WO2022065063A1 - ポリイミド樹脂組成物及び成形体 - Google Patents

ポリイミド樹脂組成物及び成形体 Download PDF

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WO2022065063A1
WO2022065063A1 PCT/JP2021/033232 JP2021033232W WO2022065063A1 WO 2022065063 A1 WO2022065063 A1 WO 2022065063A1 JP 2021033232 W JP2021033232 W JP 2021033232W WO 2022065063 A1 WO2022065063 A1 WO 2022065063A1
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Prior art keywords
polyimide resin
group
formula
polyether sulfone
carbon atoms
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PCT/JP2021/033232
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English (en)
French (fr)
Japanese (ja)
Inventor
敦史 酒井
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 JP2021570283A priority Critical patent/JP7040692B1/ja
Priority to KR1020237008900A priority patent/KR20230071124A/ko
Priority to CN202180063825.6A priority patent/CN116249732B/zh
Priority to US18/044,918 priority patent/US20230340263A1/en
Priority to EP21872194.2A priority patent/EP4219595A4/en
Publication of WO2022065063A1 publication Critical patent/WO2022065063A1/ja
Anticipated expiration legal-status Critical
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    • 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
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06—Polysulfones; Polyethersulfones
    • 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
    • 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
    • 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
    • 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 polyimide resin composition and a molded product.
  • Polyimide resin is a useful engineering plastic with high thermal stability, high strength, and high solvent resistance due to the rigidity of molecular chains, resonance stabilization, and strong chemical bonds, and is applied in a wide range of fields. Further, since the polyimide resin having crystallinity can further improve its heat resistance, strength and chemical resistance, it is expected to be used as a metal substitute or the like. However, while the polyimide resin has high heat resistance, it does not exhibit thermoplasticity and has a problem of low moldability.
  • High heat resistant resin Vespel (registered trademark) is known as a polyimide molding material (Patent Document 1), but it is difficult to mold because its fluidity is extremely low even at high temperatures, and it takes a long time under high temperature and high pressure conditions. It is also disadvantageous in terms of cost because it is necessary to perform molding. On the other hand, a resin having a melting point and fluidity at a high temperature, such as a crystalline resin, can be easily and inexpensively molded.
  • thermoplastic polyimide resin having thermoplasticity has been reported.
  • Thermoplastic polyimide resin is excellent in molding processability in addition to the heat resistance inherent in polyimide resin. Therefore, the thermoplastic polyimide resin can be applied to a molded product used in a harsh environment to which nylon or polyester, which is a general-purpose thermoplastic resin, cannot be applied.
  • Patent Document 2 describes a predetermined product obtained by reacting a tetracarboxylic acid containing at least one aromatic ring and / or a derivative thereof, a diamine containing at least one alicyclic hydrocarbon structure, and a chain aliphatic diamine.
  • a thermoplastic polyimide resin containing the repeating structural unit of the above is disclosed.
  • Patent Document 3 discloses a thermoplastic polyimide resin containing a predetermined repeating unit, and also describes that the polyimide resin is used in combination with another resin as a polymer alloy.
  • Patent Document 4 a polyimide-based resin composition containing a polyetherimide resin and a crystalline polyimide resin containing a tetracarboxylic acid component and an aliphatic diamine component is excellent in heat resistance, rigidity, and impact resistance. Is disclosed.
  • thermoplastic polyimide resin described in Patent Document 3 has crystallinity and is excellent in heat resistance, strength, chemical resistance and the like, but there is room for further improvement in tensile properties, particularly toughness among mechanical properties. It is thought that if the toughness is improved, the impact resistance, vibration damping property, etc. will also be improved, and it is expected to be applied to applications where these characteristics are important.
  • the improvement in toughness referred to here means that when a tensile stress is applied to the molded body, the elongation until it breaks becomes large, and can be evaluated by, for example, a tensile fracture strain measurement.
  • Patent Document 4 the tensile elasticity and the tensile elongation at break of a molded product made of a polyimide resin composition containing a polyetherimide resin and a crystalline polyimide resin are evaluated.
  • the tensile elongation at break has not been obtained, which is higher than that of the crystalline polyimide resin alone.
  • An object of the present invention is to provide a polyimide resin composition and a molded product having further improved toughness while maintaining high levels of heat resistance, bending characteristics, etc. derived from a crystalline thermoplastic polyimide resin.
  • the present inventors can solve the above-mentioned problems with a polyimide resin composition containing a crystalline thermoplastic polyimide resin in which specific different polyimide constituent units are combined in a specific ratio and a polyether sulfone resin in a predetermined mass ratio.
  • the present invention relates to the following. [1] The total of the repeating structural unit of the formula (1) and the repeating structural unit of the formula (2), including the repeating structural unit represented by the following formula (1) and the repeating structural unit represented by the following formula (2).
  • R 1 is a divalent group having 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure.
  • R 2 is a divalent chain aliphatic group having 5 to 16 carbon atoms.
  • X 1 And X 2 are independently tetravalent groups with 6 to 22 carbon atoms containing at least one aromatic ring.
  • the polyimide resin composition and the molded product of the present invention are excellent in heat resistance and bending characteristics and have high toughness, it is expected to be applied to applications in which impact resistance, vibration damping property, etc. are important.
  • sliding members such as gears and bearings, cutting members, structural members such as robot arms, winding coating materials such as electric wires, screws, nuts, packings, diaphragms for speakers, reflectors, 5th generation mobile communication systems (5G).
  • 5G mobile communication systems 5th generation mobile communication systems
  • 6G mobile communication system (6G) related members, various films, etc. can be applied.
  • it can be expected to be applied to a water treatment membrane or the like as an application similar to the polyether sulfone resin.
  • FIG. 6 It is a schematic diagram which shows the preparation method of the sample (ultra-thin section) used for the field emission type scanning transmission electron microscope (FE-STEM) observation.
  • 6 is a photomicrograph of the polyimide resin composition (pellet) of Example 1 cut in parallel with the flow direction (MD) when observed by FE-STEM. It is a micrograph of the polyimide resin composition (pellet) of Example 2 when the cross section cut parallel to MD was observed by FE-STEM. It is a micrograph of the polyimide resin composition (pellet) of Comparative Example 1 when the cross section cut parallel to MD was observed by FE-STEM. It is a micrograph of the pellet of the polyether sulfone resin (B1) of Reference Example 1 when the cross section cut parallel to MD was observed by FE-STEM.
  • the polyimide resin composition of 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 repeating structural unit of the formula (1) and the formula (2).
  • the mass ratio [(A) / (B)] with the component (B) is 0.1 / 99.9 to 65/35.
  • R 1 is a divalent group having 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure.
  • R 2 is a divalent chain aliphatic group having 5 to 16 carbon atoms.
  • X 1 And X 2 are independently tetravalent groups with 6 to 22 carbon atoms containing at least one aromatic ring.
  • the polyimide resin (A) used in the present invention includes a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2), and the repeating structural unit of the formula (1) and the formula (1).
  • the content ratio of the repeating constituent unit of the formula (1) to the total of the repeating constituent units of 2) is 20 to 70 mol%.
  • R 1 is a divalent group having 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure.
  • R 2 is a divalent chain aliphatic group having 5 to 16 carbon atoms.
  • X 1 And X 2 are independently tetravalent groups with 6 to 22 carbon atoms containing at least one aromatic ring.
  • the polyimide resin (A) used in the present invention is a crystalline thermoplastic resin, and its form is preferably powder or pellets.
  • the thermoplastic polyimide resin is a polyimide resin having no glass transition temperature (Tg), which is formed by closing the imide ring after being molded in the state of a polyimide precursor such as polyamic acid, or a temperature lower than the glass transition temperature. It is distinguished from the polyimide resin that decomposes in.
  • R 1 is a divalent group having 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure.
  • the alicyclic hydrocarbon structure means a ring derived from the alicyclic hydrocarbon compound, and the alicyclic hydrocarbon compound may be saturated or unsaturated, and may simply be used. It may be a ring or a polycycle.
  • Examples of the alicyclic hydrocarbon structure include, but are limited to, a cycloalkane ring such as a cyclohexane ring, a cycloalkene ring such as cyclohexene, a bicycloalkene ring such as norbornane ring, and a bicycloalkene ring such as norbornene. Do not mean. Among these, a cycloalkane ring is preferable, a cycloalkane ring having 4 to 7 carbon atoms is more preferable, and a cyclohexane ring is more preferable.
  • R 1 has 6 to 22 carbon atoms, preferably 8 to 17 carbon atoms.
  • R 1 contains at least one alicyclic hydrocarbon structure, preferably 1 to 3.
  • R 1 is preferably a divalent group represented by the following formula (R1-1) or (R1-2).
  • M 11 and m 12 are independently integers of 0 to 2, preferably 0 or 1.
  • m 13 to m 15 are independently integers of 0 to 2, preferably 0. Or it is 1.
  • R 1 is particularly preferably a divalent group represented by the following formula (R1-3).
  • R1-3 the positional relationship between the two methylene groups with respect to the cyclohexane ring may be cis or trans, and the ratio of cis to trans is Any value may be used.
  • X 1 is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.
  • the aromatic ring may be a monocyclic ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring, but the aromatic ring is not limited thereto. Among these, a benzene ring and a naphthalene ring are preferable, and a benzene ring is more preferable.
  • the number of carbon atoms of X 1 is 6 to 22, preferably 6 to 18.
  • X 1 contains at least one aromatic ring, preferably 1 to 3 aromatic rings.
  • X 1 is preferably a tetravalent group represented by any of the following formulas (X-1) to (X-4).
  • R 11 to R 18 are independently alkyl groups having 1 to 4 carbon atoms.
  • P 11 to p 13 are independently integers of 0 to 2, preferably 0.
  • P 14 , P 15 , p 16 and p 18 are independently integers of 0 to 3, preferably 0.
  • p 17 is an integer of 0 to 4, preferably 0. L 11 to L.
  • X 13 is independently a single bond, a carbonyl group, or an alkylene group having 1 to 4 carbon atoms.
  • X 1 is a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring
  • R 12 , R 13 , p 12 and p 13 in the formula (X-2) are represented by the formula (X-).
  • the tetravalent group represented by 2) is selected so that the number of carbon atoms is in the range of 10 to 22.
  • L 11 , R 14 , R 15 , p 14 and p 15 in the formula (X-3) have the carbon number of the tetravalent group represented by the formula (X-3) in the range of 12 to 22.
  • X 1 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 further preferably 8 to 10 carbon atoms.
  • the chain aliphatic group means a group derived from the chain aliphatic compound, and the chain aliphatic compound may be saturated or unsaturated, and may be linear. It may be present or branched.
  • R2 is preferably an alkylene group having 5 to 16 carbon atoms, more preferably an alkylene group having 6 to 14 carbon atoms, still more preferably an alkylene group having 7 to 12 carbon atoms, and particularly preferably an alkylene group having 8 to 10 carbon atoms. It is an alkylene group.
  • 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 is particularly preferably an octamethylene group.
  • X 2 is defined in the same manner as X 1 in the formula (1), and the preferred mode is also the same.
  • the content ratio of the repeating constituent unit of the formula (1) to the total of the repeating constituent unit of the formula (1) and the repeating constituent unit of the formula (2) is 20 to 70 mol%.
  • the content ratio of the repeating structural unit of the formula (1) is in the above range, the polyimide resin can be sufficiently crystallized even in a general injection molding cycle. If the content ratio is less than 20 mol%, the molding processability is lowered, and if it exceeds 70 mol%, the crystallinity is lowered, so that the heat resistance is lowered.
  • the content ratio of the repeating constituent unit of the formula (1) to the total of the repeating constituent unit of the formula (1) and the repeating constituent unit of the formula (2) is preferably 65 mol% or less from the viewpoint of exhibiting high crystallinity.
  • the polyimide resin (A) It is more preferably 60 mol% or less, still more preferably 50 mol% or less, still more preferably less than 40 mol%.
  • the content ratio of the repeating constituent unit of the formula (1) to the total of the repeating constituent unit of the formula (1) and the repeating constituent unit of the formula (2) is 20 mol% or more and less than 40 mol%, the polyimide resin (A) It is possible to obtain a resin molded body having higher crystallinity and more excellent heat resistance.
  • the content ratio is preferably 25 mol% or more, more preferably 30 mol% or more, still more preferably 32 mol% or more from the viewpoint of molding processability, and even more preferably from the viewpoint of exhibiting high crystallinity. Is 35 mol% or less.
  • the total content ratio of the repeating constituent unit of the formula (1) and the repeating constituent unit of the formula (2) to all the repeating constituent units constituting the polyimide resin (A) is preferably 50 to 100 mol%, more preferably 75. It is ⁇ 100 mol%, more preferably 80-100 mol%, still more preferably 85-100 mol%.
  • the polyimide resin (A) may further contain a repeating structural unit of the following formula (3).
  • the content ratio of the repeating structural unit of the formula (3) to the total of the repeating structural unit of the formula (1) and the repeating structural unit of the formula (2) is preferably 25 mol% or less.
  • the lower limit is not particularly limited and may exceed 0 mol%.
  • the content ratio is preferably 5 mol% or more, more preferably 10 mol% or more, while maintaining crystallinity, from the viewpoint of improving heat resistance. From this point of view, it is preferably 20 mol% or less, more preferably 15 mol% or less.
  • R 3 is a divalent group having 6 to 22 carbon atoms containing at least one aromatic ring.
  • X 3 is a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring.
  • R 3 is a divalent group with 6 to 22 carbon atoms containing at least one aromatic ring.
  • the aromatic ring may be a monocyclic ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring, but the aromatic ring is not limited thereto. Among these, a benzene ring and a naphthalene ring are preferable, and a benzene ring is more preferable.
  • R 3 has 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms.
  • R 3 contains at least one aromatic ring, preferably 1 to 3 aromatic rings.
  • R 3 is preferably a divalent group represented by the following formula (R3-1) or (R3-2).
  • M 31 and m 32 are independently integers of 0 to 2, preferably 0 or 1.
  • m 33 and m 34 are independently integers of 0 to 2, preferably 0. Or 1.
  • R 21 , R 22 and R 23 are independently 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.
  • p 21 , p 22 and p 23 are integers from 0 to 4, preferably 0.
  • L 21 is a single bond, a carbonyl group or an alkylene group having 1 to 4 carbon atoms.) Since R 3 is a divalent group having 6 to 22 carbon atoms containing at least one aromatic ring, m 31 , m 32 , R 21 and p 21 in the formula (R3-1) are represented by the formula (R3-). The number of carbon atoms of the divalent group represented by 1) is selected to be in the range of 6 to 22. Similarly, L 21 , m 33 , m 34 , R 22 , R 23 , p 22 and p 23 in the formula (R3-2) have the carbon number of the divalent group represented by the formula (R3-2). It is selected to fall within the range of 12-22.
  • X 3 is defined in the same manner as X 1 in the formula (1), and the preferred mode is also the same.
  • the terminal structure of the polyimide resin (A) is not particularly limited, but it is preferable to have 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.
  • the polyimide resin (A) has the above-mentioned specific group at the end, a resin composition having excellent heat aging resistance can be obtained.
  • the saturated chain aliphatic group having 5 to 14 carbon atoms include n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and n-undecyl group.
  • unsaturated chain aliphatic groups having 5 to 14 carbon atoms 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-hexenyl group, 1-heptenyl group, 2-heptenyl group, 1- Examples thereof include an octenyl group, a 2-octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group and the like.
  • the above-mentioned chain aliphatic group is preferably a saturated chain aliphatic group, and more preferably a saturated linear aliphatic group.
  • the chain aliphatic group preferably has 6 or more carbon atoms, more preferably 7 or more carbon atoms, still more preferably 8 or more carbon atoms, and preferably 12 or less carbon atoms, more preferably.
  • the above-mentioned chain aliphatic group may be only one kind or 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.
  • the polyimide resin (A) preferably has only a chain aliphatic group having 5 to 14 carbon atoms at the terminal in addition to the terminal amino group and the terminal carboxy group.
  • 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 a total of 100 of all the repeating constituent units constituting the polyimide resin (A) from the viewpoint of exhibiting excellent heat aging resistance. It is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, still more preferably 0.2 mol% or more with respect to mol%. Further, in order to secure a sufficient molecular weight and obtain good mechanical properties, the content of the chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (A) constitutes 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 lower and a glass transition temperature of 150 ° C. or higher.
  • the melting point of the polyimide resin (A) is more preferably 280 ° C. or higher, further preferably 290 ° C. or higher from the viewpoint of heat resistance, and preferably 345 ° C. or lower, more preferably from the viewpoint of exhibiting high molding processability. Is 340 ° C. or lower, more preferably 335 ° C. or lower.
  • the glass transition temperature of the polyimide resin (A) is more preferably 160 ° C. or higher, more preferably 170 ° C. or higher from the viewpoint of heat resistance, and preferably 250 ° C.
  • the polyimide resin (A) is cooled at a temperature lowering rate of 20 ° C./min after melting the polyimide resin by differential scanning calorimeter measurement.
  • the calorific value of the crystallization calorific value observed at the time of the crystallization is preferably 5.0 mJ / mg or more, and more preferably 10.0 mJ / mg or more.
  • the melting point, glass transition temperature, and crystallization calorimeter of the polyimide resin (A) can all be measured by a differential scanning calorimeter, and specifically, can be measured by the method described in Examples.
  • the weight average molecular weight Mw of the polyimide resin (A) is preferably 10,000 to 150,000, more preferably 15,000 to 100,000, still more preferably 20,000 to 80,000, still more preferably 30,. It is in the range of 000 to 70,000, more preferably 35,000 to 65,000.
  • the weight average molecular weight Mw of the polyimide resin (A) is 10,000 or more, the mechanical strength of the obtained molded product is good, and when it is 40,000 or more, the stability of the mechanical strength is good. Further, if it is 150,000 or less, the molding processability is good.
  • the weight average molecular weight Mw of the polyimide resin (A) can be measured by a gel filtration chromatography (GPC) method using polymethylmethacrylate (PMMA) as a standard sample, and specifically, can be measured by the method described in Examples. ..
  • the logarithmic viscosity of the 5% by mass concentrated sulfuric acid solution of the polyimide resin (A) at 30 ° C. is preferably in the range of 0.8 to 2.0 dL / g, more preferably 0.9 to 1.8 dL / g.
  • the logarithmic viscosity ⁇ is obtained from the following formula by measuring the flow time of concentrated sulfuric acid and the polyimide resin solution at 30 ° C. using a Canon Fenceke viscometer.
  • ⁇ ln [(ts / t 0 ) / C] t 0 : Time for concentrated sulfuric acid to flow ts: Time for polyimide resin solution to flow C: 0.5 (g / dL)
  • the polyimide resin (A) can be produced by reacting a tetracarboxylic acid component with a diamine component.
  • the tetracarboxylic acid component contains a tetracarboxylic acid containing at least one aromatic ring and / or a derivative thereof
  • the diamine component contains a diamine 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 an alkyl group may be contained in the structure. Further, the tetracarboxylic acid preferably has 6 to 26 carbon atoms. Examples of the tetracarboxylic acid include pyromellitic acid, 2,3,5,6-toluenetetracarboxylic acid, 3,3', 4,4'-benzophenonetetracarboxylic acid, 3,3', 4,4'-biphenyl. Tetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid and the like are preferable. Of these, pyromellitic acid is more preferable.
  • Examples of the derivative of the tetracarboxylic acid containing at least one aromatic ring include an anhydride or an alkyl ester of the tetracarboxylic acid containing at least one aromatic ring.
  • the tetracarboxylic acid derivative preferably has 6 to 38 carbon atoms.
  • Examples of the tetracarboxylic acid anhydride include pyromellitic acid monoanhydride, pyromellitic acid dianhydride, 2,3,5,6-toluenetetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl.
  • Sulfonitetetracarboxylic acid dianhydride 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 1,4,5,5 Examples thereof include 8-naphthalene tetracarboxylic acid dianhydride.
  • alkyl ester of tetracarboxylic acid examples include dimethyl pyromellitic acid, diethyl pyromellitic acid, dipropyl pyromellitic acid, diisopropyl pyromellitic acid, dimethyl 2,3,5,6-toluenetetracarboxylate, 3,3', 4 , 4'-Diphenylsulfonetetracarboxylate dimethyl, 3,3', 4,4'-benzophenone tetracarboxylate dimethyl, 3,3', 4,4'-biphenyltetracarboxylate dimethyl, 1,4,5,8 -Includes dimethyl naphthalenetetracarboxylate and the like.
  • the number of carbon atoms of the alkyl group is preferably 1 to 3.
  • At least one compound selected from the above may be used alone, or two or more compounds may be used in combination.
  • the number of carbon atoms of the diamine containing at least one alicyclic hydrocarbon structure is preferably 6 to 22, for example, 1,2-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-.
  • 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 the number of carbon atoms is preferably 5 to 16, more preferably 6 to 14, and even more preferably 7 to 12. Further, if the number of carbon atoms in the chain portion is 5 to 16, an ether bond may be contained between them.
  • Examples of chain aliphatic diamines include 1,5-pentamethylenediamine, 2-methylpentane-1,5-diamine, 3-methylpentane-1,5-diamine, 1,6-hexamethylenediamine, 1,7-hepta.
  • the chain aliphatic diamine may be used alone or in combination of two or more.
  • chain aliphatic diamines having 8 to 10 carbon atoms can be preferably used, and at least one selected from the group consisting of 1,8-octamethylenediamine and 1,10-decamethylenediamine is particularly preferable. Can be used.
  • the molar amount of the diamine containing at least one alicyclic hydrocarbon structure to the total amount of the diamine containing at least one alicyclic hydrocarbon structure and the chain aliphatic diamine is preferably 20 to 70 mol%.
  • the molar amount is preferably 25 mol% or more, more preferably 30 mol% or more, still more preferably 32 mol% or more, and from the viewpoint of exhibiting high crystallinity, preferably 60 mol% or less, more preferably 50. It is mol% or less, more preferably less than 40 mol%, still more preferably 35 mol% or less.
  • the diamine component may contain a diamine containing at least one aromatic ring.
  • the diamine containing at least one aromatic ring preferably has 6 to 22 carbon atoms, for example, orthoxylylene diamine, metaxylylene diamine, paraxylylene diamine, 1,2-diethynylbenzenediamine, 1,3-diethynyl.
  • the molar ratio of the amount of diamine containing at least one aromatic ring to the total amount of diamine containing at least one alicyclic hydrocarbon structure and the chain aliphatic diamine may be 25 mol% or less. It is preferable, more preferably 20 mol% or less, still more preferably 15 mol% or less.
  • the lower limit of the molar ratio is not particularly limited, but from the viewpoint of improving heat resistance, it is preferably 5 mol% or more, more preferably 10 mol% or more.
  • the molar ratio is more preferably 12 mol% or less, still more preferably 10 mol% or less, still more preferably 5 mol% or less, still more preferably. It is 0 mol%.
  • the ratio of the charged amount of the tetracarboxylic acid component to the diamine component is preferably 0.9 to 1.1 mol of the diamine component with respect to 1 mol of the tetracarboxylic acid component. ..
  • an end-capping agent may be mixed in addition to the tetracarboxylic acid component and the diamine component.
  • the terminal encapsulant at least one selected from the group consisting of monoamines and dicarboxylic acids is preferable.
  • the amount of the terminal encapsulant used may be any amount as long as a desired amount of terminal groups can be introduced into the polyimide resin (A), and 0.0001 to 0. 1 mol is preferable, 0.001 to 0.06 mol is more preferable, 0.002 to 0.035 mol is further preferable, 0.002 to 0.020 mol is more preferable, and 0.002 to 0.012 mol is more preferable. Is even more preferable.
  • a monoamine terminal encapsulant is preferable as the terminal encapsulant, and from the viewpoint of introducing the above-mentioned chain aliphatic group having 5 to 14 carbon atoms into the terminal of the polyimide resin (A) to improve heat aging resistance.
  • 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 further preferable.
  • the terminal encapsulant is particularly preferably at least one selected from the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, isononylamine, n-decylamine, and isodecylamine. , More preferably at least one selected from the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, and isononylamine, and most preferably n-octylamine, isooctylamine, and the like. And at least one selected from the group consisting of 2-ethylhexylamine.
  • polymerization method for producing the polyimide resin (A) As a polymerization method for producing the polyimide resin (A), a known polymerization method can be applied, and the method described in International Publication No. 2016/147996 can be used.
  • the polyimide resin (A) and the polyether sulfone resin (B) have a mass ratio of [(A) / (B)] of 0.1 / 99.9 to 65/35. Contains in proportion.
  • a polyimide resin composition and molding with improved toughness while maintaining high levels of heat resistance, bending characteristics, etc. by containing the polyimide resin (A) and the polyether sulfone resin (B) in a predetermined ratio. can be a body.
  • the polyether sulfone resin used as the component (B) is an amorphous thermoplastic resin containing a repeating structural unit having an ether bond and a sulfonyl group.
  • the amorphous thermoplastic resin having an ether bond and a sulfonyl group and containing a repeating structural unit having an imide bond is not included in the component (B).
  • the polyether sulfone resin (B) preferably contains at least one aromatic ring or alicyclic hydrocarbon structure, and more preferably contains an aromatic ring, from the viewpoint of obtaining good heat resistance and toughness.
  • the definitions of aromatic ring and alicyclic hydrocarbon structures are the same as described above.
  • Examples of the polyether sulfone resin (B) include those containing a repeating structural unit represented by the following formula (4).
  • R 41 and R 42 are independently 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.
  • R 43 contains an ether bond. It is a divalent group.
  • R 41 and p42 are independently integers from 0 to 4).
  • R 41 and R 42 are preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
  • R 43 is preferably a divalent group represented by —O— (CH 2 ) m42 ⁇ , where m 42 is preferably 0-4, more preferably 0-3, even more preferably 0.
  • p 41 and p 42 are preferably 0 to 2, and more preferably 0.
  • polyether sulfone resin (B) a resin having a structure represented by the following formula (I) is more preferable.
  • R indicates a terminal group and is Cl or OH.
  • N indicates the average number of repeating constituent units and is a number of 2 or more.
  • R in the formula (I) is preferably Cl.
  • R in the formula (I) contains OH, it becomes a reactive polyether sulfone resin.
  • the glass transition temperature of the polyether sulfone resin (B) is preferably 210 ° C. or higher, more preferably 215 ° C. or higher from the viewpoint of obtaining good heat resistance and toughness, and preferably 280 from the viewpoint of molding processability. ° C or lower, more preferably 260 ° C or lower.
  • the glass transition temperature can be measured by the same method as described above.
  • the intrinsic viscosity of the polyether sulfone resin (B) at 25 ° C. is preferably 0.20 to 1.00 dL / g, more preferably 0.25 to 1.00 dL / g, from the viewpoint of obtaining good heat resistance and toughness. , More preferably 0.30 to 0.80 dL / g, and even more preferably 0.35 to 0.60 dL / g.
  • the intrinsic viscosity of the polyether sulfone resin (B) can be measured by a method according to JIS K7337-5: 2000, specifically by the method described in Examples.
  • the intrinsic viscosity is preferably in the above range as a value measured at 25 ° C. using a polyether sulfone resin powder which has not been given a thermal history due to melting or the like.
  • the number average molecular weight (Mn) of the polyether sulfone resin (B) is preferably 2,000 to 25,000, more preferably 3,000 to 25,000, still more preferably 3,000 to 25,000, from the viewpoint of obtaining good heat resistance and toughness. Is 3,500 to 25,000, more preferably 3,500 to 25,000, and even more preferably 5,000 to 20,000.
  • the weight average molecular weight (Mw) of the polyether sulfone resin (B) is preferably 5,000 to 80,000, more preferably 7,000 to 80,000, still more preferably, from the viewpoint of obtaining good heat resistance and toughness. Is 8,000 to 80,000, more preferably 8,000 to 60,000, even more preferably 10,000 to 55,000, and even more preferably 12,000 to 55,000.
  • the number average molecular weight and weight average molecular weight of the polyether sulfone resin (B) can be measured by gel permeation chromatography (GPC) using polymethylmethacrylate (PMMA) as a standard sample, and are specifically described in Examples. It can be measured by the method of. It is preferable that the numerical average molecular weight and the weight average molecular weight are in the above range as the values measured by using the polyether sulfone resin powder which has not been given a thermal history due to melting or the like.
  • the polyether sulfone resin (B) may be used alone or in combination of two or more.
  • the form of the polyether sulfone resin (B) is not particularly limited, and either powder or pellets can be used, but from the viewpoint of improving the dispersibility in the polyimide resin (A), there is no thermal history such as melting. The powder is more preferable from the viewpoint of maintaining the properties.
  • a commercially available product can also be used as the polyether sulfone resin (B).
  • polyether sulfone resins examples include "Sumika Excel PES” series (3600P, 4100P, 4800P, 5200P, 5400P, 5900P, 7600P, 5003P, 5003MPS, 3600G, 4100G, 4800G) manufactured by Sumitomo Chemical Co., Ltd., BASF. "Ultra Zone E” series (E1010, E2010, E2020P, E3010, E6020P) and the like.
  • the mass ratio [(A) / (B)] of the polyimide resin (A) and the polyether sulfone resin (B) in the polyimide resin composition of the present invention is 0.1/99 from the viewpoint of obtaining good toughness. It is .9 to 65/35, preferably 1/99 to 65/35, more preferably 5/95 to 65/35, still more preferably 10/90 to 65/35, and even more preferably 15/85 to 60. It is in the range of / 40, more preferably 20/80 to 60/40, even more preferably 25/75 to 60/40, and even more preferably 25/75 to 55/45.
  • the total content of the polyimide resin (A) and the polyether sulfone resin (B) in the polyimide resin composition is preferably 50% by mass or more, more preferably 70% by mass or more from the viewpoint of obtaining the effect of the present invention. It is more preferably 80% by mass or more, and even more preferably 90% by mass or more. The upper limit is 100% by mass.
  • the polyimide resin composition of the present invention comprises a filler, a reinforcing fiber, a matting agent, a nucleating agent, a plasticizer, an antistatic agent, an antioxidant, an antigelling agent, a flame retardant, a coloring agent, and a slidability improving agent.
  • Additives such as antioxidants, ultraviolet absorbers, conductive agents, and resin modifiers may be contained, if necessary.
  • the content of the additive is not particularly limited, but from the viewpoint of exhibiting the effect of the additive while maintaining the physical properties derived from the polyimide resin (A) and the polyether sulfone resin (B), the polyimide resin composition Usually, it is 50% by mass or less, preferably 0.0001 to 30% by mass, more preferably 0.0001 to 15% by mass, and further preferably 0.001 to 10% by mass.
  • the polyimide resin composition of the present invention can take any form, but is preferably pellets. Since the polyimide resin (A) and the polyether sulfone resin (B) have thermoplasticity, for example, the polyimide resin (A), the polyether sulfone resin (B), and various optional components as necessary are melt-kneaded in an extruder. The strands can be extruded and pelleted by cutting the strands. Further, by introducing the obtained pellets into various molding machines and thermoforming by the method described later, a molded body having a desired shape can be easily manufactured.
  • the glass transition temperature of the polyimide resin composition of the present invention is preferably 160 ° C. or higher, more preferably 170 ° C. or higher from the viewpoint of heat resistance, and preferably 250 ° C. or lower from the viewpoint of exhibiting high molding processability. , More preferably 240 ° C. or lower, still more preferably 230 ° C. or lower.
  • the glass transition temperature can be measured by the same method as described above.
  • the polyimide resin composition of the present invention it is possible to provide a molded product having further improved toughness as compared with the case of the polyimide resin (A) alone or the polyether sulfone resin (B) alone.
  • the 1A type test piece specified in JIS K7161-2: 2014 obtained by molding a polyimide resin composition is in accordance with JIS K7161-1: 2014 and K7161-2: 2014.
  • the tensile fracture strain measured when a tensile test is performed at a temperature of 23 ° C., a distance between gripping tools of 50 mm, and a test speed of 5 mm / min is preferably 50% or more, more preferably 70% or more, still more preferably 90%. The above can be done.
  • the tensile fracture strain can be specifically measured by the method described in Examples.
  • the polyimide resin composition of the present invention can improve toughness as described above while maintaining a high level of bending characteristics.
  • a molded product of 80 mm ⁇ 10 mm ⁇ thickness 4 mm specified by ISO316 obtained by molding a polyimide resin composition has a temperature of 23 ° C. and a test speed of 2 mm / min in accordance with ISO178: 2010.
  • the bending strength measured when the bending test is performed in 1) can be 100 MPa or more, and the flexural modulus can be 2.2 GPa or more. Bending strength and flexural modulus can be specifically measured by the method described in Examples.
  • the polyimide resin composition of the present invention it is possible to produce a molded product having a higher whiteness than the case of the polyimide resin (A) alone and the polyether sulfone resin (B) alone. Therefore, the polyimide resin composition of the present invention and its molded product are expected to be applied to reflectors and the like. Further, since the polyimide resin composition of the present invention has the performance derived from the polyimide resin (A) which is a crystalline thermoplastic resin, the chemical resistance is also good.
  • the present invention provides a molded product containing the polyimide resin composition. Since the polyimide resin composition of the present invention has thermoplasticity, the molded product of the present invention can be easily produced by thermoforming. Examples of the heat molding method include injection molding, extrusion molding, blow molding, hot press molding, vacuum molding, pressure molding, laser molding, welding, welding, and the like, and any molding method that goes through a heat melting step can be used. Is possible.
  • the molding temperature varies depending on the thermal characteristics (melting point and glass transition temperature) of the polyimide resin composition, but for example, in injection molding, molding can be performed at a molding temperature of less than 400 ° C. and a mold temperature of 220 ° C. or lower.
  • thermoforming the polyimide resin composition As a method for producing a molded product, it is preferable to have a step of thermoforming the polyimide resin composition at a temperature of less than 400 ° C.
  • Specific procedures include, for example, the following methods. First, a polyether sulfone resin (B) and various optional components are added to the polyimide resin (A) and dry-blended, and then this is introduced into an extruder and melted at a temperature of preferably less than 400 ° C. Melt kneading and extrusion in an extruder to prepare pellets.
  • the polyimide resin (A) is introduced into the extruder, preferably melted at a temperature of less than 400 ° C., and the polyether sulfone resin (B) and various optional components are introduced therein to form the polyimide resin (A) in the extruder.
  • the above-mentioned pellets may be produced by melt-kneading and extruding. After the pellets are dried, they can be introduced into various molding machines and thermoformed preferably at a temperature of less than 400 ° C. to produce a molded product having a desired shape.
  • the molded product of the present invention is excellent in heat resistance and bending characteristics and has high toughness, it is expected to be applied to applications in which impact resistance, vibration damping property, etc. are important.
  • sliding members such as gears and bearings, cutting members, structural members such as robot arms, winding coating materials such as electric wires, screws, nuts, packings, diaphragms for speakers, reflectors, 5th generation mobile communication systems (5G).
  • 5G 5th generation mobile communication systems
  • Applicable to applications such as related materials and various films.
  • it can be expected to be applied to a water treatment membrane or the like as an application similar to the polyether sulfone resin.
  • IR measurement ⁇ Infrared spectroscopic analysis (IR measurement)> The IR measurement of the polyimide resin was performed using "JIR-WINSPEC 50" manufactured by JEOL Ltd.
  • the melting point Tm, glass transition temperature Tg, crystallization temperature Tc, and crystallization calorific value ⁇ Hm of the polyimide resin, the polyether sulfone resin, or the polyimide resin composition produced in each example are determined by a differential scanning calorimeter device (SI Nano). It was measured using "DSC-6220" manufactured by Technology Co., Ltd.). Under a nitrogen atmosphere, the polyimide resin, the polyether sulfone resin, or the polyimide resin composition was subjected to the thermal history under the following conditions.
  • the conditions of the heat history are the first temperature rise (heating rate 10 ° C./min), then cooling (heating rate 20 ° C./min), and then the second temperature rise (heating rate 10 ° C./min).
  • the melting point Tm was determined by reading the peak top value of the endothermic peak observed at the second temperature rise.
  • the glass transition temperature Tg was determined by reading the value observed at the second temperature rise.
  • the crystallization temperature Tc was determined by reading the peak top value of the exothermic peak observed during cooling. For Tm, Tg and Tc, the peak top value of each peak was read for those in which multiple peaks were observed.
  • the crystallization calorific value ⁇ Hm (mJ / mg) was calculated from the area of the exothermic peak observed during cooling.
  • ⁇ Semi-crystallization time> The semi-crystallization time of the polyimide resin was measured using a differential scanning calorimeter (“DSC-6220” manufactured by SII Nanotechnology Co., Ltd.). After holding at 420 ° C for 10 minutes in a nitrogen atmosphere to completely melt the polyimide resin, when the quenching operation was performed at a cooling rate of 70 ° C / min, the crystallization peak was observed from the time of appearance to the peak top. I calculated the time it took to reach it. In Table 1, when the semi-crystallization time is 20 seconds or less, it is expressed as " ⁇ 20".
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyimide resin and the polyether sulfone resin are determined by the following conditions using a gel permeation chromatography (GPC) measuring device "Shodex GPC-101" manufactured by Showa Denko KK. Measured at.
  • GPC gel permeation chromatography
  • the polyether sulfone resin a polyether sulfone resin powder was used as a measurement sample.
  • the intrinsic viscosity of the polyether sulfone resin was measured by the following method in accordance with JIS K7337-5: 2000. As a measurement sample, a polyether sulfone resin powder was used. N, N-dimethylformamide solutions of polyether sulfone resins with concentrations of 0.5 g / dL, 1.0 g / dL, and 1.5 g / dL were prepared. The viscosity of this solution was measured three times each using a Ubbelohde viscometer (No.
  • HDT Heat distortion temperature
  • a molded product having a size of 80 mm ⁇ 10 mm ⁇ thickness 4 mm was produced by a method described later and used for measurement. The measurement was carried out in a flatwise manner in accordance with JIS K711-1, 2: 2015. Specifically, using the HDT test device "Auto-HDT3D-2" (manufactured by Toyo Seiki Seisakusho Co., Ltd.), heat is applied under the conditions of a distance between fulcrums of 64 mm, a load of 1.80 MPa, and a heating rate of 120 ° C./hour. The deformation temperature was measured.
  • ⁇ Bending strength and flexural modulus> Using the polyimide resin, the polyether sulfone resin, or the polyimide resin composition produced in each example, a molded product having an size of 80 mm ⁇ 10 mm ⁇ thickness 4 mm specified by ISO316 was prepared by a method described later and used for measurement. Using a bend graph (manufactured by Toyo Seiki Seisakusho Co., Ltd.), a bending test was performed at a temperature of 23 ° C. and a test speed of 2 mm / min in accordance with ISO178: 2010, and bending strength and flexural modulus were measured.
  • a bend graph manufactured by Toyo Seiki Seisakusho Co., Ltd.
  • Production Example 1 (Production of Polyimide Resin 1) 500 g of 2- (2-methoxyethoxy) ethanol (manufactured by Nippon Embroidery Co., Ltd.) and pyromellitic acid dianhydride in a 2 L separable flask equipped with a Dean-Stark apparatus, a Leibich cooling tube, a thermoelectric pair, and four paddle blades. 218.12 g (1.00 mol) (manufactured by Mitsubishi Gas Chemical Company, Inc.) was introduced, and after flowing with nitrogen, the mixture was stirred at 150 rpm so as to have a uniform suspension solution.
  • the nitrogen flow state was set, and the rotation speed of the stirring blade was set to 250 rpm.
  • the dropping was completed, 130 g of 2- (2-methoxyethoxy) ethanol and 1.284 g (0.010 mol) of n-octylamine (manufactured by Kanto Chemical Co., Inc.) as a terminal encapsulant were added and further stirred. .. At this stage, a pale yellow polyamic acid solution was obtained.
  • the temperature of the polyamic acid solution in the 2 L separable flask was raised to 190 ° C.
  • polyimide resin 1 A powder (hereinafter, also simply referred to as “polyimide resin 1”) was obtained.
  • Table 1 shows the composition and evaluation results of the polyimide resin 1 in Production Example 1.
  • the mol% of the tetracarboxylic acid component and the diamine component in Table 1 is a value calculated from the amount of each component charged at the time of manufacturing the polyimide resin.
  • Examples 1 and 2 and Comparative Examples 1 and 2 polyimide resin composition, preparation and evaluation of molded product
  • Polyimide resin 1 powder obtained in Production Example 1 and polyether sulfone resin (B1) powder (“Sumika Excel 3600P” manufactured by Sumitomo Chemical Co., Ltd., intrinsic viscosity at 25 ° C.: 0.307 dL / g, Mn: 8,600, Mw: 16,500, Tg: 222 ° C.) are dry-blended at the ratios shown in Table 2, and then a biaxial kneading extruder that rotates in the same direction (“HK-25D” manufactured by Parker Corporation).
  • Examples 3 to 5 and Comparative Examples 3 to 4 polyimide resin composition, preparation and evaluation of molded product
  • Polyimide resin 1 powder obtained in Production Example 1 and polyether sulfone resin (B2) powder (“Sumika Excel 4800P” manufactured by Sumitomo Chemical Co., Ltd., intrinsic viscosity at 25 ° C.: 0.389 dL / g, Mn: 7,200, Mw: 16,200, Tg: 221 ° C.) were used in the same manner as in Examples 1 and 2 and Comparative Examples 1 and 2, except that the pellets and the molded product were prepared in the same manner as in Examples 1 and 2. It was prepared and evaluated in various ways. The results are shown in Table 2.
  • Reference example 1 The powder of the polyether sulfone resin (B1) (“Sumika Excel 3600P” manufactured by Sumitomo Chemical Co., Ltd.) is melt-mixed using a laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a barrel temperature of 360 ° C. and a screw rotation speed of 150 rpm. It was smelted and extruded. The strands extruded from the extruder were air-cooled and then pelletized by a pelletizer (“Fan Cutter FC-Mini-4 / N” manufactured by Hoshi Plastic Co., Ltd.). The obtained pellets were dried at 160 ° C. for 6 hours and then used for injection molding.
  • B1 Sudika Excel 3600P” manufactured by Sumitomo Chemical Co., Ltd.
  • Reference example 2 Reference Example 1 except that the powder of the polyether sulfone resin (B2) (“Sumika Excel 4800P” manufactured by Sumitomo Chemical Co., Ltd.) was used instead of the powder of the polyether sulfone resin (B1) in Reference Example 1. Pellets and molded bodies were prepared in the same manner as in the above, and various evaluations were performed. The results are shown in Table 2.
  • Reference example 3 The powder of the polyimide resin 1 obtained in Production Example 1 was melt-kneaded and extruded using a laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a barrel temperature of 360 ° C. and a screw rotation speed of 150 rpm. The strands extruded from the extruder were air-cooled and then pelletized by a pelletizer (“Fan Cutter FC-Mini-4 / N” manufactured by Hoshi Plastic Co., Ltd.). The obtained pellets were dried at 150 ° C. for 12 hours and then used for injection molding.
  • the molded product made of the material includes Comparative Examples 1 and 2 in which the ratio of the polyimide resin (A1) and the polyether sulfone resin (B1) is out of the above range, Reference Example 1 consisting of only the polyether sulfone resin (B1), and polyimide.
  • the tensile fracture strain was improved as compared with the molded body of Reference Example 3 composed of only the resin (A1).
  • molding comprising the polyimide resin composition of Examples 3 to 5 containing the polyimide resin (A1) and the polyether sulfone resin (B2) in the range of 0.1 / 99.9 to 65/35 by mass ratio.
  • Comparative Examples 3 and 4 in which the ratio of the polyimide resin (A1) and the polyether sulfone resin (B2) is out of the above range, Reference Example 2 composed of only the polyether sulfone resin (B2), and the polyimide resin (A1). The tensile fracture strain was improved as compared with the molded body of Reference Example 3 consisting of only.
  • polyimide resin compositions of Examples 1 to 5 have higher L values and whiteness than the polyimide resin compositions of Comparative Examples and the resins of Reference Examples.
  • Example 1 the dispersed state of the polyimide resin (A1) and the polyether sulfone resin (B1) in each pellet was confirmed by the following method. ..
  • Each pellet was cut using a microtome ("ULTRACUT E” manufactured by REICHERT-JUNG LIMITED) in parallel with the flow direction (MD) of the pellet (that is, so as to have a TD cross section) as shown in FIG. Ultrathin sections were made.
  • 1 is a pellet and 2 is an ultrathin section.
  • an ultrathin section was prepared by the same method as described above using the pellet made of only the polyether sulfone resin (B1) obtained in Reference Example 1, and FE was not stained with ruthenium tetroxide. -The micrograph observed by STEM is shown in FIG.
  • the polyimide resin composition and the molded product of the present invention are excellent in heat resistance and bending characteristics and have high toughness, it is expected to be applied to applications in which impact resistance, vibration damping property, etc. are important.
  • sliding members such as gears and bearings, cutting members, structural members such as robot arms, winding coating materials such as electric wires, screws, nuts, packings, diaphragms for speakers, reflectors, 5th generation mobile communication systems (5G).
  • 5G mobile communication systems 5th generation mobile communication systems
  • 6G mobile communication system (6G) related members, various films, etc. can be applied.
  • it can be expected to be applied to a water treatment membrane or the like as an application similar to the polyether sulfone resin.

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