WO2023058334A1 - 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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WO2023058334A1
WO2023058334A1 PCT/JP2022/031146 JP2022031146W WO2023058334A1 WO 2023058334 A1 WO2023058334 A1 WO 2023058334A1 JP 2022031146 W JP2022031146 W JP 2022031146W WO 2023058334 A1 WO2023058334 A1 WO 2023058334A1
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Prior art keywords
polyimide resin
group
resin composition
formula
carbon atoms
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English (en)
French (fr)
Japanese (ja)
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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 EP22878205.8A priority Critical patent/EP4414423A4/en
Priority to JP2023552723A priority patent/JPWO2023058334A1/ja
Priority to US18/694,547 priority patent/US20240384097A1/en
Priority to KR1020247010911A priority patent/KR20240072166A/ko
Priority to CN202280066607.2A priority patent/CN118076699A/zh
Publication of WO2023058334A1 publication Critical patent/WO2023058334A1/ja
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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
    • C08G73/1042—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
    • 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
    • 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
    • C08G73/1075—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

Definitions

  • the present invention relates to polyimide resin compositions and molded articles.
  • polyimide resin Due to the rigidity of the molecular chain, resonance stabilization, and strong chemical bonding, polyimide resin is a useful engineering plastic with high thermal stability, high strength, and high solvent resistance, and is applied in a wide range of fields. Polyimide resins having crystallinity can further improve their heat resistance, strength and chemical resistance, and thus are expected to be used as metal substitutes. However, although the polyimide resin has high heat resistance, it does not show thermoplasticity and has a problem of low moldability.
  • Patent Document 1 As polyimide molding materials, highly heat-resistant resin Vespel (registered trademark) and the like are known (Patent Document 1). Since it is necessary to perform molding, it is also disadvantageous in terms of cost. On the other hand, a resin such as a crystalline resin that has a melting point and is fluid at high temperatures can be molded easily and inexpensively.
  • thermoplastic polyimide resins have been reported.
  • Thermoplastic polyimide resins are excellent in moldability in addition to the inherent heat resistance of polyimide resins. Therefore, thermoplastic polyimide resins can also be applied to moldings used in harsh environments where general-purpose thermoplastic resins such as nylon and polyester could not be applied.
  • Patent Document 2 a predetermined A thermoplastic polyimide resin is disclosed that contains a repeating unit of
  • Patent Document 3 discloses a thermoplastic polyimide resin containing a predetermined repeating unit, and also describes the use of the polyimide resin in combination with another resin as a polymer alloy.
  • thermoplastic polyimide resin described in Patent Document 3 has crystallinity and is excellent in heat resistance, strength, chemical resistance, etc., but depending on the application, a high level of dimensional stability in a wide temperature range is required. There was room for further improvement.
  • An object of the present invention is to provide a polyimide resin composition which has a low coefficient of linear thermal expansion and which can be used to form a molded article having excellent dimensional stability.
  • the present inventors have found that a polyimide resin composition containing a crystalline thermoplastic polyimide resin in which specific different polyimide structural units are combined in a specific ratio and an amorphous resin having a specific structure can solve the above problems. Found it. That is, the present invention relates to the following.
  • a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2) are included, and the sum of the repeating structural unit of the formula (1) and the repeating structural unit of the formula (2) Containing a polyimide resin (A) having a content ratio of 20 to 70 mol% of the repeating structural unit of the formula (1) and an amorphous resin (B) containing a repeating structural unit represented by the following formula (I) polyimide resin composition.
  • R 1 is a C 6-22 divalent group containing at least one alicyclic hydrocarbon structure.
  • R 2 is a C 5-16 divalent chain aliphatic group.
  • X 1 and X 2 are each independently a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring.) (R 4 is a single bond or a divalent group having 6 to 22 carbon atoms containing at least one aromatic ring.n is the number of repeating constituent units and is greater than 1.) [2] A molded article containing the polyimide resin composition according to [1] above.
  • the polyimide resin composition and molded article of the present invention have a low coefficient of linear thermal expansion and excellent dimensional stability, and therefore are suitable for, for example, films, copper-clad laminates, electrical and electronic members that require a low coefficient of thermal expansion. .
  • FIG. 2 is a schematic diagram showing a method of preparing a sample used for observation with a field emission scanning electron microscope (FE-SEM); 1 is a micrograph of a cross section of the polyimide resin composition (pellet) of Example 2 taken perpendicularly to the flow direction (MD) and observed by FE-SEM. 1 is a micrograph of a cross section of the polyimide resin composition (pellet) of Example 3 taken perpendicularly to the machine direction (MD) and observed by FE-SEM. 1 is a micrograph of a cross section cut perpendicular to the machine direction (MD) of the polyimide resin composition (pellet) of Example 5, observed by FE-SEM.
  • FE-SEM field emission scanning electron microscope
  • the polyimide resin composition of the present invention comprises a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2), wherein the repeating structural unit of the formula (1) and the formula (2) A polyimide resin (A) having a content ratio of 20 to 70 mol% of repeating structural units of the formula (1) with respect to the total repeating structural units of and an amorphous resin containing a repeating structural unit represented by the following formula (I) (B) and.
  • R 1 is a C 6-22 divalent group containing at least one alicyclic hydrocarbon structure.
  • R 2 is a C 5-16 divalent chain aliphatic group.
  • X 1 and X 2 are each independently a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring.) (R 4 is a single bond or a divalent group having 6 to 22 carbon atoms containing at least one aromatic ring.n is the number of repeating constituent units and is greater than 1.)
  • the polyimide resin composition of the present invention is a polyimide resin composition having a low coefficient of linear thermal expansion (hereinafter also referred to as “CTE”) and capable of producing a molded article having excellent dimensional stability.
  • CTE coefficient of linear thermal expansion
  • Component (A) is a crystalline resin
  • component (B) is an amorphous resin
  • component (B) has a sulfonyl group which is a polar group. Therefore, component (A) and component (B) are difficult to be mixed together even when melted and kneaded, but because of their high mutual dispersibility, they are mutually dispersed at the micro to nano level in the resulting resin composition and molded article.
  • a microphase separation structure such as a sea-island structure.
  • a compact in which component (A) or component (B) is finely dispersed at the micro to nano level is likely to disperse stress even when stress is applied. be done.
  • component (A) and component (B) are resins having relatively high heat resistance among thermoplastic resins, it is believed that higher dimensional stability can be maintained even in a high temperature range.
  • a molded article obtained by molding the polyimide resin composition of the present invention preferably has a microphase-separated structure from the viewpoint of achieving a lower CTE.
  • the microphase-separated structure is formed by phase separation of component (A) and component (B), and may be a sea-island structure or a co-continuous structure, but preferably a sea-island structure. In the sea-island structure, either component may form the "sea" depending on the mass ratio of component (A) and component (B) in the compact.
  • whether or not the molded body has a microphase-separated structure can be determined by observing the surface or cross section of the molded body with a scanning electron microscope (SEM).
  • ⁇ Hm 0 is the crystallization heat value of the component (A) alone and ⁇ Hm is the crystallization heat value of the molded body.
  • the heat of crystallization can be specifically measured by the method described in Examples.
  • 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 repeating structural unit of the formula (1) and the formula (
  • the content ratio of the repeating structural units of formula (1) to the total repeating structural units of 2) is 20 to 70 mol %.
  • R 1 is a C 6-22 divalent group containing at least one alicyclic hydrocarbon structure.
  • R 2 is a C 5-16 divalent chain aliphatic group.
  • X 1 and X 2 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 crystalline thermoplastic resin, and its form is preferably powder or pellets.
  • the thermoplastic polyimide resin is formed by closing the imide ring after molding in the state of a polyimide precursor such as polyamic acid, for example, a polyimide resin having no glass transition temperature (Tg), or a temperature lower than the glass transition temperature It is distinguished from polyimide resin that decomposes at
  • R 1 is a C 6-22 divalent group containing at least one alicyclic hydrocarbon structure.
  • the alicyclic hydrocarbon structure means a ring derived from an alicyclic hydrocarbon compound, and the alicyclic hydrocarbon compound may be saturated or unsaturated, and It may be cyclic or polycyclic.
  • Examples of the alicyclic hydrocarbon structure include, but are not limited to, cycloalkane rings such as cyclohexane ring, cycloalkene rings such as cyclohexene, bicycloalkane rings such as norbornane ring, and bicycloalkene rings such as norbornene. Do not mean.
  • 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.
  • R 1 has 6 to 22 carbon atoms, preferably 8 to 17 carbon atoms.
  • R 1 contains at least one, preferably 1 to 3, alicyclic hydrocarbon structures.
  • R 1 is preferably a divalent group represented by the following formula (R1-1) or (R1-2).
  • (m 11 and m 12 are each independently an integer of 0 to 2, preferably 0 or 1;
  • m 13 to m 15 are each independently 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 with respect to the cyclohexane ring may be cis or trans, and the ratio of cis to trans may be can be any value.
  • X 1 is a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring.
  • the aromatic ring may be a single ring or a condensed ring, and examples include, but are not limited to, benzene ring, naphthalene ring, anthracene ring, and tetracene ring. Among these, benzene ring and naphthalene ring are preferred, and benzene ring is more preferred.
  • X 1 has 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms.
  • X 1 contains at least one, preferably 1 to 3, aromatic rings.
  • X 1 is preferably a tetravalent group represented by any one of formulas (X-1) to (X-4) below.
  • 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, a carbonyl group or an alkylene group having 1 to 4 carbon atoms.) Since X 1 is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring, R 12 , R 13 , p 12 and p 13 in formula (X-2) are represented by formula (X- The number of carbon atoms in the tetravalent group represented by 2) is selected within the range of 10 to 22. Similarly, L 11 , R 14 , R 15 , p 14 and p 15 in formula (X-3) are in the range of 12 to 22 carbon atoms in the tetravalent group represented by formula (X-3).
  • L 12 , L 13 , R 16 , R 17 , R 18 , p 16 , p 17 and p 18 in formula (X-4) are selected to contain the tetravalent is selected so that the number of carbon atoms in the group is in the range of 18-22.
  • X 1 is particularly preferably a tetravalent group represented by the following formula (X-5) or (X-6).
  • 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, still more preferably 8 to 10 carbon atoms.
  • the chain aliphatic group means a group derived from a chain aliphatic compound, the chain aliphatic compound may be saturated or unsaturated, straight-chain It may be branched or branched.
  • R 2 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 most preferably an alkylene group having 8 to 10 carbon atoms. It is an alkylene group.
  • the alkylene group may be a straight-chain alkylene group or a branched alkylene group, but is preferably a straight-chain alkylene group.
  • R 2 is preferably at least one selected from the group consisting of octamethylene group and decamethylene group, and particularly preferably octamethylene group.
  • 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, the polyimide resin can be sufficiently crystallized even in a general injection molding cycle.
  • the content ratio is less than 20 mol %, moldability is deteriorated, and when it exceeds 70 mol %, crystallinity is deteriorated, resulting in deterioration of heat resistance.
  • 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 preferably 65 mol% or less, from the viewpoint of expressing high crystallinity.
  • the polyimide resin (A) The crystallinity of is increased, and a resin molding having more excellent heat resistance can be obtained.
  • the content ratio is preferably 25 mol% or more, more preferably 30 mol% or more, and still more preferably 32 mol% or more from the viewpoint of moldability, and is even more preferable from the viewpoint of expressing high crystallinity. is 35 mol % or less.
  • the total content ratio of the repeating structural units of the formula (1) and the repeating structural units of the formula (2) with respect to all repeating structural units constituting the polyimide resin (A) is preferably 50 to 100 mol%, more preferably 75 ⁇ 100 mol%, more preferably 80 to 100 mol%, still more preferably 85 to 100 mol%.
  • Polyimide resin (A) may further contain a repeating structural unit of the following formula (3).
  • the content ratio of the repeating structural unit of formula (3) to the sum of the repeating structural units of formula (1) and the repeating structural units of formula (2) is preferably 25 mol % or less.
  • the lower limit is not particularly limited as long as it exceeds 0 mol %.
  • the content ratio is preferably 5 mol% or more, more preferably 10 mol% or more, from the viewpoint of improving heat resistance, while maintaining crystallinity. From the standpoint of doing so, it is preferably 20 mol % or less, more preferably 15 mol % or less.
  • R 3 is a C 6-22 divalent group containing at least one aromatic ring.
  • X 3 is a C 6-22 tetravalent group containing at least one aromatic ring.
  • R 3 is a C 6-22 divalent group containing at least one aromatic ring.
  • the aromatic ring may be a single ring or a condensed ring, and examples include, but are not limited to, benzene ring, naphthalene ring, anthracene ring, and tetracene ring. Among these, benzene ring and naphthalene ring are preferred, and benzene ring is more preferred.
  • R 3 has 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms.
  • R 3 contains at least one, 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 each independently an integer of 0 to 2, preferably 0 or 1;
  • m 33 and m 34 are each independently an integer of 0 to 2, preferably 0 or 1.
  • R 21 , R 22 and R 23 are each 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 of 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 and containing at least one aromatic ring, m 31 , m 32 , R 21 and p 21 in formula (R3-1) are represented by formula (R3- It is selected so that the number of carbon atoms of the divalent group represented by 1) falls within the range of 6-22. Similarly, L 21 , m 33 , m 34 , R 22 , R 23 , p 22 and p 23 in formula (R3-2) have It is chosen to fall within the range of 12-22.
  • X3 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, it preferably has a chain aliphatic group having 5 to 14 carbon atoms at its terminal.
  • the chain aliphatic group may be saturated or unsaturated, linear or branched.
  • saturated chain aliphatic groups 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, n-undecyl group, Lauryl group, n-tridecyl group, n-tetradecyl group, isopentyl group, neopentyl group, 2-methylpentyl group, 2-methylhexyl group, 2-ethylpentyl group, 3-ethylpentyl group, isooctyl group, 2-ethylhexyl group , 3-ethylhexyl group, isononyl group, 2-ethyloctyl group, isodecyl group, isododecyl group, isotridecyl group, isotetradecyl group and the like.
  • Examples of unsaturated chain aliphatic groups having 5 to 14 carbon atoms include 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-hexenyl group, 1-heptenyl group, 2-heptenyl group, 1- octenyl group, 2-octenyl group, nonenyl group, decenyl group, dodecenyl group, tridecenyl group, tetradecenyl group and the like.
  • the chain aliphatic group is preferably a saturated chain aliphatic group, and more preferably a saturated straight chain 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 12 or less carbon atoms. has 10 or less carbon atoms, more preferably 9 or less carbon atoms. Only one type of chain aliphatic group may be used, or two or more types may be used.
  • the chain aliphatic group is particularly preferably at least one selected from the group consisting of n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, n-decyl group and isodecyl group. More preferably at least one selected from the group consisting of n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group and isononyl group, most preferably n-octyl group, isooctyl group and It is at least one selected from the group consisting of 2-ethylhexyl groups.
  • the polyimide resin (A) preferably has only chain aliphatic groups having 5 to 14 carbon atoms at its terminals in addition to terminal amino groups and terminal carboxy groups.
  • the content thereof is preferably 10 mol % or less, more preferably 5 mol % or less, relative to 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 100 in total of all repeating structural units constituting the polyimide resin (A). It is preferably 0.01 mol % or more, more preferably 0.1 mol % or more, and still more preferably 0.2 mol % or more based on mol %.
  • 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, still more preferably 3.5 mol% or less, even more preferably 2.0 mol% or less, more preferably 100 mol% or less of all repeating structural units More preferably, it is 1.2 mol % or less.
  • the content of the chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (A) can be obtained by depolymerizing the polyimide resin (A).
  • 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 preferably 280° C. or higher, more preferably 290° C. or higher, from the viewpoint of heat resistance, and is preferably 345° C. or lower, more preferably 345° C. or lower, from the viewpoint of achieving high moldability. is 340° C. or less, more preferably 335° C. or less.
  • 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. from the viewpoint of expressing high moldability.
  • the polyimide resin (A) is measured by a differential scanning calorimeter, and after melting the polyimide resin, it is cooled at a cooling rate of 20 ° C./min.
  • the heat quantity at the crystallization exothermic peak (hereinafter also simply referred to as “crystallization exothermic value”) observed when the It is preferably 17.0 mJ/mg or more, and more preferably 17.0 mJ/mg or more.
  • the upper limit of the crystallization heat value is not particularly limited, it is usually 45.0 mJ/mg or less.
  • the melting point, glass transition temperature, and crystallization heat value of the polyimide resin (A) can all be measured by a differential scanning calorimeter, and specifically by the methods 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, 000 to 70,000, 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 molded article obtained is good, and if it is 40,000 or more, the stability of the mechanical strength is good, It becomes easy to form the microphase-separated structure mentioned above, and a lower CTE can be achieved. Also, if it is 150,000 or less, moldability will be good.
  • the weight average molecular weight Mw of the polyimide resin (A) can be measured by a gel permeation chromatography (GPC) method using polymethyl methacrylate (PMMA) as a standard sample, and specifically can be measured by the method described in Examples. .
  • the logarithmic viscosity at 30° C. of a 5 mass % concentrated sulfuric acid solution of the polyimide resin (A) 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 times of concentrated sulfuric acid and the polyimide resin solution at 30° C. using a Canon Fenske viscometer.
  • ⁇ ln [(ts/t 0 )/C] t 0 : Flow time of concentrated sulfuric acid ts: Flow time of polyimide resin solution C: 0.5 (g/dL)
  • Polyimide resin (A) can be produced by reacting a tetracarboxylic acid component and a diamine component.
  • the tetracarboxylic acid component contains a tetracarboxylic acid and/or derivative thereof containing at least one aromatic ring
  • the diamine component contains a diamine containing at least one alicyclic hydrocarbon structure and a linear 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.
  • Examples of the tetracarboxylic acid include pyromellitic acid, 2,3,5,6-toluenetetracarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, and 3,3′,4,4′-biphenyl. Tetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid and the like are preferred. Among these, pyromellitic acid is more preferable.
  • 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 derivative preferably has 6 to 38 carbon atoms.
  • Anhydrides of tetracarboxylic acids include pyromellitic monoanhydride, pyromellitic dianhydride, 2,3,5,6-toluenetetracarboxylic dianhydride, 3,3′,4,4′-diphenyl sulfonetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride and the like are included.
  • alkyl esters of tetracarboxylic acids 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′-benzophenonetetracarboxylate dimethyl, 3,3′,4,4′-biphenyltetracarboxylate dimethyl, 1,4,5,8 -Naphthalenetetracarboxylate dimethyl and the like.
  • the alkyl group preferably has 1 to 3 carbon atoms.
  • At least one compound selected from the above may be used alone, or two or more compounds may be used in combination.
  • the diamine containing at least one alicyclic hydrocarbon structure preferably has 6 to 22 carbon atoms, such as 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, 4,4'-Diaminodicyclohexylpropane and the like are preferred.
  • 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 preferably has 5 to 16 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 7 to 12 carbon atoms. In addition, if the chain portion has 5 to 16 carbon atoms, an ether bond may be included therebetween.
  • Chain aliphatic diamines such as 1,5-pentamethylenediamine, 2-methylpentane-1,5-diamine, 3-methylpentane-1,5-diamine, 1,6-hexamethylenediamine, 1,7-hepta methylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-trideca Methylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine, 2,2'-(ethylenedioxy)bis(ethyleneamine) and the like are preferred.
  • Chain aliphatic diamines may be used singly or in combination. Among these, 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. Available.
  • the molar amount of the diamine charged containing at least one alicyclic hydrocarbon structure with respect to the total amount of the diamine containing at least one alicyclic hydrocarbon structure and the chain aliphatic diamine The ratio is preferably 20-70 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 expressing high crystallinity, preferably 60 mol% or less, more preferably 50 mol% or more.
  • 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, such as orthoxylylenediamine, metaxylylenediamine, paraxylylenediamine, 1,2-diethynylbenzenediamine, 1,3-diethynyl.
  • the molar ratio of the charged 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 25 mol% or less. It is preferably 20 mol % or less, still more preferably 15 mol % or less. Although the lower limit of the molar ratio is not particularly limited, it is preferably 5 mol % or more, more preferably 10 mol % or more, from the viewpoint of improving heat resistance.
  • the molar ratio is more preferably 12 mol% or less, even more preferably 10 mol% or less, even more preferably 5 mol% or less, and even more preferably 0 mol %.
  • the charged amount ratio of the tetracarboxylic acid component and 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.
  • a terminal blocking agent may be mixed in addition to the tetracarboxylic acid component and the diamine component.
  • the terminal blocking agent at least one selected from the group consisting of monoamines and dicarboxylic acids is preferable.
  • the amount of the terminal blocking agent to be used may be any amount that can introduce a desired amount of terminal groups into the polyimide resin (A), and is 0.0001 to 0.001 to 0.0001 to 0.001 per 1 mol of the tetracarboxylic acid and/or derivative thereof.
  • a monoamine terminal blocking agent is preferable as the terminal blocking agent, and from the viewpoint of improving heat aging resistance by introducing the chain aliphatic group having 5 to 14 carbon atoms described above at the end of the polyimide resin (A). , monoamines having a chain aliphatic group of 5 to 14 carbon atoms are more preferred, and monoamines having a saturated linear aliphatic group of 5 to 14 carbon atoms are even more preferred.
  • the terminal blocking 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. , more preferably at least one selected from the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, and isononylamine, most preferably n-octylamine, isooctylamine, and 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 composition of the present invention contains the polyimide resin (A) and an amorphous resin (B) containing a repeating structural unit represented by the following formula (I).
  • R 4 is a single bond or a divalent group having 6 to 22 carbon atoms containing at least one aromatic ring.n is the number of repeating constituent units and is greater than 1.
  • the polyimide resin composition of the present invention can produce a molded article with a low CTE. It should be noted that the amorphous resin (B) in the present invention does not contain a repeating structural unit having an imide bond.
  • the divalent group having 6 to 22 carbon atoms containing at least one aromatic ring in R 4 of formula (I) preferably contains an ether bond from the viewpoint of achieving a lower CTE. It is a divalent aromatic group of 6 to 22, more preferably a divalent group represented by any one of the following general formulas (a) to (c). (R 41 and R 42 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group having 1 to 4 carbon atoms in R 41 and R 42 includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. is mentioned. From the viewpoint of achieving a lower CTE, R 41 and R 42 are each independently preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, more preferably a hydrogen atom or a methyl group, More preferably, it is a methyl group.
  • R 4 in formula (I) is preferably a single bond or a divalent represented by any of the general formulas (a) to (c), from the viewpoint of achieving a lower CTE and reducing the water absorption rate. and more preferably a single bond or a divalent group represented by any one of the general formulas (b) and (c).
  • Component (B) more preferably contains a repeating structural unit represented by any one of the following formulas (I-1) to (I-3) from the viewpoint of achieving a lower CTE and reducing the water absorption rate.
  • Amorphous resin more preferably 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass of repeating structural units represented by any of the following formulas (I-1) to (I-3) It is an amorphous resin containing at least 90% by mass, more preferably at least 95% by mass, more preferably at least 95% by mass.
  • R 41 and R 42 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • n is the number of repeating constituent units, and is a number exceeding 1.
  • the alkyl group having 1 to 4 carbon atoms in R 41 and R 42 is the same as described above, and from the viewpoint of achieving a lower CTE, it is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. , more preferably a hydrogen atom or a methyl group, still more preferably a methyl group.
  • amorphous resin (B1) an amorphous resin containing a repeating structural unit represented by formula (I-1)
  • amorphous resin (B1) an amorphous resin containing a repeating structural unit represented by formula (I-2)
  • amorphous resin (B1) an amorphous resin containing a repeating structural unit represented by formula (I-2)
  • amorphous resin (B2) an amorphous resin containing a repeating structural unit represented by formula (I-3) is also referred to as "amorphous resin (B3)”.
  • the amorphous resin (B1) is an amorphous resin containing a repeating structural unit represented by the following formula (I-1). n is the number of repeating structural units and is a number exceeding one. More preferably, the amorphous resin (B1) includes a resin having a structure represented by the following formula (I-1a). (Wherein, R represents a terminal group and is Cl or OH. n is the same as above.) From the viewpoint of achieving a lower CTE, R in formula (I-1a) is preferably Cl.
  • the glass transition temperature of the amorphous resin (B1) is preferably 210° C. or higher, more preferably 215° C. or higher from the viewpoint of achieving a lower CTE, and preferably 280° C. or lower from the viewpoint of moldability. , more preferably 260° C. or less.
  • the glass transition temperature can be measured by a method similar to that described above.
  • the intrinsic viscosity of the amorphous resin (B1) at 25° C. is preferably 0.20 to 1.00 dL/g, more preferably 0.25 to 1.00 dL/g, more preferably 0.25 to 1.00 dL/g, from the viewpoint of achieving a lower CTE. It is preferably 0.30 to 0.80 dL/g.
  • the intrinsic viscosity of the amorphous resin (B1) can be measured by a method according to JIS K7367-5:2000, specifically by the method described in Examples.
  • the intrinsic viscosity is preferably within the above range when measured at 25° C. using a powder of the amorphous resin (B1) that has not been subjected to heat history such as melting.
  • the number average molecular weight (Mn) of the amorphous resin (B1) is preferably 2,000 to 25,000, more preferably 3,000 to 25,000, still more preferably 3, from the viewpoint of achieving a lower CTE. , 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 amorphous resin (B1) is preferably 5,000 to 80,000, more preferably 7,000 to 80,000, still more preferably 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 amorphous resin (B1) can be measured by gel permeation chromatography (GPC) using polymethyl methacrylate (PMMA) as a standard sample, and are specifically described in Examples. can be measured by the method of The number-average molecular weight and weight-average molecular weight are preferably within the above ranges when measured using a powder of the amorphous resin (B1) that has not been subjected to heat history such as melting.
  • the form of the amorphous resin (B1) is not particularly limited, and either powder or pellets can be used.
  • the morphology of the resulting resin composition and molded article may be different from when powder is used, resulting in mechanical properties of the obtained molded article. may differ.
  • the use of pellets as the amorphous resin (B1) tends to improve the toughness of the obtained molded body as compared with the use of powder.
  • powder is more preferable.
  • a commercially available product can also be used as the amorphous resin (B1).
  • B1 Sumitomo Chemical Co., Ltd. "Sumika Excel PES” series (3600P, 4100P, 4800P, 5200P, 5400P, 5900P, 7600P, 5003P, 5003MPS, 3600G, 4100G, 4800G) , BASF "Ultrazone E” series (E1010, E2010, E2020P, E3010, E6020P) and the like.
  • the amorphous resin (B2) is an amorphous resin containing a repeating structural unit represented by the following formula (I-2), more preferably an amorphous resin represented by the following formula (I-2). .
  • n is the number of repeating structural units and is a number exceeding one.
  • the glass transition temperature of the amorphous resin (B2) is preferably 170° C. or higher, more preferably 180° C. or higher from the viewpoint of achieving a lower CTE, and preferably 230° C. or lower from the viewpoint of moldability. is.
  • the glass transition temperature can be measured by a method similar to that described above.
  • the intrinsic viscosity of the amorphous resin (B2) at 25° C. is preferably 0.20 to 1.00 dL/g, more preferably 0.25 to 1.00 dL/g, and further It is preferably 0.30 to 0.80 dL/g.
  • the intrinsic viscosity of the amorphous resin (B2) can be measured by the same method as described above.
  • a commercially available product can also be used as the amorphous resin (B2).
  • amorphous resins (B2) include "Ultrason S” series (S2010, S3010, S6010) manufactured by BASF, represented by formula (I-2).
  • the amorphous resin (B3) is an amorphous resin containing a repeating structural unit represented by the following formula (I-3), more preferably an amorphous resin represented by the following formula (I-3).
  • R 41 and R 42 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is the number of repeating constituent units, and is a number exceeding 1.
  • the alkyl group having 1 to 4 carbon atoms in R 41 and R 42 is the same as described above, and from the viewpoint of achieving a lower CTE, it is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.
  • the amorphous resin (B3) is more preferably an amorphous resin containing a repeating structural unit represented by the following formula (I-3c), more preferably an amorphous resin represented by the following formula (I-3c): It is a crystalline resin.
  • n is the number of repeating structural units and is a number exceeding one.
  • the glass transition temperature of the amorphous resin (B3) is preferably 190° C. or higher, more preferably 200° C. or higher from the viewpoint of achieving a lower CTE, and preferably 230° C. or lower from the viewpoint of moldability. is.
  • the glass transition temperature can be measured by a method similar to that described above.
  • a commercially available product can also be used as the amorphous resin (B3).
  • amorphous resins (B3) include "Ultrason P” series (P3010) manufactured by BASF, represented by formula (I-3c).
  • Component (B) can be used alone or in combination of two or more.
  • the component (B) is more preferably the group consisting of the amorphous resin (B2) and the amorphous resin (B3) from the viewpoint of achieving a lower CTE and reducing the water absorption rate. and more preferably one selected from the group consisting of the amorphous resin represented by the formula (I-2) and the amorphous resin represented by the formula (I-3c) more than seeds.
  • the mass ratio of component (A) to the total mass of component (A) and component (B) in the polyimide resin composition [(A) / ⁇ (A) + (B) ⁇ ] obtains the effects of the present invention From the viewpoint, it is preferably 0.01 or more and 0.99 or less.
  • the 0.50 or more, still more preferably 0.60 or more, and from the viewpoint of achieving a lower CTE it is more preferably 0.90 or less, still more preferably 0.80 or less, and even more preferably 0.75 or less. be.
  • the component (B) is an amorphous resin (B1) containing a repeating structural unit represented by the formula (I-1)
  • the total mass of the component (A) and the component (B1) in the polyimide resin composition The mass ratio [(A)/ ⁇ (A)+(B1) ⁇ ] of the component (A) to the 99 or less, more preferably more than 0.65 and 0.95 or less, still more preferably 0.70 or more and 0.90 or less.
  • the total content of the polyimide resin (A) and the amorphous 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 effects of the present invention. It is preferably 80% by mass or more, and more preferably 90% by mass or more. Moreover, an upper limit is 100 mass %.
  • the polyimide resin composition of the present invention contains a filler, a reinforcing fiber, a matting agent, a nucleating agent, a plasticizer, an antistatic agent, an anti-coloring agent, an anti-gelling agent, a flame retardant, a coloring agent, a slidability improver, Additives such as antioxidants, ultraviolet absorbers, conductive agents, and resin modifiers may be contained as necessary.
  • the content of the additive is not particularly limited, but from the viewpoint of expressing the effect of the additive while maintaining the physical properties derived from the polyimide resin (A) and the amorphous resin (B), the polyimide resin composition , usually 50% by mass or less, preferably 0.0001 to 30% by mass, more preferably 0.0001 to 15% by mass, still more preferably 0.001 to 10% by mass.
  • the polyimide resin composition of the present invention can take any form, pellets are preferred. Since the polyimide resin (A) and the amorphous resin (B) have thermoplasticity, for example, the polyimide resin (A), the amorphous resin (B), and optionally various optional components are melt-kneaded in an extruder. The strands can be extruded with a tumbler and pelletized by cutting the strands. Further, by introducing the obtained pellets into various molding machines and thermoforming them by the method described below, a molded article having a desired shape can be easily produced.
  • 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, still more preferably 180 ° C. or higher, and still more preferably 200 ° C. or higher. From the viewpoint of exhibiting moldability, the temperature is preferably 250° C. or lower, more preferably 240° C. or lower, and even more preferably 230° C. or lower.
  • the glass transition temperature can be measured by a method similar to that described above.
  • a low CTE molded article can be produced.
  • the molded article used for CTE measurement is preferably a non-stretched molded article, more preferably an injection molded article.
  • Injection-molded articles also have a machine direction (MD) and a direction perpendicular to it (TD), and the MD and TD may have different CTEs.
  • MD machine direction
  • TD direction perpendicular to it
  • the linear thermal expansion coefficient of at least one of MD and TD is preferably 60 ppm/°C or less, more preferably both MD and TD are 60 ppm/°C or less.
  • the coefficient of linear thermal expansion which is lower among MD and TD, is more preferably 55 ppm/°C or less, more preferably 50 ppm/°C. Below, more preferably 45 ppm/°C or less, still more preferably 40 ppm/°C or less, and even more preferably 35 ppm/°C or less.
  • the total value of the linear thermal expansion coefficients of MD and TD is preferably 100 ppm/° C. or less, more preferably 95 ppm/° C. or less. , and more preferably 90 ppm/°C or less.
  • the thermal linear expansion coefficient of the molded article is a value measured in compression mode by thermomechanical analysis (TMA method), and can be specifically measured by the method described in Examples.
  • a molded article with low water absorption can be produced.
  • the water absorption rate when immersed in water at 23 ° C. for 24 hours, measured in accordance with JIS K7209: 2000, of a molded body of 30 mm ⁇ 20 mm ⁇ thickness 4 mm obtained by molding a polyimide resin composition preferably 0.30% or less, more preferably 0.25% or less, and still more preferably 0.20% or less.
  • the water absorption rate is obtained from the following formula when the mass of the molded article before immersion in water is (W 0 ) and the mass of the molded article after immersion in water at 23° C. for 24 hours is (W 1 ). It is a calculated value.
  • Water absorption (%) [(W 1 -W 0 )/W 0 ] x 100 Specifically, the water absorption can be measured by the method described in Examples.
  • the present invention provides a molded article containing the polyimide resin composition. Since the polyimide resin composition of the present invention has thermoplasticity, the molded article of the present invention can be easily produced by thermoforming.
  • Thermoforming methods include injection molding, extrusion molding, blow molding, hot press molding, vacuum molding, pressure molding, laser molding, welding, welding, etc. Any molding method involving a heat melting process can be used. is possible.
  • the molding temperature varies depending on the thermal properties (melting point and glass transition temperature) of the polyimide resin composition. 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 less.
  • a method for producing a molded article preferably includes a step of thermoforming the polyimide resin composition at a temperature of less than 400°C.
  • Specific procedures include, for example, the following method. First, the polyimide resin (A), the amorphous resin (B), and optionally various optional components are added and dry blended, and then introduced into an extruder, preferably melted at less than 400 ° C. The mixture is then melt-kneaded and extruded in an extruder to produce pellets. Alternatively, the polyimide resin (A) is introduced into the extruder, preferably melted at less than 400 ° C., and the amorphous resin (B) and various optional components are introduced into the extruder with the polyimide resin (A).
  • the aforementioned pellets may be produced by melt-kneading and extrusion. After drying the pellets, they can be introduced into various molding machines and thermoformed preferably at a temperature of less than 400° C. to produce a molded body having a desired shape.
  • the molded article of the present invention has a low coefficient of linear thermal expansion, excellent dimensional stability, and low water absorption. Therefore, it is suitable for, for example, films, copper-clad laminates, electrical and electronic members that require a low coefficient of thermal expansion. is.
  • IR measurement ⁇ Infrared spectroscopic analysis (IR measurement)>
  • the IR measurement of the polyimide resin was performed using "JIR-WINSPEC50" manufactured by JEOL Ltd.
  • the melting point Tm of the polyimide resin, and the glass transition temperature Tg, crystallization temperature Tc, and crystallization heat value ⁇ Hm of the polyimide resin, amorphous resin, and polyimide resin composition were measured using a differential scanning calorimeter (SII Nanotechnology ( Measured using a "DSC-6220" manufactured by Co., Ltd.).
  • the crystallization temperature Tc the resin powder for the polyimide resin and the amorphous resin (B1), the amorphous resin (B2), the amorphous resin (B3), and the pellet for the polyimide resin composition were used as measurement samples.
  • the measurement sample was subjected to thermal history under the following conditions.
  • the thermal history conditions were a first temperature increase (temperature increase rate of 10° C./min), then cooling (temperature decrease rate of 20° C./min), and then a second temperature increase (temperature increase rate of 10° C./min).
  • the melting point Tm was determined by reading the peak top value of the endothermic peak observed the second time the temperature was raised.
  • the glass transition temperature Tg was determined by reading the value observed at 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 crystallization heat 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 performing a rapid cooling operation at a cooling rate of 70 ° C./min, the peak top from the appearance of the observed crystallization peak. Calculate the time it took to reach In addition, in Table 1, when the semi-crystallization time was 20 seconds or less, it was described as " ⁇ 20".
  • the weight-average molecular weight (Mw) of the polyimide resin, the weight-average molecular weight and number-average molecular weight of the amorphous resin (B1) were measured using a gel permeation chromatography (GPC) measuring device "Shodex GPC-101" manufactured by Showa Denko Co., Ltd. was used and measured under the following conditions.
  • GPC gel permeation chromatography
  • ⁇ Intrinsic viscosity [ ⁇ ]> The intrinsic viscosities of the amorphous resins (B1) and (B2) were measured according to JIS K7367-5:2000 by the following method. As measurement samples, powder of the amorphous resin (B1) and pellets of the amorphous resin (B2) were used. N,N-dimethylformamide solutions of measurement samples 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 in a constant temperature bath at 25 ⁇ 0.05° C. using an Ubbelote viscometer (No. 0B), and the reduced viscosity (unit: dL/g) was calculated from the average value.
  • the concentration (g / dL) of the measurement sample is plotted on the horizontal axis and the reduced viscosity (dL / g) is plotted on the vertical axis to draw a calibration curve, and the viscosity value extrapolated to a concentration of 0 g / dL is the intrinsic viscosity (unit: dL / g).
  • the polyimide resin of Production Example 1 the amorphous resin, or the polyimide resin composition produced in each example, an injection molded body was produced by the method described later, and cut into a size of 30 mm ⁇ 20 mm ⁇ 4 mm in thickness. This was conditioned in an environment of 23° C. and relative humidity of 50% for 24 hours or longer before being used for measurement. After the molded article was dried in a hot air circulation oven at 50°C for 24 hours, it was returned to room temperature in a desiccator, and the mass (W 0 ) was measured under an environment of 23°C and a relative humidity of 50%.
  • CTE ⁇ Coefficient of thermal expansion
  • JIS K7197:2012 JIS K7197:2012.
  • a thermomechanical analyzer "TMA7100C” manufactured by Hitachi High-Tech Science Co., Ltd. was used in a nitrogen stream (150 mL/min) in compression mode with a load of 49 mN and a heating rate of 5 ° C./min.
  • the TMA measurement was performed by raising the temperature from 23 to 300° C. under the conditions of .
  • the TMA measurement was performed in the machine direction (MD) and the direction (TD) perpendicular to the machine direction (MD) of the injection molded product, and the CTE was obtained from the measured values at 23 to 220°C.
  • Production Example 1 (Production of Polyimide Resin 1)
  • a 2 L separable flask equipped with a Dean-Stark apparatus, a Liebig condenser, a thermocouple, and four paddle blades 500 g of 2-(2-methoxyethoxy) ethanol (manufactured by Nippon Nyukazai Co., Ltd.) and pyromellitic dianhydride ( 218.12 g (1.00 mol) of Mitsubishi Gas Chemical Co., Ltd.) was introduced, and after nitrogen flow, the mixture was stirred at 150 rpm to form a uniform suspension.
  • 1,8- A mixed diamine solution was prepared by dissolving 93.77 g (0.65 mol) of octamethylenediamine (manufactured by Kanto Chemical Co., Ltd.) in 250 g of 2-(2-methoxyethoxy)ethanol. The mixed diamine solution was added slowly using a plunger pump. Heat was generated by the dropwise addition, but the internal temperature was adjusted to be within the range of 40 to 80°C.
  • polyimide resin 1 In the process of increasing the temperature, precipitation of polyimide resin powder and dehydration due to imidization were confirmed when the liquid temperature was 120 to 140°C. After holding at 190° C. for 30 minutes, the mixture was allowed to cool to room temperature and filtered. The obtained polyimide resin powder was washed with 300 g of 2-(2-methoxyethoxy)ethanol and 300 g of methanol, filtered, and then dried in a dryer at 180° C. for 10 hours to obtain 317 g of crystalline thermoplastic polyimide resin 1. (hereinafter also simply referred to as "polyimide resin 1”) was obtained.
  • Table 1 shows the composition and evaluation results of polyimide resin 1 in Production Example 1.
  • the mol % of the tetracarboxylic acid component and the diamine component in Table 1 are values calculated from the amount of each component charged during the production of the polyimide resin.
  • amorphous resin B1
  • Examples 2 to 5 polyimide resin composition, production and evaluation of molded body
  • An injection molded body was produced in the same manner as in Example 1, except that the polyimide resin 1 powder obtained in Production Example 1 and the amorphous resin (B) were used in the proportions shown in Table 2. Various evaluations were performed. Table 2 shows the results. A powder was used for the amorphous resin (B1), and pellets were used for the amorphous resins (B2) and (B3).
  • Comparative example 1 ⁇ Preparation of injection molded body>
  • the polyimide resin 1 powder obtained in Production Example 1 was melt-kneaded and extruded using Laboplastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a barrel temperature of 360° C. and a screw rotation speed of 150 rpm. After the strand extruded from the extruder was air-cooled, it was pelletized by a pelletizer ("Fan Cutter FC-Mini-4/N" manufactured by Hoshi Plastics Co., Ltd.). The obtained pellets were dried at 150° C. for 12 hours and then used for injection molding.
  • injection molding is performed with a barrel temperature of 350°C, a mold temperature of 200°C, and a molding cycle of 50 seconds. A molded body for water absorption and CTE measurement was produced. Various evaluations were performed by the methods described above using the obtained injection molded article. Table 2 shows the results.
  • Comparative example 2 ⁇ Preparation of injection molded body> A powder of amorphous resin (B1) ("Sumika Excel 3600P” manufactured by Sumitomo Chemical Co., Ltd.) was melted and mixed using a Laboplastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a barrel temperature of 360 ° C. and a screw rotation speed of 150 rpm. smelted and extruded. After the strand extruded from the extruder was air-cooled, it was pelletized by a pelletizer ("Fan Cutter FC-Mini-4/N" manufactured by Hoshi Plastics Co., Ltd.). The obtained pellets were dried at 160° C. for 6 hours and then used for injection molding.
  • injection molding is performed with a barrel temperature of 350°C, a mold temperature of 180°C, and a molding cycle of 60 seconds.
  • a molded body for water absorption and CTE measurement was produced.
  • Various evaluations were performed by the methods described above using the obtained injection molded article. Table 2 shows the results.
  • Comparative example 3 ⁇ Preparation of injection molded body> Pellets of amorphous resin (B2) ("Ultrason S2010" manufactured by BASF) are molded using an injection molding machine ("ROBOSHOT ⁇ -S30iA” manufactured by Fanuc Corporation) at a barrel temperature of 370°C and a mold temperature of Injection molding was performed at 160° C. and a molding cycle of 60 seconds, and a predetermined size was cut out to prepare a molded body for water absorption and CTE measurement. Various evaluations were performed by the methods described above using the obtained injection molded article. Table 2 shows the results.
  • B2 amorphous resin
  • ROBOSHOT ⁇ -S30iA manufactured by Fanuc Corporation
  • Comparative example 4 ⁇ Preparation of injection molded body> Pellets of amorphous resin (B3) ("Ultrason P3010" manufactured by BASF) were molded using an injection molding machine ("ROBOSHOT ⁇ -S30iA” manufactured by Fanuc Corporation) at a barrel temperature of 370°C and a mold temperature of Injection molding was performed at 160° C. and a molding cycle of 60 seconds, and a predetermined size was cut out to prepare a molded body for water absorption and CTE measurement. Various evaluations were performed by the methods described above using the obtained injection molded article. Table 2 shows the results.
  • B3 amorphous resin
  • ROBOSHOT ⁇ -S30iA manufactured by Fanuc Corporation
  • the molded bodies made of the polyimide resin composition of the present invention have a lower linear thermal expansion coefficient than the molded bodies of Comparative Examples 1 to 4 and excellent dimensional stability. It can be seen that the water absorption rate is also low. Further, in Examples 1 to 5, the difference between the measured value of crystallization exotherm ⁇ Hm and the value of “ ⁇ Hm 0 ⁇ mass ratio of component (A)” was within ⁇ 30%. It can be inferred that the compact of has a microphase-separated structure.
  • each pellet was cut perpendicularly to the flow direction (MD) of the pellet 1 as shown in FIG. 1 (that is, so that a TD cross section appears) using a microtome ("EM UC 7" manufactured by LEICA MICROSYSTEMS). After staining this cut surface with ruthenium tetroxide for 30 minutes in the gas phase, a field emission scanning electron microscope (FE-SEM, "GeminiSEM500” manufactured by ZEISS) was used at an acceleration voltage of 1 kV and an observation magnification of 3000 times. observed (Figs. 2-4).
  • FE-SEM field emission scanning electron microscope
  • the polyimide resin composition and molded article of the present invention have a low coefficient of linear thermal expansion and excellent dimensional stability, and therefore are suitable for, for example, films, copper-clad laminates, electrical and electronic members that require a low coefficient of thermal expansion. .

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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)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2022/031146 2021-10-05 2022-08-18 ポリイミド樹脂組成物及び成形体 Ceased WO2023058334A1 (ja)

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EP22878205.8A EP4414423A4 (en) 2021-10-05 2022-08-18 POLYIMIDE RESIN COMPOSITION AND MOLDED BODIES
JP2023552723A JPWO2023058334A1 (https=) 2021-10-05 2022-08-18
US18/694,547 US20240384097A1 (en) 2021-10-05 2022-08-18 Polyimide resin composition and molded body
KR1020247010911A KR20240072166A (ko) 2021-10-05 2022-08-18 폴리이미드 수지 조성물 및 성형체
CN202280066607.2A CN118076699A (zh) 2021-10-05 2022-08-18 聚酰亚胺树脂组合物和成型体

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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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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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WO2019220969A1 (ja) * 2018-05-17 2019-11-21 三菱瓦斯化学株式会社 樹脂成形体
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US20240384097A1 (en) 2024-11-21
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