point when the measurement sample was heated to a temperature above the melting point at a heating rate of 10°C/min to melt, cooled at a heating rate of 20°C/min, and melted again at a heating rate of 10°C/min.
  • the heat of crystallization Hc was calculated from the area of the heat of crystallization peak observed when the measurement sample was heated to a temperature above the melting point at a heating rate of 10°C/min to melt, and then cooled at a heating rate of 20°C/min.
  • ⁇ Crystallization half time> The half-crystallization time of the polyimide resin was measured using a differential scanning calorimeter (DSC-6220, manufactured by SII NanoTechnology, Inc.). The polyimide resin was kept at 420°C for 10 minutes in a nitrogen atmosphere to completely melt the polyimide resin, and then rapidly cooled at a cooling rate of 70°C/min. The time taken from the appearance of the observed crystallization peak to the peak top was calculated. In Table 1, a half crystallization time of 20 seconds or less is indicated as " ⁇ 20".
  • the dielectric constant and dielectric loss tangent were measured at a temperature of 23 ° C., humidity of 50%, and a measurement frequency of 10 GHz by the cavity resonator perturbation method in accordance with IEC 62810.
  • the test piece was conditioned at a temperature of 23 ° C. and humidity of 50% for 24 hours or more, and then immediately used for measurement.
  • Production Example 1 (Production of Polyimide Resin 1) 500 g of 2-(2-methoxyethoxy)ethanol (manufactured by Nippon Nyukazai Co., Ltd.) and 218.12 g (1.00 mol) of pyromellitic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) were introduced into a 2 L separable flask equipped with a Dean-Stark apparatus, a Liebig condenser, a thermocouple, and four paddle blades, and after nitrogen flow, the mixture was stirred at 150 rpm to obtain a uniform suspension solution.
  • 2-(2-methoxyethoxy)ethanol manufactured by Nippon Nyukazai Co., Ltd.
  • 218.12 g (1.00 mol) of pyromellitic dianhydride manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • the mixed diamine solution was dropped under nitrogen flow conditions, and the stirring blade rotation speed was 250 rpm. After the drop was completed, 130 g of 2-(2-methoxyethoxy)ethanol and 1.284 g (0.010 mol) of n-octylamine (manufactured by Kanto Chemical Co., Ltd.), which is an end-capping agent, were added and further stirred. At this stage, a pale yellow polyamic acid solution was obtained. Next, the stirring speed was increased to 200 rpm, and the polyamic acid solution in the 2L separable flask was heated to 190°C. During the temperature increase, precipitation of polyimide resin powder and dehydration due to imidization were confirmed when the liquid temperature was between 120 and 140°C.
  • polyimide resin 1 crystalline thermoplastic polyimide resin 1 (hereinafter also simply referred to as “polyimide resin 1”) powder.
  • the IR spectrum of the polyimide resin 1 was measured, and the characteristic absorption of the imide ring was observed at ⁇ (C ⁇ O) 1768, 1697 (cm ⁇ 1 ).
  • the inherent viscosity was 1.30 dL/g, Tm was 323° C., Tg was 184° C., Tc was 266° C., heat of fusion was 26.7 mJ/mg, heat of crystallization was 30.0 mJ/mg, crystallization half time was 20 seconds or less, and Mw was 55,000.
  • Production Example 2 (Production of Polyimide Resin 2) 769 g of 2-(2-methoxyethoxy)ethanol (manufactured by Nippon Nyukazai Co., Ltd.) and 174.50 g (0.80 mol) of pyromellitic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) were introduced into a 2 L separable flask equipped with a Dean-Stark apparatus, a Liebig condenser, a thermocouple, and four paddle blades, and after nitrogen flow, the mixture was stirred at 150 rpm to obtain a uniform suspension solution.
  • 2-(2-methoxyethoxy)ethanol manufactured by Nippon Nyukazai Co., Ltd.
  • pyromellitic dianhydride manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • the mixed diamine solution was dropped under nitrogen flow conditions, and the stirring blade rotation speed was 250 rpm. After the drop was completed, 10 g of 2-(2-methoxyethoxy)ethanol and 1.027 g (0.008 mol) of n-octylamine (manufactured by Kanto Chemical Co., Ltd.), which is an end-capping agent, were added and further stirred. At this stage, a pale yellow polyamic acid solution was obtained. Next, the stirring speed was increased to 200 rpm, and the polyamic acid solution in the 2L separable flask was heated to 185°C. During the temperature increase, precipitation of polyimide resin powder and dehydration due to imidization were confirmed when the liquid temperature was between 120 and 140°C.
  • polyimide resin 2 crystalline thermoplastic polyimide resin 2 (hereinafter also simply referred to as “polyimide resin 2”) powder.
  • Polyimide resin 2 had a Tm of 344° C., a Tg of 166° C., a Tc of 299° C., a heat of fusion of 40 mJ/mg, a heat of crystallization of 35 mJ/mg, and a Mw of 36,000.
  • compositions and evaluation results of the polyimide resins obtained in Production Examples 1 and 2 are shown in Table 1.
  • the mole percentages of the tetracarboxylic acid component and diamine component in Table 1 are values calculated from the amounts of each component charged when the polyimide resin was produced.
  • Example 1 (Resin composition, preparation and evaluation of molded article) The powder of polyimide resin 1 obtained in Production Example 1 and the powder of poly(2,6-dimethyl-1,4-phenylene ether) ("PX100F” manufactured by Polyxylenol Singapore Pte.
  • the strand extruded from the extruder was air-cooled and then pelletized with a pelletizer ("Fan Cutter FC-Mini-4/N" manufactured by Hoshi Plastics Co., Ltd.).
  • the obtained pellets were dried at 80°C for 12 hours and then used for injection molding.
  • injection molding machine FANUC Corporation's "ROBOSHOT ⁇ -S30iA"
  • injection molding was performed at a barrel temperature of 360°C, a mold temperature of 180°C, and a molding cycle of 72 seconds to produce injection molded articles of a predetermined shape to be used in the above evaluation.
  • the pellets or injection molded articles thus obtained were subjected to various evaluations by the methods described above. The results are shown in Table 2.
  • Example 2 Comparative Examples 2 to 4 Pellets and injection molded articles were produced and various evaluations were performed in the same manner as in Example 1, except that the powder of polyimide resin 1 obtained in Production Example 1 and the powder of poly(2,6-dimethyl-1,4-phenylene ether) "PX100F" were used in the ratio shown in Table 2 and injection molding was performed with a molding cycle in the range of 65 to 72 seconds (Example 2: 73 seconds, Comparative Example 2: 65 seconds, Comparative Example 3: 67 seconds, Comparative Example 4: 77 seconds). The results are shown in Table 2.
  • Comparative Example 1 The powder of polyimide resin 1 obtained in Production Example 1 was melt-kneaded and extruded using a Labo Plastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a barrel temperature of 360°C and a screw rotation speed of 150 rpm. The strand extruded from the extruder was air-cooled and then pelletized using a pelletizer (Hoshi Plastics Co., Ltd.'s "Fan Cutter FC-Mini-4/N"). The obtained pellets were dried at 150°C for 12 hours and then used for injection molding.
  • a Labo Plastomill manufactured by Toyo Seiki Seisakusho Co., Ltd.
  • the strand extruded from the extruder was air-cooled and then pelletized using a pelletizer (Hoshi Plastics Co., Ltd.'s "Fan Cutter FC-Mini-4/N"). The obtained pellets were dried at 150°C for 12 hours and then used for injection molding.
  • injection molding was performed at a barrel temperature of 350°C, a mold temperature of 200°C, and a molding cycle of 50 seconds to produce an injection molded article having a predetermined shape to be used in the evaluation (HDT measurement).
  • the pellets or injection molded articles thus obtained were subjected to various evaluations by the methods described above. The results are shown in Table 2.
  • the molded bodies made from the resin compositions of Examples 1 and 2 have improved oxygen indexes and higher flame retardancy than the molded bodies of Comparative Examples 1 to 4.
  • the molded bodies made from the resin compositions of Examples 3 and 4 also have a higher oxygen index and are more flame retardant than the molded bodies of Comparative Examples 5 and 6.
  • Example 1 Furthermore, the morphology of the pellets obtained in Example 1 was confirmed by the following method.
  • the pellet obtained in Example 1 was cut using an ultramicrotome (Leica Microsystems'"EMUC7") in a direction perpendicular to the flow direction (MD) of the pellet as shown in Figure 1 (i.e., so that the TD cross section is visible) to prepare an ultrathin section.
  • MD flow direction
  • Figure 1 1 is the pellet and 2 is the ultrathin section.
  • the slice was stained in the gas phase of ruthenium tetroxide for 30 minutes, and then observed in transmission using a field emission scanning transmission electron microscope (FE-STEM, Carl Zeiss Gemini SEM500) with an acceleration voltage of 30 kV, column mode: Normal, aperture size: 20 ⁇ m, working distance: 3.6 mm, detection signal: aSTEM A, and observation magnification: 10,000 times, using a STEM detector (FIG. 2).
  • FE-STEM Carl Zeiss Gemini SEM500
  • FIG. 2 the dark areas correspond to the stained areas
  • the light areas correspond to the non-stained areas.
  • the dark areas were determined to be composed of resin (B) that is easily stained by ruthenium tetroxide.
  • the polyimide resin (A) and the resin (B) form a microphase-separated structure (sea-island structure) in the pellet obtained in Example 1. It is also presumed that the polyimide resin (A) forms the islands and the resin (B) forms the sea.
  • Example 1A (Preparation and Evaluation of Film, and Evaluation of Adhesion Between Film and Copper Foil) ⁇ Film Preparation>
  • the pellets of the resin composition obtained in Example 1 were dried at 150° C. for 10 hours, and then fed into a ⁇ 20 mm single-screw extruder equipped with a T-die with a width of 150 mm, and melt-kneaded at a resin temperature of 350 to 360° C.
  • the melt-kneaded resin composition was continuously extruded from the T-die of the single-screw extruder, and then cooled with a metal roll, which was a cooling roll at 140° C., to obtain a film with a thickness of 70 ⁇ m.
  • the temperature of the ⁇ 20 mm single screw extruder was set to 335 to 340°C
  • the temperature of the T-die was set to 335°C.
  • a 10 cm x 10 cm film 3 produced by the above method and a 10 cm x 10 cm x 12 ⁇ m thick copper foil 4 (rolled copper foil, JX Metals Corporation "TQ-MS-VSP") were prepared.
  • Another release paper was placed on top of this and heat sealed using a thermal gradient tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., heater: upper side).
  • the heat sealing conditions were a temperature of 250°C, a pressure of 0.4 MPa (gauge pressure) for 60 seconds.
  • the release paper was removed and the film shown in Fig. 3(a) was cut in the MD direction to prepare a rectangular test piece with a width of 1 cm (Fig. 3(b)).
  • the adhesive area between the film 3' and the copper foil 4' in Fig. 3(b) is 1 cm2.
  • the short sides of the film 3' of the obtained test piece were held and hung so that the long sides were parallel to the direction of gravity as shown in Figure 4. If the copper foil 4' on the lower side did not fall within 30 seconds, it was determined that there was adhesion.
  • Test pieces were prepared in the same manner as in the evaluation of "adhesion between film and copper foil” and used for the evaluation. The test pieces were placed in the gripping tool of a universal testing machine ("Strograph VG" manufactured by Toyo Seiki Seisakusho Co., Ltd.) with the film on the upper side and the copper foil on the lower side, and with the long side parallel to the direction of gravity. A tensile shear test was carried out in accordance with JIS K 6849-1994 under the conditions of temperature: 23°C, test range: 200N, and test speed: 5mm/min, to determine the tensile adhesive strength (N/cm 2 ).
  • Example 2A A film was produced and evaluated in the same manner as in Example 1A, except that the resin composition used for producing the film was changed to the resin composition obtained in Example 2. The results are shown in Table 4.
  • the film made of the resin composition of the present invention has adhesion to copper foil, and therefore can be used for metal foil laminates such as copper-clad laminates.
  • the present invention provides a resin composition and molded article that can exhibit high flame retardancy even when using little or no flame retardant.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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WO2015020020A1 (ja) * 2013-08-06 2015-02-12 三菱瓦斯化学株式会社 ポリイミド樹脂組成物及びポリイミド樹脂－繊維複合材
WO2016147996A1 (ja) 2015-03-19 2016-09-22 三菱瓦斯化学株式会社 ポリイミド樹脂
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WO2021100716A1 (ja) * 2019-11-19 2021-05-27 三菱瓦斯化学株式会社 樹脂組成物、樹脂成形体及びその製造方法

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WO2015020020A1 (ja) * 2013-08-06 2015-02-12 三菱瓦斯化学株式会社 ポリイミド樹脂組成物及びポリイミド樹脂－繊維複合材
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