WO2022270375A1 - Composition - Google Patents

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Publication number
WO2022270375A1
WO2022270375A1 PCT/JP2022/023930 JP2022023930W WO2022270375A1 WO 2022270375 A1 WO2022270375 A1 WO 2022270375A1 JP 2022023930 W JP2022023930 W JP 2022023930W WO 2022270375 A1 WO2022270375 A1 WO 2022270375A1
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polymer
group
film
mass
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PCT/JP2022/023930
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English (en)
Japanese (ja)
Inventor
洋行 塚田
勇輔 小沼
宏司 西岡
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住友化学株式会社
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Publication of WO2022270375A1 publication Critical patent/WO2022270375A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; 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 composition capable of forming a film that can be used as a substrate material compatible with high-frequency band printed circuit boards and antenna substrates, and the film.
  • a copper-clad laminate called CCL has a structure in which copper foils are laminated on both surfaces of a resin layer via an adhesive. Since the transmission loss of the CCL can be suppressed by reducing the dielectric loss, particularly the dielectric loss tangent and the dielectric constant of the resin layer that serves as the transmission path, films with a low dielectric loss tangent are being studied.
  • Patent Document 1 discloses a low dielectric resin composition containing a resin (A) such as a polyimide resin and a cyclic olefin (co)polymer (B), and a film having a low dielectric loss tangent formed from the composition. is disclosed.
  • a resin (A) such as a polyimide resin and a cyclic olefin (co)polymer (B)
  • an object of the present invention is to provide a composition capable of forming a film with excellent moisture absorption resistance and the film.
  • the present inventors arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention includes the following preferred embodiments.
  • the phenolic antioxidant has the formula (P): [In formula (P), R p , R q , R r and R s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms, and * represents a bond] wherein the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom has an aromatic ring which may have a substituent.
  • composition according to [1] or [2], wherein the aromatic ring is a monocyclic aromatic hydrocarbon ring having 6 to 15 carbon atoms.
  • the polymer (B) is particulate.
  • the polymer (B) is at least one polymer selected from the group consisting of olefin-based polymers, polyimide-based polymers, fluorine-based polymers, silicone-based polymers, liquid-crystal polymers, aramid polymers, styrene-based polymers, and ether-based polymers.
  • [8] The composition according to any one of [1] to [7], wherein the polymer (B) is a cycloolefin polymer.
  • the cycloolefin-based polymer has the formula (I): [In formula (I), m represents an integer of 0 or more, R 7 to R 18 each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 11 to R When there are a plurality of 14 , they may be the same or different, and R 16 and R 17 may be bonded to each other to form a ring together with the carbon atom to which they are bonded.]
  • the content of the monomer unit (I) in the cycloolefin-based polymer is 60 mol% or more relative to the total molar amount of repeating units constituting the cycloolefin-based polymer, according to [9].
  • composition [11] containing a polyimide resin (A), a polymer (B) and a phenolic antioxidant,
  • the phenolic antioxidant has the formula (P): [In formula (P), R p , R q , R r and R s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms, and * represents a bond]
  • a film wherein the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom has an aromatic ring which may have a substituent.
  • a composition capable of forming a film with excellent moisture absorption resistance and the film can be provided.
  • the composition of the present invention comprises a polyimide resin (A), a polymer (B) and a phenolic antioxidant, wherein the phenolic antioxidant has the formula (P): [In the formula (P), R p , R q , R r and R s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms, and * represents a bond] Including a substituent P (sometimes referred to as a phenolic active site) represented by the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom is an aromatic that may have a substituent has a ring.
  • a substituent P (sometimes referred to as a phenolic active site) represented by the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom is an aromatic that may have a substituent has a ring.
  • the "film formed from the composition” may be simply referred to as "film”.
  • the dielectric property means a property related to dielectric including dielectric loss, relative permittivity and dielectric loss tangent. It shows that the dielectric loss tangent is reduced.
  • the present inventors have investigated the moisture absorption resistance of a film formed from a composition containing a polyimide resin (A), a polymer (B), and a solvent, and found that during film formation of the composition, for example, at high temperature It has been found that the polymer (B) is oxidized during the heat treatment of No. 2, resulting in the generation of polar groups, which may reduce the moisture absorption resistance of the film formed from the composition. Therefore, the present inventors focused on the oxidation of the polymer (B) and proceeded with further studies. It has been found that the use of a specific phenolic antioxidant possessed can effectively suppress the oxidation of the polymer (B) during film formation and improve the hygroscopic resistance of the formed film. Therefore, the composition of the present invention can form films having excellent resistance to moisture absorption.
  • the composition of the present invention comprises a phenolic antioxidant, said phenolic antioxidant having the formula (P): [In formula (P), R p , R q , R r and R s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms, and * represents a bond]
  • the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom is an aromatic ring optionally having a substituent (sometimes referred to as a substituent Q) (where the aromatic ring is different from the substituent P).
  • the phenol-based antioxidant has the above aromatic ring as structure S, oxidation during film formation of the polymer (B) contained in the composition of the present invention and the formation of polar groups due to this can be effectively suppressed. A film with excellent hygroscopicity can be formed. Furthermore, even when the resulting film is exposed to a high-temperature environment, deterioration due to oxidation of the polymer (B) can be effectively suppressed, and excellent heat resistance can be exhibited. Although the reason for this is not clear, when the structure S excluding the phenolic active site has an aromatic ring which may have a substituent, in addition to improving the heat resistance of the antioxidant itself, It is presumed that this is because the affinity increases.
  • R p , R q , R r and R s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms.
  • alkyl groups having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Neopentyl group, n-hexyl group, n-octyl group, tert-amyl group and the like.
  • the cycloalkyl group having 5 to 12 carbon atoms include cyclopentyl group, cyclohexyl group, cyclohexylmethyl group and the like.
  • R p , R q , R r and R s are at least R p , R q , R r and R s from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the film.
  • one is not a hydrogen atom, more preferably one of R p and R q is not a hydrogen atom, still more preferably at least one of R p , R q , R r and R s is a bulky substituent and more preferably at least one of R p and R q is a bulky substituent, and particularly preferably both R p and R q are a bulky substituent.
  • the bulky substituent may be a tert-butyl group, a neopentyl group, a tert-amyl group, etc., preferably a tert-butyl group.
  • the structures of the substituents P may be the same or different. That is, when there are multiple substituents P, R p , R q , R r and R s in each substituent P may be the same or different.
  • R p and R q When at least one of R p and R q is not a hydrogen atom, preferably at least one of R p and R q is a bulky substituent, it reacts with unstable radicals such as carbon radicals and peroxy radicals, When converted to phenoxy radicals, the phenoxy radicals are further stabilized, so that the oxidation of the polymer (B) is easily suppressed, and the hygroscopic resistance and heat resistance of the obtained film are easily improved.
  • unstable radicals such as carbon radicals and peroxy radicals
  • the structure S in which the substituent P is substituted with a hydrogen atom has an aromatic ring that may have a substituent.
  • the aromatic ring is different from the substituent P.
  • the aromatic ring is preferably an aromatic ring having 5 to 20 carbon atoms.
  • Aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles.
  • aromatic hydrocarbon rings examples include monocyclic aromatic hydrocarbon rings, condensed polycyclic aromatic hydrocarbon rings, and ring-assembled aromatic hydrocarbon rings.
  • the monocyclic aromatic hydrocarbon ring is preferably a monocyclic aromatic hydrocarbon ring having 6 to 15 carbon atoms, examples of which include a benzene ring.
  • the condensed polycyclic aromatic hydrocarbon ring is preferably a condensed polycyclic aromatic hydrocarbon ring having 10 to 20 carbon atoms, examples of which include naphthalene ring, anthracene ring, phenanthrene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.
  • the ring-assembled aromatic hydrocarbon ring is two or more monocyclic aromatic hydrocarbon rings, two or more condensed polycyclic aromatic hydrocarbon rings, or one or more monocyclic aromatic hydrocarbon rings and one or more and the condensed polycyclic aromatic hydrocarbon rings of are bonded to each other via a single bond, and ring-assembled aromatic hydrocarbon rings having 10 to 40 carbon atoms are preferred. Examples thereof include biphenyl ring, phenylnaphthyl ring, terphenyl ring, perylene ring and the like.
  • a benzene ring, a naphthalene ring, a biphenyl ring and the like are preferable, and a benzene ring is more preferable, from the viewpoint of easily increasing the hygroscopic resistance and heat resistance of the film.
  • aromatic heterocycles examples include monocyclic aromatic heterocycles, condensed polycyclic aromatic heterocycles, and ring-assembled aromatic heterocycles.
  • the aromatic heterocycle also includes rings having tautomers, and even if the ring itself has no aromaticity, if the tautomers have aromaticity, the term " included in "aromatic heterocycle".
  • the isocyanuric ring s-triazine-2,4,6-trione ring
  • is s-triazine-2,4,6-triol which has an aromatic tautomer.
  • the monocyclic aromatic heterocycle contains at least one heteroatom selected from a sulfur atom, a nitrogen atom and an oxygen atom, and is preferably an aromatic heterocycle having 5 to 15 carbon atoms and heteroatoms, examples of which include: pyrrole ring, pyrazole ring, imidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, isocyanuric ring, diazabenzene ring, furan ring, thiophene ring, azole ring, diazole ring, triazole ring, oxazole ring, oxazi An azole ring, a thiadiazole ring, and the like can be mentioned.
  • the condensed polycyclic aromatic heterocycle contains at least one heteroatom selected from a sulfur atom, a nitrogen atom and an oxygen atom, and is preferably a condensed polycyclic aromatic heterocycle having 8 to 20 carbon atoms and heteroatoms, Examples thereof include azanaphthalene (quinoline) ring, diazanaphthalene ring, carbazole ring, dibenzofuran ring, dibenzothiophene ring, dibenzosilole ring, phenoxazine ring, phenothiazine ring, acridine ring, indole ring, pyrroloimidazole ring, pyrrolopyrazole ring.
  • azanaphthalene (quinoline) ring diazanaphthalene ring
  • carbazole ring dibenzofuran ring
  • dibenzothiophene ring dibenzosilole ring
  • phenoxazine ring phenothia
  • pyrrolopyrrole ring thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, thiazole ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanth Lysine ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like.
  • Ring-assembled aromatic heterocycles are two or more monocyclic aromatic heterocycles, two or more condensed polycyclic aromatic heterocycles, one or more monocyclic aromatic heterocycles and one or more condensed polycyclic aromatic rings. and one or more monocyclic aromatic hydrocarbon rings and one or more condensed polycyclic aromatic heterocycles, or one or more monocyclic rings It also includes those in which the formula aromatic heterocycle and one or more condensed polycyclic aromatic hydrocarbon rings are bonded to each other through a single bond.
  • the ring-assembled aromatic heterocycle is preferably a ring-assembled aromatic heterocycle having 10 to 40 carbon atoms, and examples thereof include bipyridine ring, terpyridine ring and the like.
  • a triazine ring, an isocyanuric ring, and the like are preferable, and a triazine ring is more preferable, from the viewpoint of easily increasing the hygroscopic resistance and heat resistance of the film.
  • the structure S in the phenolic antioxidant may have one or more aromatic rings different from the substituent P.
  • the aromatic ring may have a structure different from that of the substituent P, and may have a substituent other than the substituent P.
  • Each aromatic ring may be linked by a divalent or higher valent hydrocarbon group, more preferably a divalent or trivalent hydrocarbon group, still more preferably an alkylene group.
  • Examples of the alkylene group include groups obtained by removing one hydrogen atom from the above-exemplified alkyl groups having 1 to 12 carbon atoms.
  • a carbon atom in the alkylene may be replaced with at least one selected from a sulfur atom, a nitrogen atom and an oxygen atom.
  • aromatic hydrocarbon rings are preferable from the viewpoint of facilitating the enhancement of dielectric properties in addition to the hygroscopic resistance and heat resistance of the film.
  • a cyclic aromatic hydrocarbon ring and/or a condensed polycyclic aromatic hydrocarbon ring is more preferable, a monocyclic aromatic hydrocarbon ring is more preferable, and a benzene ring is particularly preferable.
  • Examples of the substituent Q that the aromatic ring may have include a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an alkylamino group, a cycloalkylamino group, an acyl group, and a mercapto group. , an amino group, a hydroxyl group, a group having an ester bond, and the like. These substituents Q can be used alone or in combination of two or more.
  • the halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
  • the alkyl group includes, for example, the above-exemplified alkyl groups having 1 to 12 carbon atoms.
  • the cycloalkyl group includes, for example, the above-exemplified cycloalkyl groups having 5 to 12 carbon atoms.
  • alkoxy groups include those having 1 to 12 carbon atoms such as methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butoxy, isobutoxy, tert-butoxy, pentyloxy and hexyloxy groups. An alkoxy group etc.
  • Cycloalkoxy groups include, for example, cycloalkoxy groups having 5 to 12 carbon atoms such as cyclohexyloxy.
  • alkylthio groups include alkylthio groups having 1 to 12 carbon atoms such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, tert-butylthio, pentylthio and hexylthio. etc.
  • the cycloalkylthio group includes, for example, cycloalkylthio groups having 5 to 12 carbon atoms such as cyclohexylthio group.
  • alkylamino groups include monoalkylamino groups and dialkylamino groups in which the alkyl moiety is the above-exemplified alkyl group having 1 to 12 carbon atoms.
  • examples of the cycloalkylamino group include monoalkylamino groups and dialkylamino groups in which the cycloalkyl moiety is the above-exemplified cycloalkyl group having 5 to 12 carbon atoms.
  • substituents an alkyl group, an alkoxy group, or the like is preferable, an alkyl group is more preferable, and an alkyl group having 1 to 12 carbon atoms is even more preferable, from the viewpoint of easily increasing the moisture absorption resistance and heat resistance of the film.
  • 1 to 4 alkyl groups are even more preferred, with methyl and/or ethyl groups being particularly preferred.
  • the aromatic ring in structure S may or may not have a substituent, but from the viewpoint of easily increasing the moisture absorption resistance and heat resistance of the film, it has a substituent. is preferred.
  • the number of substituents on the aromatic ring in structure S is not particularly limited, but is preferably 0 or more, more preferably 1 or more, still more preferably 2 or more, still more preferably 3 or more, particularly preferably 4 or more, and particularly preferably 4 or more.
  • the number of substituents P is not particularly limited, but is 1 or more, preferably 2 or more, preferably 6 or less, more preferably 6 or less, from the viewpoint of easily increasing the moisture absorption resistance and heat resistance of the film. is 5 or less, more preferably 4 or less, and even more preferably 3.
  • the structure of the phenolic antioxidant is a structure in which the bond of the substituent P is attached to the part of the structure S from which the hydrogen atoms have been removed.
  • the structure S is an aromatic ring having a methyl group as the substituent Q
  • it may be a structure in which a bond of the substituent P is attached to a portion obtained by removing one hydrogen atom from the methyl group, and from the aromatic ring
  • a structure in which a bond of the substituent P is bonded to a portion from which one hydrogen atom has been removed may also be used.
  • the substituent P may be bonded to the aromatic ring of the structure S, and bonded to a substituent obtained by removing one hydrogen atom from the substituent Q of the aromatic ring (also referred to as a substituent Q'). or if there are multiple substituents P, they may be bonded to both of them.
  • the substituent P is preferably bonded to at least the substituent Q' of the aromatic ring.
  • the case where the substituent P is bonded to the aromatic ring is meant to include the case where it is bonded to a heteroatom (for example, a nitrogen atom).
  • the bonding position of the substituent P relative to the aromatic ring is not particularly limited.
  • the aromatic ring is a benzene ring
  • the substituents P are attached to It is preferably bonded to non-adjacent carbon atoms directly or via a substituent Q', and more preferably bonded directly or via a substituent Q' to the 1,3-position or 1,3,5-position.
  • it is more preferably bonded to the 1, 3, and 5-positions via the substituent Q'.
  • the substituent P is directly or via the substituent Q' at the 2,4-position or at the 2,4-position. It is more preferably bonded to the 6-position, and more preferably bonded to the 2-, 4-, and 6-positions via the substituent Q'.
  • the aromatic ring is an isocyanuric ring
  • the substituent P is directly or via the substituent Q 'at the 1,3-position or at the 1,3,5-position. is preferably bonded to the nitrogen atoms of , more preferably directly bonded to the nitrogen atoms at the 1, 3, and 5 positions.
  • phenolic antioxidants include, for example, those having the following structures. [In each formula, R p , R q , R r and R s are the same as defined above] In the above structure, R p , R q , R r and R s in the substituent P may be the same or different in each phenolic antioxidant. With the structure as described above, the moisture absorption resistance and heat resistance of the film are likely to be improved.
  • phenolic antioxidants include 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6- trimethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert -butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 4-[[4,6-bis(n-octylthio)-1,3 ,5-triazin-2-yl]amino]-2,6-di-tert-butylphenol, 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine, tris isocyanurate ( 4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) and the
  • the content of the phenolic antioxidant contained in the composition of the present invention is preferably 0.01 parts by mass or more, more preferably 0 parts by mass with respect to 100 parts by mass of the polymer (B). 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.2 parts by mass or more, particularly preferably 0.5 parts by mass or more, and even more preferably 2 parts by mass or more.
  • the content of the phenolic antioxidant is at least the above lower limit, the polymer (B) is easily covered with the phenolic antioxidant, and the oxidation of the polymer (B) is easily suppressed. Easy to improve heat resistance.
  • the content of the phenolic antioxidant is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 7 parts by mass or less, and particularly preferably 5 parts by mass with respect to 100 parts by mass of the polymer (B). It is below. If the content of the phenolic antioxidant is equal to or less than the above upper limit, the dielectric properties of the film are likely to be enhanced.
  • the polymer (B) is a polymer different from the polyimide resin (A).
  • the polymer (B) may be a polyimide-based resin that differs in type from the polyimide-based resin (A), for example, the types and contents of the monomer units constituting the resin are different.
  • the polymer (B) may be particulate, acicular or fibrous, preferably particulate.
  • the polymer (B) is in the form of particles, the dispersibility of the polymer (B) in the composition and in the resulting film can be easily increased, and the hygroscopic resistance and heat resistance of the film can be easily improved.
  • the "particle size of the particulate polymer (B)" may be simply referred to as "particle size”.
  • the polymer (B) is not particularly limited, and examples thereof include olefin-based polymers, polyimide-based polymers, fluorine-based polymers, silicone-based polymers, liquid crystal polymers, aramid polymers, styrene-based polymers, and ether-based polymers.
  • Polymer (B) can be used alone or in combination of two or more. When these are used as the polymer (B), the affinity with the phenolic antioxidant is improved, so that the phenolic antioxidant easily covers the periphery of the polymer (B). In addition, aggregation of the polymer (B) can be easily suppressed, and dispersibility of the polymer (B) can be easily improved.
  • a film having excellent moisture absorption resistance and heat resistance can be formed.
  • it is selected from the group consisting of olefin-based polymers, polyimide-based polymers, fluorine-based polymers, liquid crystal polymers, styrene-based polymers and ether-based polymers, from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the resulting film.
  • At least one polymer is preferred, more preferably at least one polymer selected from the group consisting of olefinic polymers and fluoropolymers, more preferably olefinic polymers, polyethylene, high density polyethylene, polypropylene, polymethylpentene and cycloolefin At least one polymer selected from the group consisting of cycloolefin-based polymers is even more preferred, with cycloolefin-based polymers being particularly preferred.
  • the cycloolefin-based polymer has formula (I) [In the formula (I), m represents an integer of 0 or more, R 7 to R 18 each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R 11 to R 14 are present, they are each independently the same may be different, and R 16 and R 17 may be bonded to each other to form a ring together with the carbon atom to which they are bonded] It preferably contains a cycloolefin-derived monomer unit (I) represented by
  • m is an integer of 0 or more.
  • the upper limit of m is preferably an integer of 3 or less, more preferably an integer of 2 or less, More preferably, it is an integer of 1 or less.
  • hydrocarbon groups having 1 to 20 carbon atoms which are members of the substituents of R 7 to R 18 include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group and dodecyl group.
  • Aryl groups such as phenyl group, tolyl group and naphthyl group; Aralkyl groups such as benzyl group and phenethyl group; mentioned.
  • an alkyl group, an aryl group, or an aralkyl group is preferable from the viewpoint of easily improving the dispersibility of the polymer (B) and the hygroscopic resistance and heat resistance of the resulting film.
  • R 7 to R 18 are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms. More preferably, it is an alkyl group having 1 to 10 carbon atoms.
  • cycloolefins represented by formula (I) include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, and tricyclodecene. , tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene and the like.
  • norbornene is preferable from the viewpoint of easy availability of raw material monomers, dispersibility of the polymer (B), and easiness in improving the hygroscopic resistance and heat resistance of the resulting film.
  • the cycloolefins represented by formula (I) may be used alone or in combination of two or more.
  • the cycloolefin-based polymer preferably contains a double chain structure of monomeric units (I).
  • the heat resistance is likely to be improved as compared with a polymer having a similar content of the monomer unit (I).
  • the presence or absence of a double-chain structure can be determined by 13 C-NMR spectrum analysis.
  • signals derived from ethylene-tetracyclodecene-ethylene chains which are isolated chains of tetracyclodecene, appear near 54.7 ppm and 51.1 ppm, and endo-exo bonds
  • the signal derived from the ethylene-tetracyclodecene-tetracyclodecene-ethylene chain which is the double chain of tetracyclodecene, is near 51.5 ppm and 50.8 ppm, and the ethylene-tetracyclodecene-tetracyclo Since the signals derived from the decene-ethylene chain appear near 55.3 ppm and 54.3 ppm, the pattern of signals near 55 ppm and 50 ppm can be determined.
  • the two-chain structure of the monomer unit (I) includes a meso-type two-chain structure represented by the following structural formula (II-1) or the following structural formula (II-2), and/or the following structural formula (III- 1) or a racemo-type double linkage represented by the following structural formula (III-2).
  • the ratio of the meso-type double chain to the racemo-type double chain is preferably 0.50 or less, more preferably 0.40 or less, and still more preferably It is 0.30 or less, particularly preferably 0.20 or less, preferably 0.01 or more, and more preferably 0.05 or more.
  • the ratio of the meso-form bichain to the racemo-form bichain can be determined, for example, using 13 C-NMR, as described in RA Wendt, G.
  • the content of the monomer unit (I) in the cycloolefin-based polymer is preferably 60 mol% or more, more preferably 65 mol% or more, relative to the total molar amount of repeating units constituting the cycloolefin-based polymer, It is more preferably 70 mol % or more, particularly preferably 75 mol % or more, preferably 100 mol % or less, more preferably 99 mol % or less, still more preferably 98 mol % or less.
  • Tg glass transition temperature
  • the content of the monomeric unit (I) is determined using 13 C-NMR, based on the assignment described in "RA Wendt, G. Fink, Macromol. Chem. Phys., 2001, 202, 3490.” For example, it can be calculated by the method described in Examples.
  • the cycloolefin-based polymer consists of ethylene, a linear ⁇ -olefin having 3 to 20 carbon atoms, and an aromatic vinyl compound having 8 to 20 carbon atoms, from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the film. It preferably contains a monomeric unit (II) derived from at least one selected from the group.
  • Linear ⁇ -olefins having 3 to 20 carbon atoms include, for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene. be done. Among these, propylene, 1-butene, 1-hexene, or 1-octene is preferable, and propylene is more preferable, from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the film.
  • Linear ⁇ -olefins having 3 to 20 carbon atoms may be used singly or in combination of two or more.
  • the term "straight-chain ⁇ -olefin" refers to a straight-chain olefin having a carbon-carbon unsaturated double bond at the ⁇ -position.
  • aromatic vinyl compounds having 8 to 20 carbon atoms include styrene, methylstyrene, dimethylstyrene, ethylstyrene, tert-butylstyrene, vinylnaphthalene, vinylanthracene, diphenylethylene, isopropenylbenzene, isopropenyltoluene, and isopropenyl.
  • styrene methylstyrene, or dimethylstyrene is preferred, and styrene is more preferred, from the viewpoints of easy availability of raw material monomers and easy improvement of hygroscopic resistance and heat resistance of the film.
  • the aromatic vinyl compounds having 8 to 20 carbon atoms may be used singly or in combination of two or more.
  • the cycloolefin-based polymer is preferably selected from the group consisting of ethylene, propylene and styrene from the viewpoints of easy availability of raw material monomers and easy improvement of moisture absorption resistance and heat resistance of the film. It preferably contains monomer units (II) derived from at least one, more preferably monomer units (II) derived from at least one selected from the group consisting of ethylene and styrene.
  • the content of the monomer unit (II) in the cycloolefin-based polymer is preferably 0 mol% or more, more preferably 0.01 mol%, relative to the total molar amount of repeating units constituting the cycloolefin-based polymer. More preferably 1 mol% or more, still more preferably 2 mol% or more, preferably 40 mol% or less, more preferably 35 mol% or less, still more preferably 30 mol% or less, particularly preferably 25 mol% It is below.
  • the content of the monomer unit (II) is at least the above lower limit, mechanical properties such as bending resistance, workability, and moldability of the film can be easily improved.
  • the content of the monomer unit (II) is equal to or less than the above upper limit, the hygroscopic resistance and heat resistance of the film are likely to be improved.
  • the cycloolefin-based polymer is preferably a cycloolefin copolymer from the viewpoint of easily improving mechanical properties such as heat resistance, processability, and bending resistance, and moisture absorption resistance, and the formula (I ) and a cycloolefin-derived monomer unit (I) represented by ethylene, a linear ⁇ -olefin having 3 to 20 carbon atoms and an aromatic vinyl compound having 8 to 20 carbon atoms.
  • the cycloolefin-based polymer contains at least one monomeric unit (II) derived from norbornene-derived monomeric unit (I) and ethylene-derived monomeric unit (II) or a styrene-norbornene copolymer containing monomeric units (I) derived from norbornene and monomeric units (II) derived from styrene.
  • the cycloolefin-based polymer may contain other monomer units (III).
  • Other monomers constituting the monomer unit (III) include, for example, conjugated dienes such as butadiene or isoprene; non-conjugated dienes such as 1,4-pentadiene; acrylic acid; methyl acrylate or acrylic acid; acrylic acid esters such as ethyl; methacrylic acid; methacrylic acid esters such as methyl methacrylate or ethyl methacrylate; and vinyl acetate.
  • Other monomeric units (III) can be used singly or in combination of two or more.
  • the polymer (B) can be used alone or in combination of two or more.
  • the olefin-based polymer other than the cycloolefin-based polymer includes, for example, the monomer unit (II); the monomer unit (III); 3-methyl-1-butene, 3-methyl- at least one monomer unit selected from the group consisting of 1-pentene, 4-methyl-1-pentene and vinylcycloalkane; Polyethylene, polypropylene or polymethylpentene is preferable, and polypropylene or polymethylpentene is more preferable from the viewpoint of enhancing heat resistance.
  • polyimide-based polymers include, for example, polyimide-based polymers that are soluble in the second solvent described later.
  • the fluorine-based polymer is an olefin polymer containing fluorine or a modified product thereof.
  • fluoroolefins such as tetrafluoroethylene, trifluoroethylene, chlorotrifluoro Polymers and copolymers containing at least one monomer unit selected from the group consisting of ethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, etc., such as polytetrafluoroethylene (PTFE), perfluoroalkoxyalkanes, perfluoroethylene propene copolymers, ethylene-tetrafluoroethylene copolymers, polyvinylidene fluoride, polychlorotrifluoroethylene, polyhexafluoropropylene and the like.
  • PTFE polytetrafluoroethylene
  • PTFE polytetrafluoroethylene
  • perfluoroalkoxyalkanes perfluoroethylene propene copolymers
  • the fluoropolymer is preferably a polymer having structural units derived from tetrafluoroethylene, and more preferably the molar ratio of the structural units derived from tetrafluoroethylene to the total of all structural units is 0.5. 25 or more, more preferably 0.30 or more, still more preferably 0.50 or more, and particularly preferably 0.75 or more.
  • the molar ratio of each structural unit of the fluoropolymer can be obtained by NMR measurement. (HFP)-Tetrafluoroethylene (TFE)”, Macromolecules, 2015, Vol. 48, No. 11, p.3563-3576.
  • liquid crystal polymers include polymers having repeating units such as aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, and aliphatic diols.
  • monomers that give aromatic hydroxycarboxylic acid repeating units include parahydroxybenzoic acid, metahydroxybenzoic acid, orthohydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and 5-hydroxy-2-naphthoic acid.
  • 3-hydroxy-2-naphthoic acid, 4′-hydroxyphenyl-4-benzoic acid, 3′-hydroxyphenyl-4-benzoic acid, 4′-hydroxyphenyl-3-benzoic acid and other aromatic hydroxycarboxylic acids, Alkyl-, alkoxy- or halogen-substituted products thereof, and ester-forming derivatives thereof are included.
  • parahydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are preferred from the viewpoint of easily improving the moisture absorption resistance, mechanical properties and heat resistance of the film.
  • monomers that provide aromatic dicarboxylic acid repeating units include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4 -naphthalenedicarboxylic acid, aromatic dicarboxylic acids such as 4,4′-dicarboxybiphenyl, alkyl-, alkoxy- or halogen-substituted products thereof, and ester-forming derivatives thereof.
  • terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid are preferable from the viewpoint of easily improving the moisture absorption resistance, mechanical properties and heat resistance of the film.
  • monomers that give aromatic diol repeating units include hydroquinone, resorcinol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4, Aromatic diols such as 4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl and 4,4'-dihydroxybiphenyl ether, their alkyl, alkoxy or halogen substituted products, and these and ester-forming derivatives of Among them, hydroquinone and 3,3'-dihydroxybiphenyl are preferable from the viewpoint of easily improving the moisture absorption resistance, mechanical properties and heat resistance of the film.
  • monomers that provide aliphatic diol repeating units include aliphatic diols such as ethylene glycol, 1,4-butanediol and 1,6-hexanediol, and acylated products thereof.
  • ethylene glycol is preferable from the viewpoint of easily improving the hygroscopic resistance, mechanical properties and heat resistance of the film.
  • the styrenic polymer is a resin containing at least one styrene in the repeating structural unit.
  • examples include polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AS resin (acrylonitrile - styrene copolymer) and the like.
  • polystyrene is preferable from the viewpoint of easily increasing dielectric properties.
  • a polymer having both a styrene-derived monomer unit and a cycloolefin-derived monomer unit as repeating structural units is classified as a cycloolefin-based polymer.
  • the ether-based polymer is a resin containing at least one repeating unit containing an ether group in the main chain, such as polyetherimide, polyphenylene ether, polyethersulfone, polyetherketone, polyether ether ketone and the like.
  • polyetherimide polyphenylene ether
  • polyethersulfone polyetherketone
  • polyether ether ketone polyether ketone
  • polyphenylene ether, polyether sulfone, and polyether ether ketone are preferable from the viewpoint of easily improving the moisture absorption resistance, heat resistance, and dielectric properties of the film.
  • At least one of the glass transition temperature and melting point of the polymer (B) is preferably 100°C or higher.
  • the Tg of the polymer (B) is preferably 100° C. or higher, more preferably 140° C. or higher, still more preferably 160° C. or higher, even more preferably 180° C. or higher, particularly preferably 200° C. or higher, and particularly preferably 220° C. or higher. , particularly preferably 240° C. or higher, particularly more preferably 260° C. or higher, preferably 500° C. or lower, more preferably 400° C. or lower, and still more preferably 320° C. or lower.
  • the melting point of the polymer (B) is preferably 100° C. or higher, more preferably 140° C. or higher, still more preferably 160° C. or higher, still more preferably 180° C. ° C. or higher, particularly preferably 200 ° C. or higher, particularly more preferably 220 ° C. or higher, even more preferably 240 ° C. or higher, most preferably 260 ° C. or higher, preferably 500 ° C. or lower, more preferably 400 ° C. or lower, further preferably is below 350°C.
  • the CTE of the film is likely to be reduced, and mechanical properties such as wet water resistance, heat resistance and bending resistance are likely to be enhanced.
  • the mechanical properties of the film particularly resistance to repeated bending, are likely to be enhanced.
  • the Tg of polymer (B) is a softening temperature measured by TMA based on JIS K 7196, and can be measured, for example, by the method described in Examples.
  • the method of adjusting the Tg and melting point of the polymer (B) is not particularly limited, but for example, a method of appropriately adjusting the content of the monomer unit (I), the Mw of the polymer (B), the degree of crystallinity, etc. mentioned.
  • the Tg and melting point of the polymer (B) tend to increase as at least one selected from the group consisting of the content of the monomer unit (I), the Mw of the polymer (B), and the degree of crystallinity increases.
  • the melting point of the polymer (B) can be determined, for example, by using a differential scanning calorimeter (DSC) and measuring the melting peak temperature from the resulting melting curve.
  • DSC differential scanning calorimeter
  • the DSC is not particularly limited, for example, a DSC manufactured by Hitachi High-Tech Science Co., Ltd. may be used.
  • the weight average molecular weight of the polymer (B) (hereinafter the weight average molecular weight may be abbreviated as Mw) is preferably 10,000 or more, more preferably 15,000, and still more preferably 20. ,000 or more, still more preferably 30,000 or more, particularly preferably 50,000 or more, particularly more preferably 70,000 or more, particularly preferably 90,000 or more, preferably 2,000,000 or less, and more It is preferably 1,000,000 or less, more preferably 700,000 or less.
  • Mw is at least the above lower limit, it is easy to increase the hygroscopic resistance and heat resistance of the film, and it is easy to improve the strength.
  • the Mw is equal to or less than the above upper limit, the moisture absorption resistance, mechanical properties and moldability of the film are likely to be improved.
  • the ratio (Mw/Mn) between the Mw and the number average molecular weight (hereinafter the number average molecular weight may be abbreviated as Mn) of the polymer (B) is preferably 2.0 in terms of polystyrene. 5 or less, more preferably 2.2 or less, still more preferably 2.0 or less, even more preferably 1.95 or less, particularly preferably 1.90 or less, preferably 1.30 or more, more preferably 1.90 or less. It is 50 or more, more preferably 1.60 or more, and particularly preferably 1.65 or more.
  • Mw/Mn ratio When the Mw/Mn ratio is at most the above upper limit, the hygroscopic resistance, heat resistance, and mechanical properties of the film are likely to be enhanced, and at the above lower limit or above, the formability is likely to be enhanced.
  • Mw and Mn can be obtained by performing gel permeation chromatography (hereinafter sometimes abbreviated as GPC) measurement and converting to standard polystyrene, for example, by the method described in Examples.
  • GPC gel permeation chromatography
  • the refractive index of the polymer (B) is preferably 1.600 or less, more preferably 1.570 or less, still more preferably 1.570 or less, from the viewpoint of easily obtaining a film with a reduced CTE. It is 550 or less, preferably 1.500 or more, more preferably 1.520 or more.
  • the refractive index of the polymer (B) can be measured with a refractometer, for example, by the method described in Examples.
  • the CTE of polymer (B) is preferably 58 ppm/K or less, more preferably 55 ppm/K or less, even more preferably 50 ppm/K or less, preferably 0 ppm/K or more, more preferably is 0.01 ppm/K or more, more preferably 1 ppm/K or more, and even more preferably 5 ppm/K or more.
  • the CTE of the polymer (B) is equal to or less than the above upper limit, the CTE of the resulting film is likely to be reduced.
  • the CTE of the film In the case of producing a copper-clad laminate by bonding with copper foil, it is preferable to adjust the CTE of the film to around 20 ppm/K from the viewpoint of preventing peeling of the laminate film.
  • the polymer (B) with the optimum CTE can be selected.
  • CTE can be measured, for example, by thermomechanical analysis (hereinafter sometimes referred to as TMA), and is determined by the method described in Examples.
  • the median diameter of the particulate polymer (B) in the composition of the present invention is preferably 0.01 ⁇ m or more, more preferably 0.03 ⁇ m. More preferably 0.05 ⁇ m or more, preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 5 ⁇ m or less, even more preferably 3 ⁇ m or less, particularly preferably 1 ⁇ m or less, and particularly preferably 0.8 ⁇ m or less , and more preferably 0.5 ⁇ m or less.
  • the median diameter of the particulate polymer (B) in the composition is at least the above lower limit, the dielectric properties of the film formed from the composition are likely to be enhanced, and the film is easily produced.
  • the median diameter of the particulate polymer (B) in the composition is equal to or less than the above upper limit, the dispersibility of the polymer (B) in the composition and in the film is likely to be increased, and the resulting film has hygroscopic resistance and heat resistance. Easy to improve.
  • the method for determining the median diameter of the particulate polymer (B) in the composition is not particularly limited, it can be determined, for example, using a centrifugal sedimentation particle size distribution analyzer or an ultrasonic attenuation particle size distribution analyzer.
  • the polyimide resin (A) and the phenolic antioxidant are added to the particulate polymer (B) dispersion in an amount that does not affect the particle size of the particulate polymer (B) to form a composition.
  • the median diameter of the particulate polymer (B) in the dispersion can be measured in advance and used as the median diameter of the particulate polymer (B) in the composition.
  • the median diameter is also referred to as D50, and indicates a value at which the number of particles of the particulate polymer (B) on the side smaller than that value is equal to the number of particles on the larger side.
  • the term "particle size” means the median size and/or average primary particle size of the particulate polymer (B), unless otherwise specified.
  • the content of the polymer (B) contained in the composition of the present invention is usually 1% by mass or more with respect to the total mass of the polyimide resin (A) and the polymer (B), Preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably 10% by mass or more, particularly preferably 20% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably is 35% by mass or less.
  • the content of the polymer (B) contained in the composition is at least the above lower limit, the formation of aggregates of the polymer (B) is likely to be suppressed, and thus the dispersibility of the polymer (B) is likely to be enhanced.
  • the content of the polymer (B) contained in the composition is equal to or less than the above upper limit, film formation is facilitated, which is advantageous from the viewpoint of film production. If the dispersibility of the polymer (B) in the film is high, the uniformity of thermal conductivity and CTE will be high. easier to suppress.
  • Polymer (B) may be a commercially available product or may be produced by a conventional method.
  • polymer (B) is preferably a cycloolefinic polymer.
  • the method for producing the cycloolefin-based polymer is not particularly limited. at least one monomer selected from the group consisting of a cycloolefin represented by formula (I), the ethylene, a linear ⁇ -olefin having 3 to 20 carbon atoms and an aromatic vinyl compound having 8 to 20 carbon atoms; It is preferably prepared by polymerizing one monomer, and optionally said other monomers.
  • transition metal complex ( ⁇ ) represented by the formula (IV) is used in the production of the cycloolefin-based polymer in the present invention, the content of the monomer unit (I) in the cycloolefin-based polymer is significantly increased. It is easy to adjust Tg within the above range.
  • M represents a transition metal element in Group 4 of the periodic table of the elements
  • Cp represents a group having a cyclopentadienyl skeleton
  • A represents an atom of Group 16 of the Periodic Table of the Elements
  • T represents an atom of Group 14 of the Periodic Table of the Elements
  • D 1 and D 2 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon number It represents an aryloxy group having 6 to 20 carbon atoms or a disubstituted amino group having 2 to 20 carbon atoms, which may be the same or different.
  • R 1 to R 6 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. represents an aryloxy group having 6 to 20 carbon atoms, a disubstituted amino group having 2 to 20 carbon atoms or a silyl group having 1 to 20 carbon atoms, which may be the same or different, and are optionally bonded may form a ring.
  • M is a transition metal element in Group 4 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989), for example, titanium atom, zirconium atom, hafnium atom, and the like.
  • Cp is a group having a cyclopentadienyl skeleton, such as cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl, substituted fluorenyl and the like.
  • a cyclopentadienyl group such as cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl, substituted fluorenyl and the like.
  • Specific examples include a cyclopentadienyl group, a methylcyclopentadienyl group, a tetramethylcyclopentadienyl group, an n-propylcyclopentadienyl group, an n-butylcyclopentadienyl group, and an isobutylcyclopentadienyl group.
  • phenylcyclopentadienyl group indenyl group, methylindenyl group, n-propylindenyl group, n-butylindenyl group, isobutylindenyl group, phenylindenyl group, fluorenyl group, methylfluorenyl group, n -Propylfluorenyl group, phenylfluorenyl group, dimethylfluorenyl group and the like.
  • cyclopentadienyl group methylcyclopentadienyl group, tetramethylcyclopentadienyl group, n-butylcyclopentadienyl group, isobutylcyclopentadienyl group, indenyl group and methylindenyl group are preferred. or a fluorenyl group.
  • A is an atom of Group 16 of the periodic table of elements, and includes, for example, an oxygen atom and a sulfur atom. Among these, an oxygen atom is preferable.
  • T is an atom of Group 14 of the periodic table of elements, and includes, for example, a carbon atom, a silicon atom, a germanium atom, and the like. Among these, a carbon atom or a silicon atom is preferred.
  • D 1 and D 2 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or It is an aryloxy group having 6 to 20 carbon atoms or a disubstituted amino group having 2 to 20 carbon atoms, which may be the same or different.
  • a halogen atom is preferable.
  • D 1 and D 2 being halogen atoms include fluorine, chlorine, bromine and iodine atoms.
  • D 1 and D 2 are hydrocarbon groups
  • the number of carbon atoms is preferably 1-10.
  • the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group and n-hexyl. group, n-octyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, naphthyl group, benzyl group and the like.
  • D 1 and D 2 being halogenated hydrocarbon groups include fluoromethyl group, difluoromethyl group, 1-fluoroethyl group, 1,1-difluoroethyl group, 1,2-difluoroethyl group, 1,1,2-trifluoroethyl group, tetrafluoroethyl group, chloromethyl group, dichloromethyl group, 1-chloroethyl group, 1,1-dichloroethyl group, 1,2-dichloroethyl group, 1,1,2 -trichloroethyl group, 1,1,2,2-tetrachloroethyl group, bromomethyl group, dibromomethyl group, 1-bromoethyl group, 1,1-dibromoethyl group, 1,2-dibromoethyl group, 1,1,2 -tribromoethyl group, 1,1,2,2-tetrabromoethyl group, 2-fluoroph
  • D 1 and D 2 being alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n- pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group and the like.
  • D 1 and D 2 being aryloxy groups include phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy and naphthyloxy groups.
  • the disubstituted amino group is an amino group in which two substituents are bonded.
  • Specific examples thereof include a dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, diisobutylamino group, di-sec-butylamino group and di-tert-butyl.
  • R 1 to R 6 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or represents an aryloxy group having 6 to 20 carbon atoms, a disubstituted amino group having 2 to 20 carbon atoms or a silyl group having 1 to 20 carbon atoms, which may be the same or different, and are optionally They may be combined to form a ring.
  • hydrocarbon groups having 1 to 20 carbon atoms are preferred.
  • R 1 to R 6 being halogen atoms include fluorine, chlorine, bromine and iodine atoms.
  • R 1 to R 6 are hydrocarbon groups, they preferably have 1 to 10 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group and n-hexyl group.
  • n-octyl group phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group , 2,6-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, pentamethylphenyl group and the like.
  • R 1 to R 6 are a halogen atom, a halogenated hydrocarbon group, an alkoxy group, an aryloxy group, or a disubstituted amino group
  • D 1 and D 2 being a halogen atom or a halogenated hydrocarbon group
  • an alkoxy group, an aryloxy group, and a disubstituted amino group include those exemplified above.
  • R 1 to R 6 are silyl groups include trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, triisobutylsilyl group, tri -sec-butylsilyl group, tri-tert-butylsilyl group, triphenylsilyl group and the like.
  • Such compounds represented by formula (IV) include isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(methylcyclo pentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(dimethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropyl Lidene (trimethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) ) titanium dichloride, isopropylidene (n-propylcyclopentadienyl) (3-tert-buty
  • the transition metal complex ( ⁇ ) represented by formula (IV) above can be used as a catalyst for producing the polymer (B) according to one embodiment of the present invention in combination with various cocatalysts.
  • a co-catalyst is a compound that interacts with the transition metal complex ( ⁇ ) to generate polymerization active species for cyclic olefins and alkenyl aromatic hydrocarbons. Examples thereof include organoaluminum compounds ( ⁇ ) and/or boron compounds ( ⁇ ) represented by any of the following formulas ( ⁇ 1) to ( ⁇ 3). The structure of the polymerization active species generated by this is not clear.
  • B represents a boron atom in a trivalent state
  • Q 1 to Q 4 each independently represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, or a silyl group having 1 to 20 carbon atoms.
  • J + represents an inorganic or organic cation
  • L represents a neutral Lewis base
  • (LH) + represents a Bronsted acid.
  • a known organoaluminum compound can be used as the organoaluminum compound ( ⁇ ).
  • Specific examples include an organoaluminum compound represented by formula ( ⁇ 1), a cyclic aluminoxane having a structure represented by formula ( ⁇ 2), and a linear aluminoxane having a structure represented by formula ( ⁇ 3). , these can be used alone or in combination of two or more.
  • E 1 , E 2 and E 3 each independently represent a hydrocarbon group having 1 to 8 carbon atoms, all E 1 , all E 2 and all E 3 may be the same or different, Z represents hydrogen or halogen, all Z may be the same or different, a represents an integer of 0 to 3 , b represents an integer of 2 or more, and c represents an integer of 1 or more.
  • formula ( ⁇ 1) include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride; Dialkylaluminum chlorides such as dihexylaluminum chloride; Alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride; dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride , dialkylaluminum hydride such as dihexylaluminum, di
  • E 2 and E 3 in formula ( ⁇ 2) and formula ( ⁇ 3) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group and neopentyl. and alkyl groups such as Among these, a methyl group or an isobutyl group is preferred.
  • b is an integer of 2 or more, preferably an integer of 2-40.
  • c is an integer of 1 or more, preferably an integer of 1-40.
  • the above aluminoxanes are made by various methods.
  • the method is not particularly limited, and it may be produced according to a known method.
  • a method of contacting with a metal salt containing water of crystallization, such as copper sulfate hydrate, can be exemplified.
  • any one of the boron compounds represented by formula ( ⁇ 1), formula ( ⁇ 2), or formula ( ⁇ 3) can be used.
  • B represents a boron atom in a trivalent state
  • Q 1 to Q 3 each independently represent a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, represents a halogenated hydrocarbon group, a substituted silyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a disubstituted amino group having 2 to 20 carbon atoms, which may be the same or different; good too.
  • Q 1 to Q 3 are each independently preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.
  • boron compound represented by formula ( ⁇ 1) include tris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane, tris(2,3,4,5- tetrafluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane, phenylbis(pentafluorophenyl)borane and the like, preferably tris (Pentafluorophenyl)borane can be mentioned.
  • B represents a trivalent boron atom
  • Q 1 to Q 4 are the same as Q 1 to Q 3 in formula ( ⁇ 1) above.
  • J + represents an inorganic or organic cation.
  • Inorganic cations in J + include ferrocenium cations, alkyl-substituted ferrocenium cations, silver cations, and the like.
  • Examples of organic cations for J + include triphenylmethyl cations.
  • (BQ 1 Q 2 Q 3 Q 4 ) - includes tetrakis(pentafluorophenyl)borate anion, tetrakis(2,3,5,6-tetrafluorophenyl)borate anion, tetrakis(2,3,4,5- tetrafluorophenyl)borate anion, tetrakis(3,4,5-trifluorophenyl)borate anion, tetrakis(2,2,4-trifluorophenyl)borate anion, phenylbis(pentafluorophenyl)borate anion, tetrakis(3 ,5-bistrifluoromethylphenyl)borate anion and the like.
  • Specific combinations thereof include ferroceniumtetrakis(pentafluorophenyl)borate, 1,1'-dimethylferroceniumtetrakis(pentafluorophenyl)borate, silver tetrakis(pentafluorophenyl)borate, triphenylmethyltetrakis (Pentafluorophenyl)borate, triphenylmethyltetrakis(3,5-bistrifluoromethylphenyl)borate and the like, preferably triphenylmethyltetrakis(pentafluorophenyl)borate.
  • B represents trivalent boron
  • Q 1 to Q 4 are the same as Q 1 to Q 3 in formula ( ⁇ 1) above.
  • L represents a neutral Lewis base and (LH) + represents a Bronsted acid.
  • Bronsted acid (LH) + includes trialkyl-substituted ammonium cations, N,N-dialkylanilinium cations, dialkylammonium cations, and triarylphosphonium cations.
  • (BQ 1 Q 2 Q 3 Q 4 ) - includes the same groups as those described above.
  • the co-catalyst it is preferable to use the organoaluminum compound ( ⁇ ) and the compound ( ⁇ ) together.
  • transition metal complex ( ⁇ ), organoaluminum compound ( ⁇ ) and/or compound ( ⁇ ) represented by formula (IV) can be used in any order during polymerization, but any of these compounds You may use the reactant obtained by contacting previously the combination of.
  • the molar ratio of cocatalyst/transition metal complex ( ⁇ ) is preferably 0.01 to 10,000, more preferably 0.5 to 2,000.
  • concentration of the transition metal complex ( ⁇ ) is preferably 0.0001-5 mmol/L, more preferably 0.001-1 mmol/L.
  • the amount of catalyst component used is preferably 0.00001 to 1 mol %, more preferably 0.0001 to 0.1 mol %, based on the total amount of all monomers used.
  • the polymerization method of the polymer (B) according to one embodiment of the present invention is not particularly limited. Any method such as a method or a slurry polymerization method can be adopted.
  • solvents When using a solvent, various solvents can be used provided that they do not deactivate the catalyst.
  • solvents include hydrocarbon solvents such as benzene, toluene, pentane, hexane, heptane, and cyclohexane; Examples thereof include halogenated hydrocarbon solvents such as dichloromethane and ethylene dichloride.
  • the ethylene partial pressure in the system during polymerization is, for example, 50 to 400 kPa, preferably 50 to 300 kPa, and the hydrogen partial pressure is preferably 0 to 100 kPa.
  • ethylene and hydrogen are introduced into the system, it is preferable to pressurize with the partial pressure of hydrogen and then pressurize with the partial pressure of ethylene.
  • toluene may be added after charging the solution of the cycloolefin represented by the formula (I) into the polymerization reactor.
  • the polymerization temperature is preferably 50°C or higher, more preferably 50 to 150°C, still more preferably 50 to 100°C.
  • a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the polymer.
  • the polyimide resin (A) is a resin containing a repeating structural unit containing an imide group (hereinafter sometimes referred to as a polyimide resin), and a resin containing a repeating structural unit containing both an imide group and an amide group (hereinafter (sometimes referred to as polyamide-imide resin), as well as precursors prior to production of polyimide-based resins by imidization.
  • the precursor prior to manufacturing the polyimide resin is polyamic acid.
  • a "repeating structural unit” may be called a "structural unit.”
  • a "constituent unit derived from” may be simply referred to as a "unit”, and for example, a constituent unit derived from a compound may be referred to as a compound unit.
  • the polyimide resin (A) has the formula (1): [In formula (1), X represents a divalent organic group, Y represents a tetravalent organic group, and * represents a bond] It is preferable to have a structural unit represented by With such a polyimide resin, the dispersibility of the polymer (B) in the composition and film can be easily improved, and the hygroscopic resistance and heat resistance of the obtained film can be easily improved.
  • Each X in formula (1) independently represents a divalent organic group, preferably a divalent organic group having 2 to 100 carbon atoms.
  • the divalent organic group include a divalent aromatic group and a divalent aliphatic group.
  • the divalent aliphatic group include a divalent acyclic aliphatic group and a divalent Cycloaliphatic groups are included.
  • 2 Preferred are divalent cycloaliphatic groups and divalent aromatic groups, more preferred are divalent aromatic groups.
  • a divalent aromatic group is a divalent organic group having an aromatic group, and may contain an aliphatic group or other substituents in part of its structure.
  • a divalent aliphatic group is a divalent organic group having an aliphatic group, and may contain other substituents in part of its structure, but does not contain an aromatic group.
  • the polyimide resin (A) may contain multiple types of X, and the multiple types of X may be the same or different.
  • X in formula (1) includes, for example, groups (structures) represented by formulas (2) to (8); hydrogen atoms in groups represented by formulas (5) to (8) are methyl groups. , ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, fluoro group, chloro group or trifluoromethyl group.
  • R a and R b are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a represents an aryl group, hydrogen atoms contained in R a and R b may be independently substituted with halogen atoms, and W is independently a single bond, —O—, —CH 2 — , -CH 2 -CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -COO-, -OOC-, -SO 2 -, -S -, -CO- or -N(R c )-, where R c represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom, n is 0 to is an integer of 4, t is an integer
  • ring A represents a cycloalkane having 3 to 8 carbon atoms
  • R d represents an alkyl group having 1 to 20 carbon atoms
  • r is 0 or more (the number of carbon atoms in ring A is -2)
  • S1 and S2 independently represent integers from 0 to 20, and * represents a bond.
  • X in formula (1) examples include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, propylene group, 1,2-butanediyl group and 1,3-butanediyl group. , 1,12-dodecanediyl group, 2-methyl-1,2-propanediyl group, 2-methyl-1,3-propanediyl group and other linear or branched alkylene groups such as divalent acyclic Aliphatic groups are included. Hydrogen atoms in the divalent acyclic aliphatic group may be substituted with halogen atoms, and carbon atoms may be substituted with heteroatoms such as oxygen atoms, nitrogen atoms, and the like.
  • the polyimide resin (A) in the present invention preferably contains a structure represented by formula (2) and/or a structure represented by formula (3) as X in formula (1), and formula (2 ) is more preferred.
  • each benzene ring or cyclohexane ring are ortho-, meta- or para-positions, or ⁇ -, ⁇ - or ⁇ -positions relative to -W-. It may be bonded to any position, and from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the resulting film, it is preferably at the meta-position or para-position, or at the ⁇ -position or at the ⁇ -position, more preferably at the para-position or at the ⁇ -position.
  • R a and R b each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
  • alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2 -methyl-butyl group, 3-methylbutyl group, 2-ethyl-propyl group, n-hexyl group and the like.
  • alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy and cyclohexyloxy groups. mentioned.
  • Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, tolyl group, xylyl group, naphthyl group and biphenyl group.
  • Hydrogen atoms contained in R a and R b may be independently substituted with halogen atoms, and examples of the halogen atoms include fluorine, chlorine, bromine and iodine atoms.
  • R a and R b are each independently an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group having 1 to 6 carbon atoms, from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the resulting film.
  • group more preferably an alkyl group having 1 to 3 carbon atoms or a fluorinated alkyl group having 1 to 3 carbon atoms, further preferably a methyl group or a trifluoromethyl group.
  • t and u are independently integers of 0 to 4, and from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the resulting film, preferably 0 to 2. , more preferably 0 or 1.
  • W is independently a single bond, —O—, —CH 2 —, —CH 2 —CH 2 —, —CH(CH 3 )—, —C(CH 3 ) represents 2 -, -C(CF 3 ) 2 -, -COO-, -OOC-, -SO 2 -, -S-, -CO- or -N(R c )-, and Single bonds, —O—, —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 are preferred from the viewpoint of easily improving hygroscopicity, heat resistance and mechanical properties, especially bending resistance.
  • R c represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom.
  • Examples of monovalent hydrocarbon groups having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n- pentyl group, 2-methyl-butyl group, 3-methylbutyl group, 2-ethyl-propyl group, n-hexyl group, n-heptyl group, n-octyl group, tert-octyl group, n-nonyl group and n-decyl group etc., which may be substituted with a halogen atom.
  • Halogen atoms include those mentioned above.
  • n is an integer of 0 to 4, which facilitates increasing the dispersibility of the polymer (B) in the composition and film, and improves the moisture absorption resistance and heat resistance of the resulting film. It is preferably an integer of 0 to 3, more preferably 1 or 2, from the viewpoint of easy improvement.
  • n is 2 or more, a plurality of W, R a , and t may be the same or different, and the position of the bond of each benzene ring relative to -W- is also the same. may be different.
  • W, n, R a , R b , t and u may be independently the same as or different from W, n, R a , R b , t and u in formula (3) .
  • ring A represents a cycloalkane having 3 to 8 carbon atoms.
  • Cycloalkanes include, for example, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and cyclooctane, preferably cycloalkanes having 4 to 6 carbon atoms.
  • each bond may or may not be adjacent to each other.
  • the two bonds may have a positional relationship of ⁇ -position, ⁇ -position or ⁇ -position, preferably ⁇ -position or ⁇ -position.
  • R d in formula (4) represents an alkyl group having 1 to 20 carbon atoms.
  • the alkyl group having 1 to 20 carbon atoms include those exemplified above as the hydrocarbon group having 1 to 20 carbon atoms in R 7 to R 18 , preferably an alkyl group having 1 to 10 carbon atoms.
  • r in formula (4) represents an integer of 0 or more and (the number of carbon atoms in ring A - 2) or less. r is 0 or more, preferably 4 or less.
  • S1 and S2 in formula (4) each independently represent an integer of 0 to 20.
  • S1 and S2 are each independently preferably 0 or more, more preferably 2 or more, and preferably 15 or less.
  • X in formula (1) when X in formula (1) includes a structure represented by formula (2) and/or formula (3), X in formula (1) is represented by formula (2) and/or the proportion of the structural unit represented by formula (3) is preferably 30 mol% or more, more preferably 50 mol% or more, relative to the total molar amount of the structural units represented by formula (1), It is more preferably 70 mol % or more, particularly preferably 90 mol % or more, and preferably 100 mol % or less.
  • the proportion of structural units represented by formula (2) and/or formula (3) for X in formula (1) is within the above range, the formation of aggregates of the polymer (B) is easily suppressed, and the polymer It is easy to improve the dispersibility of (B).
  • the proportion of structural units in which Y in formula (1) is represented by formula (2) and/or formula (3) can be measured using, for example, 1 H-NMR, or calculated from the feed ratio of raw materials. You can also
  • Y independently represents a tetravalent organic group, preferably a tetravalent organic group having 4 to 40 carbon atoms, more preferably a tetravalent organic group having 4 to 40 carbon atoms and having a cyclic structure. represents a valent organic group.
  • Cyclic structures include alicyclic, aromatic and heterocyclic structures.
  • a hydrogen atom in the organic group may be substituted with a halogen atom, a hydrocarbon group, an alkoxy group, or a halogenated hydrocarbon group. In this case, the number of carbon atoms in these groups is preferably 1 to 8. is.
  • the polyimide resin (A) in the present invention may contain multiple types of Y, and the multiple types of Y may be the same or different.
  • Y is a group (structure) represented by formulas (31) to (38); hydrogen atoms in the groups represented by formulas (34) to (38) are methyl group, ethyl group, n-propyl a group substituted with a group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, fluoro group, chloro group or trifluoromethyl group; tetravalent C1-8 chain formula A hydrocarbon group etc. are mentioned.
  • R 19 to R 26 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a representing an aryl group, hydrogen atoms contained in R 19 to R 26 may be independently substituted with halogen atoms, V 1 and V 2 are each independently a single bond, —O—, —CH 2 —, —CH 2 —CH 2 —, —CH(CH 3 )—, —C(CH 3 ) 2 —, —C (CF 3 ) 2 -, -COO-, -OOC-, -SO 2 -, -S-, -CO-, -N(R j )-, formula (a) or formula (b) (In formula (a), R 27 to R 30 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Z is a single bond, —C(CH 3 )
  • the polyimide resin in the present invention has the formula (1) Y in the above preferably contains at least one structure selected from the group consisting of a structure represented by formula (31), a structure represented by formula (32), or a structure represented by formula (33) , more preferably a structure represented by formula (31).
  • R 19 to R 26 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. represents a group.
  • the alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms and the aryl group having 6 to 12 carbon atoms are respectively the alkyl group having 1 to 6 carbon atoms and the carbon
  • the alkoxy groups having 1 to 6 carbon atoms and the aryl groups having 6 to 12 carbon atoms are exemplified above.
  • the hydrogen atoms contained in R 19 to R 26 may be independently substituted with halogen atoms, and the halogen atoms include those exemplified above.
  • R 19 to R 26 are each independently hydrogen.
  • An atom or an alkyl group having 1 to 6 carbon atoms is preferred, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is more preferred, and a hydrogen atom is even more preferred.
  • V 1 and V 2 are each independently a single bond, —O—, —CH 2 —, —CH 2 —CH 2 —, —CH(CH 3 )—, —C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -COO-, -OOC-, -SO 2 -, -S-, -CO-, -N(R j )-, formula (a) or formula (b ), preferably a single bond, —O—, —CH 2 from the viewpoint of easily increasing the dispersibility of the polymer (B) in the composition and film and easily improving the moisture absorption resistance and heat resistance of the resulting film.
  • R j represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include those exemplified above.
  • e in formula (31) is 0, it indicates that formula (31) does not have -V 1 - (two benzene rings are not bonded at -V 1 -), and d is 0, it indicates that formula (31) does not have -V 2 - (the two benzene rings are not linked at -V 2 -).
  • f represents an integer of 1 to 3, and from the viewpoint of easily improving the dispersibility of the polymer (B) in the composition and film and improving the hygroscopic resistance and heat resistance of the resulting film, Preferably 1 or 2, more preferably 1.
  • f 2
  • a structure in which R 23 and R 24 are bonded to a naphthalene ring is shown
  • f 3
  • a structure in which R 23 and R 24 are bonded to an anthracene ring is shown.
  • R 27 to R 30 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the alkyl group having 1 to 6 carbon atoms include those exemplified above as the alkyl group having 1 to 6 carbon atoms in the formulas (2) and (3).
  • R 27 to R 30 are each independently hydrogen.
  • An atom or an alkyl group having 1 to 3 carbon atoms is more preferred, a hydrogen atom or a methyl group is more preferred, and a hydrogen atom is even more preferred.
  • Z represents a single bond, -C(CH 3 ) 2 - or -C(CF 3 ) 2 -.
  • Z has such a structure, the dispersibility of the polymer (B) in the composition and film can be easily improved, and the hygroscopic resistance and heat resistance of the obtained film can be easily improved.
  • i represents an integer of 1 to 3, preferably 1 or 2 from the viewpoint of easily increasing the dispersibility of the polymer (B) in the composition and film and easily improving the moisture absorption resistance and heat resistance of the resulting film. be.
  • i is 2 or more, a plurality of Zs and R 27 to R 30 may be the same or different.
  • Y in formula (1) contains at least one selected from the group consisting of structures represented by formulas (31) to (33)
  • Y is represented by at least one selected from the group consisting of structures represented by formulas (31) to (33).
  • the amount is preferably 30 mol % or more, more preferably 50 mol % or more, still more preferably 70 mol % or more, particularly preferably 90 mol % or more, and preferably 100 mol % or less.
  • Y in formula (1) is selected from the group consisting of structures represented by formulas (31) to (33). It is easy to improve the dispersibility of the polymer (B) inside and in the film, and it is easy to improve the moisture absorption resistance and heat resistance of the obtained film.
  • Y in formula ( 1 ) is represented by at least one selected from the group consisting of structures represented by formulas (31) to (33). It can be measured or calculated from the feed ratio of raw materials.
  • the polyimide resin (A) in the present invention includes, in addition to the structural unit represented by formula (1), the structural unit represented by formula (52), the structural unit represented by formula (53), and the formula ( 54) may contain at least one selected from the group consisting of structural units represented by
  • Y 1 represents a tetravalent organic group
  • Y 2 represents a trivalent organic group
  • X 1 and X 2 independently represent a divalent organic group
  • * represents a bond
  • G and X independently represent a divalent organic group
  • * represents a bond
  • Y 1 has the same meaning as Y in formula (1)
  • X 1 and X 2 have the same meaning as X in formula (1).
  • Y 2 in formula (53) is preferably a group in which one of the bonds of Y in formula (1) is replaced with a hydrogen atom.
  • Y 2 is a group in which any one of the bonds (structures) of the groups (structures) represented by formulas (31) to (38) is replaced with a hydrogen atom; a trivalent chain hydrocarbon having 1 to 8 carbon atoms and the like.
  • the polyimide resin may contain multiple types of Y 1 or Y 2 , and the multiple types of Y 1 or Y 2 may be the same or different.
  • each G is independently a divalent organic group, preferably substituted with a hydrocarbon group having 1 to 8 carbon atoms or a fluorine-substituted hydrocarbon group having 1 to 8 carbon atoms. may be substituted with a divalent organic group having 2 to 100 carbon atoms, more preferably a hydrocarbon group having 1 to 8 carbon atoms or a fluorine-substituted hydrocarbon group having 1 to 8 carbon atoms. It represents a divalent organic group having 2 to 100 carbon atoms and having a cyclic structure. Cyclic structures include alicyclic, aromatic and heterocyclic structures.
  • Examples of the organic group for G include, for example, a group in which two non-adjacent bonds among the bonds of the groups represented by formulas (31) to (38) are replaced with hydrogen atoms, and a divalent carbon chain having 6 or less carbon atoms. Examples thereof include hydrogen groups, and preferably groups in which two non-adjacent bonds of the groups represented by formulas (39) to (51) are replaced with hydrogen atoms.
  • X in formula (54) is synonymous with X in formula (1), and when the polyimide resin contains a structural unit represented by formula (1) and a structural unit represented by formula (54), each X in the structural units may be the same or different.
  • the polyimide resin may contain multiple types of X or G, and the multiple types of X or G may be the same or different.
  • the polyimide resin (A) is a structural unit represented by formula (1), and optionally a structural unit represented by formula (52), represented by formula (53) It consists of at least one structural unit selected from structural units and structural units represented by formula (54).
  • the polyimide resin (A) has the formula (1)
  • the ratio of the structural units represented by all the structural units contained in the polyimide resin, for example, the structural unit represented by formula (1), and optionally the structural unit represented by formula (52), the formula (53) Based on the total molar amount of at least one structural unit selected from structural units represented by and structural units represented by formula (54), preferably 80 mol% or more, more preferably 90 mol% or more, and further Preferably, it is 95 mol % or more.
  • the upper limit of the proportion of the structural unit represented by formula (1) is 100 mol % or less.
  • the above ratio can be measured, for example, using 1 H-NMR, or can be calculated from the charging ratio of raw materials.
  • the polyimide resin (A) in the present invention is preferably a polyimide from the viewpoint of easily improving the dispersibility of the polymer (B) in the composition and the film and easily improving the moisture absorption resistance and heat resistance of the resulting film. Resin.
  • the polyimide-based resin (A) in the present invention may contain halogen atoms, preferably fluorine atoms, which can be introduced by, for example, the above halogen-containing atom substituents.
  • halogen atoms preferably fluorine atoms
  • the polyimide resin (A) contains a halogen atom, preferably a fluorine atom, it is easy to increase the dispersibility of the polymer (B) in the composition and the film, and the resulting film tends to be improved in hygroscopic resistance and heat resistance. In addition, it is easy to improve the optical characteristics.
  • Preferred fluorine-containing substituents for allowing the polyimide resin (A) to contain fluorine atoms include, for example, a fluoro group and a trifluoromethyl group.
  • the content of the halogen atoms in the polyimide resin (A) is preferably 0.1 to 40% by mass, based on the mass of the polyimide resin (A), More preferably 1 to 35 mass %, still more preferably 5 to 30 mass %.
  • the halogen atom content is at least the above lower limit, the dispersibility of the polymer (B) in the composition and film is likely to be enhanced, and the hygroscopic resistance and heat resistance of the resulting film are likely to be enhanced.
  • the halogen atom content is equal to or less than the above upper limit, the CTE of the film can be reduced, and synthesis is facilitated.
  • the imidization rate of the polyimide resin (A) is preferably 90% or more, more preferably 93% or more, still more preferably 95% or more, and usually 100% or less. From the viewpoint of easily improving the dielectric properties, optical properties, moisture absorption resistance, and heat resistance of the film, the imidization rate is preferably at least the above lower limit.
  • the imidization rate indicates the ratio of the molar amount of imide bonds in the polyimide resin (A) to twice the molar amount of the structural units derived from the tetracarboxylic acid compound in the polyimide resin (A).
  • the polyimide resin (A) contains a tricarboxylic acid compound
  • a value twice the molar amount of the structural unit derived from the tetracarboxylic acid compound in the polyimide resin (A), and derived from the tricarboxylic acid compound It shows the ratio of the molar amount of the imide bond in the polyimide resin (A) to the total of the molar amount of the constituent units.
  • the imidization rate can be determined by IR method, NMR method, or the like.
  • the polyimide resin (A) in the present invention includes a precursor before imidization of the polyimide resin, as described above.
  • the polyimide resin (A) is a polyamic acid
  • the polyamic acid has the formula (1′): [In formula (1′), Y and X respectively represent Y and X in formula (1)] Including the structural unit represented by.
  • Tg of the polyimide resin (A) is preferably 100°C or higher, more preferably 150°C or higher, still more preferably 200°C or higher, still more preferably 220°C, particularly preferably 300°C or higher, and particularly preferably 350°C. above, preferably 550° C. or below.
  • Tg of the polyimide resin (A) is at least the above lower limit, it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
  • the Tg of the polyimide resin (A) is equal to or less than the above upper limit, the mechanical properties are likely to be improved.
  • the Tg of the polyimide resin (A) can be obtained, for example, by performing dynamic viscoelasticity measurement (hereinafter sometimes abbreviated as DMA measurement), and can be measured by the method described in Examples.
  • DMA measurement dynamic viscoelasticity measurement
  • Mw of the polyimide resin (A) is preferably 50,000 or more, more preferably 100,000 or more, more preferably 150,000 or more, still more preferably 200,000 or more, still more preferably 250 in terms of polystyrene. ,000 or more, particularly preferably 300,000 or more, preferably 1,000,000 or less, more preferably 800,000 or less, even more preferably 700,000 or less, even more preferably 500,000 or less, particularly preferably is less than or equal to 450,000.
  • Mw of the polyimide resin (A) is at least the above lower limit, it is easy to improve the hygroscopic resistance, heat resistance and mechanical properties of the resulting film.
  • the Mw of the polyimide resin (A) is equal to or less than the above upper limit, the moldability is likely to be improved.
  • the Mw of the polyimide resin (A) can be obtained, for example, by GPC measurement and standard polystyrene conversion, for example, by the method described in Examples.
  • the content of the polyimide resin (A) contained in the composition of the present invention is preferably 50 mass with respect to the total mass of the polyimide resin (A) and the polymer (B). % or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 93% by mass or less, and even more preferably 90% by mass % or less, particularly preferably 80 mass % or less.
  • the content of the polyimide resin (A) is at least the above lower limit, film formation is facilitated, which is advantageous from the viewpoint of film production.
  • the content of the polyimide-based resin (A) is equal to or less than the above upper limit, the dispersibility of the polymer (B) in the composition is likely to be improved, and thus the hygroscopic resistance and heat resistance of the resulting film are likely to be improved.
  • the method for producing the polyimide resin (A) is not particularly limited, but for example, it can be produced by a method including a step of reacting a diamine compound and a tetracarboxylic acid compound to obtain a polyamic acid, and a step of imidizing the polyamic acid. .
  • a step of obtaining polyamic acid may be carried out.
  • a dicarboxylic acid compound and a tricarboxylic acid compound may be reacted.
  • the tetracarboxylic acid compound used in the synthesis of the polyimide resin (A) includes aromatic tetracarboxylic acid compounds such as aromatic tetracarboxylic dianhydride; and aliphatic tetracarboxylic acid compounds such as aliphatic tetracarboxylic dianhydride. acid compounds and the like.
  • a tetracarboxylic acid compound may be used independently and may be used in combination of 2 or more type.
  • the tetracarboxylic acid compound may be a dianhydride or a tetracarboxylic acid compound analog such as an acid chloride compound.
  • tetracarboxylic acid compounds include pyromellitic anhydride (hereinafter sometimes abbreviated as PMDA), 4,4'-(4,4'-isopropylidenediphenoxy) diphthalic anhydride (hereinafter abbreviated as BPADA).
  • PMDA pyromellitic anhydride
  • BPADA 4,4'-(4,4'-isopropylidenediphenoxy) diphthalic anhydride
  • 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride (hereinafter sometimes abbreviated as BPDA), 4,4'-(Hexafluoroisopropylidene)diphthalic dianhydride (hereinafter sometimes abbreviated as 6FDA), 4,4'-oxydiphthalic anhydride (hereinafter sometimes abbreviated as ODPA), 2,2 ',3,3'-, 2,3,3',4'- or 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic acid acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3',3,4'-diphenylethertetracarboxylic dianhydride, bis(2,3-dicarboxy
  • PMDA BPDA
  • 6FDA BPADA
  • ODPA ODPA
  • HPMDA HPMDA
  • CBDA CBDA
  • TAHQ tetracarboxylic acid compounds
  • Diamine compounds used for synthesizing the polyimide resin (A) include, for example, aliphatic diamines, aromatic diamines, and mixtures thereof.
  • the “aromatic diamine” represents a diamine having an aromatic ring, and may contain an aliphatic group or other substituents in a part of its structure.
  • This 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 fluorene ring. Among these, a benzene ring is preferred.
  • the term "aliphatic diamine” refers to a diamine having an aliphatic group, which may contain other substituents in part of its structure, but does not have an aromatic ring.
  • diamine compounds include 1,4-diaminocyclohexane, 4,4'-diamino-2,2'-dimethylbiphenyl (hereinafter sometimes referred to as m-TB), 4,4'-diamino- 3,3'-dimethylbiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl (hereinafter sometimes referred to as TFMB), 4,4'-diaminodiphenyl ether, 1,3 -bis(3-aminophenoxy)benzene (hereinafter sometimes abbreviated as 1,3-APB), 1,4-bis(4-aminophenoxy)benzene (hereinafter sometimes abbreviated as 1,4-APB) , 1,3-bis(4-aminophenoxy)benzene, 2,2′-bis[4-(4-aminophenoxy)phenyl]propane (hereinafter sometimes referred to as BAPP
  • 1,4-diaminocyclohexane, 4,4'-diaminodiphenyl ether, TFMB, and 4 are preferred from the viewpoint of easily increasing the dispersibility of the polymer (B) and easily improving the moisture absorption resistance and heat resistance of the resulting film.
  • the polyimide resin (A) in addition to the tetracarboxylic acid compound used in the resin synthesis, other tetracarboxylic acids, dicarboxylic acids and tricarboxylic acids and their Anhydrides and derivatives may be further reacted.
  • tetracarboxylic acids include water adducts of the above tetracarboxylic acid compound anhydrides.
  • dicarboxylic acid compounds include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, their analogous acid chloride compounds, acid anhydrides, and the like, which may be used alone or in combination of two or more. Specific examples include terephthalic acid; isophthalic acid; naphthalenedicarboxylic acid; 4,4′-biphenyldicarboxylic acid; 3,3′-biphenyldicarboxylic acid; compounds in which two benzoic acids are linked by a single bond, —O—, —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —SO 2 — or a phenylene group, and their acid chloride compounds.
  • tricarboxylic acid compounds include aromatic tricarboxylic acids, aliphatic tricarboxylic acids, their analogous acid chloride compounds, acid anhydrides, and the like, which may be used alone or in combination of two or more. Specific examples include anhydride of 1,2,4-benzenetricarboxylic acid; 2,3,6-naphthalenetricarboxylic acid-2,3-anhydride; a single bond between phthalic anhydride and benzoic acid; , —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —SO 2 — or compounds linked by a phenylene group.
  • the amounts of the diamine compound, the tetracarboxylic acid compound, the dicarboxylic acid compound and the tricarboxylic acid compound to be used can be appropriately selected according to the desired ratio of each structural unit of the resin.
  • the amount of the diamine compound used is preferably 0.94 mol or more, more preferably 0.96 mol or more, still more preferably 0.98 mol or more, and particularly It is preferably 0.99 mol or more, preferably 1.20 mol or less, more preferably 1.10 mol or less, still more preferably 1.05 mol or less, and particularly preferably 1.02 mol or less.
  • the amount of the diamine compound used relative to the tetracarboxylic acid compound is within the above range, the dispersibility of the polymer (B) in the composition and the film is easily improved, and the moisture absorption resistance and heat resistance of the resulting film are easily improved.
  • the reaction temperature of the diamine compound and the tetracarboxylic acid compound is not particularly limited, and may be, for example, 5 to 200° C.
  • the reaction time is also not particularly limited, and may be, for example, about 0.5 to 72 hours.
  • the reaction temperature is preferably 5-50° C., more preferably 10-40° C.
  • the reaction time is preferably 3-24 hours. With such a reaction temperature and reaction time, it is easy to improve the dispersibility of the polymer (B) in the composition and the film, and it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
  • the reaction between the diamine compound and the tetracarboxylic acid compound is preferably carried out in a solvent.
  • the solvent is not particularly limited as long as it does not affect the reaction, but examples include water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, Alcohol solvents such as 2-butoxyethanol and propylene glycol monomethyl ether; Phenolic solvents such as phenol and cresol; Ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, ⁇ -butyrolactone (hereinafter sometimes referred to as GBL) , ⁇ -valerolactone, propylene glycol methyl ether acetate, ethyl lactate and other ester solvents; acetone, methyl ethyl ketone, cyclopentanone, cyclohexan
  • the reaction between the diamine compound and the tetracarboxylic acid compound may be carried out under an inert atmosphere such as a nitrogen atmosphere or an argon atmosphere or under reduced pressure conditions, for example, an inert atmosphere such as a nitrogen atmosphere or an argon atmosphere. It is preferable to carry out with stirring in a strictly controlled dehydrated solvent.
  • imidization may be performed using an imidization catalyst, imidization by heating, or a combination thereof.
  • the imidization catalyst used in the imidization step include aliphatic amines such as tripropylamine, dibutylpropylamine and ethyldibutylamine; N-ethylpiperidine, N-propylpiperidine, N-butylpyrrolidine, N-butylpiperidine, and alicyclic amines (monocyclic) such as N-propylhexahydroazepine; azabicyclo[2.2.1]heptane, azabicyclo[3.2.1]octane, azabicyclo[2.2.2]octane, and Alicyclic amines (polycyclic) such as azabicyclo[3.2.2]nonane; and pyridine, 2-methylpyridine (2-picoline), 3-methylpyridine (3-picoline), 4-methylpyridine (4
  • Acid anhydrides include conventional acid anhydrides used in imidization reactions, and specific examples thereof include aliphatic acid anhydrides such as acetic anhydride, propionic anhydride and butyric anhydride, and aromatic acid anhydrides such as phthalic acid. and acid anhydrides.
  • the imidization step by heating may be performed in a solvent in which the polyamic acid is dissolved, or may be performed in a film state as described later.
  • the reaction temperature is usually 20 to 250°C, and the reaction time is preferably 0.5 to 24 hours, more preferably 1 to 12 hours.
  • the polyimide resin (A) can be separated and purified by a conventional method such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination thereof.
  • the resin can be isolated by adding a large amount of alcohol such as methanol to the reaction solution containing the resin to precipitate the resin, followed by concentration, filtration, drying, and the like.
  • the composition of the present invention contains a polyimide resin (A), a polymer (B) and a phenolic antioxidant, the phenolic antioxidant contains a substituent P, and the substituent P in the phenolic antioxidant is
  • the structure S in which the hydrogen atom is substituted has an aromatic ring which may have a substituent. Therefore, it is excellent in moisture absorption resistance, and can effectively suppress deterioration of dielectric properties due to moisture absorption of the film. In addition, it is excellent in heat resistance, and even if the film is placed in a high-temperature environment, deterioration due to oxidation of the polymer (B) can be effectively suppressed. Therefore, the film formed from the composition of the present invention can have both excellent moisture absorption resistance and excellent heat resistance.
  • the specific phenolic antioxidant can effectively suppress the oxidation of the polymer (B) during film formation, which can reduce moisture resistance and the like.
  • deterioration of moisture absorption resistance etc. can also occur due to deterioration of deposits adhering to the surface (for example, dispersants such as surfactants and protective materials). It is thought that the alteration of the
  • the distance between the HSP values of the polymer (B) and the phenolic antioxidant is preferably 2.1 or more, more preferably 2.3 or more, still more preferably 2.5 or more, and More preferably 3.0 or more, particularly preferably 3.2 or more.
  • the affinity between the phenolic antioxidant and the polymer (B) is not too high, and the phenolic antioxidant tends to uniformly cover the polymer (B). It is easy to suppress the oxidation of (B), and it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
  • the distance between the HSP values of the phenolic antioxidant and the polymer (B) is preferably 16.0 or less, more preferably 12.0 or less, even more preferably 9.0 or less, still more preferably 6.0 or less, and even more preferably 6.0 or less. is preferably 5.5 or less, particularly preferably 5.0 or less, even more preferably 4.5 or less, and even more preferably 4.0 or less.
  • the distance between the HSP values is equal to or less than the above upper limit, the phenolic antioxidant tends to approach or adsorb to the polymer (B), and tends to cover the polymer (B), thereby suppressing oxidation of the polymer (B). It is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
  • the distance between HSP values between polymer (B) and structure S is preferably 1.5 or more, more preferably 2.0 or more, still more preferably 2.4 or more, still more preferably 2.6 or more.
  • the affinity between the phenolic antioxidant and the polymer (B) is not too high, and the phenolic antioxidant tends to uniformly cover the polymer (B). It is easy to suppress the oxidation of (B), and it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
  • the distance between the HSP values of structure S and polymer (B) is preferably 15.5 or less, more preferably 12.0 or less, still more preferably 10.0 or less, even more preferably 7.5 or less, even more preferably is 5.0 or less, particularly preferably 4.0 or less, particularly more preferably 3.5 or less, and even more preferably 3.0 or less.
  • the phenolic antioxidant tends to approach or adsorb to the polymer (B), and tends to cover the polymer (B), thereby suppressing oxidation of the polymer (B). It is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
  • the distance between the HSP values between the structure S and the polymer (B) is the HSP value between the phenolic antioxidant and the polymer (B) It is preferably smaller than the inter-HSP value distance (hereinafter also referred to as inter-HSP value distance (2)).
  • inter-HSP value distance (2) the inter-HSP value distance
  • the fact that the HSP value distance (1) is smaller than the HSP value distance (2) means that the portion of the structure S of the phenolic antioxidant has a particularly high affinity with the polymer (B), and oxidation Since the portion of the structure S of the inhibitor is easily adsorbed to the polymer (B) so that it is in contact with the polymer (B), the substituent P of the phenolic antioxidant tends to be uniformly present around the polymer (B), and as a result, the polymer ( The unstable radicals generated by the oxidation in B) are likely to be trapped by the substituent P. The radical of the substituent P generated by trapping the radical can further trap the radical of the polymer (B) and inactivate the polymer (B).
  • the absolute value of the difference between the distance between HSP values (1) and the distance between HSP values (2) is preferably 0.1 or more, more preferably is 0.2 or more, more preferably 0.3 or more, even more preferably 0.4 or more, and particularly preferably 0.5 or more.
  • the absolute value of the difference between the distance between HSP values (1) and the distance between HSP values (2) is such that the phenolic antioxidant easily adsorbs uniformly to the polymer (B), and the phenolic antioxidant Preferably 4.0 or less, more preferably 3.0 or less, still more preferably 2.0 or less, and even more preferably is 1.5 or less, particularly preferably 1.0 or less.
  • the distance between the HSP values of the phenolic antioxidant and the polyimide resin (A) suppresses the oxidation of the polymer (B) because the phenolic antioxidant easily covers the polymer (B). from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the film, preferably 5.0 or more, more preferably 8.0 or more, still more preferably 8.5 or more, still more preferably 9.5 or more, It is particularly preferably 10.0 or more, and particularly more preferably 11.0 or more. Further, the distance between the HSP values of the phenolic antioxidant and the polyimide resin (A) is preferably 16.0 or less, from the viewpoint of easily preventing aggregation of the phenolic antioxidant in the composition or film. It is more preferably 15.0 or less, still more preferably 13.0 or less, and even more preferably 12.5 or less.
  • the distance between the HSP values of the structure S and the polyimide resin (A) is preferably 5.0 or more, more preferably 7.0 or more, still more preferably 8.0 or more, and still more Preferably 9.0 or more, particularly preferably 10.0 or more, preferably 15.0 or less, more preferably 14.0 or less, still more preferably 13.0 or less, still more preferably 12.0 or less .
  • the distance between HSP values is equal to or less than the upper limit or equal to or more than the lower limit, it is easy to suppress oxidation of the polymer (B), and it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
  • the distance between the HSP values of the polyimide resin (A) and the polymer (B) is preferably 6.0 or more, more preferably 6.5 or more, still more preferably 7.0 or more, Even more preferably, it is 8.0 or more. If the distance between the HSP values of the polyimide resin (A) and the polymer (B) is at least the above lower limit, an interface is likely to form between the polymer (B) and the polyimide resin (A), so phenolic oxidation The inhibitor is easily adsorbed so as to cover the polymer (B), and the polymer (B) is easily prevented from being oxidized.
  • the distance between the HSP values of the polyimide resin (A) and the polymer (B) is preferably 30.0 or less, more preferably 25.0 or less, still more preferably 20, from the viewpoint of affinity between the resin and the polymer. .0 or less, and even more preferably 15.0 or less.
  • the composition of the present invention may further contain a solvent.
  • the distance between the HSP values of the phenolic antioxidant and the solvent is preferably 12.0 or more.
  • the polymer (B) contained in the composition of the present invention is hardly oxidized even during film formation, and the composition of the present invention is Easy to form a film with excellent moisture absorption resistance. This is because when the distance between the HSP values between the phenolic antioxidant and the solvent is 12.0 or more, the phenolic antioxidant is difficult to dissolve and disperse in the solvent, so the affinity with the polymer (B) is relatively high.
  • the phenolic antioxidant becomes more likely to approach the polymer (B), and the phenolic antioxidant covers the polymer (B), so that the phenolic antioxidant can oxidize the polymer (B). It is considered that this is because the preventive effect increases. Furthermore, since the polymer (B) is formed into a film so as to cover the surroundings thereof, the polymer (B) is likely to exhibit a heat resistance function, and even when the resulting film is exposed to a high temperature environment, oxidation of the polymer (B) is likely to be suppressed.
  • the distance between the HSP values of the phenolic antioxidant and the solvent is preferably 12.5 or more, more preferably 13.0 or more, still more preferably 14.0 or more, still more preferably 16 0.0 or more, particularly preferably 16.5 or more, and particularly more preferably 17.0 or more.
  • the phenolic antioxidant tends to surround the polymer (B), and the phenolic antioxidant surrounds the polymer (B) to form a film. Therefore, oxidation of the polymer (B) is easily suppressed, and the hygroscopic resistance and heat resistance of the obtained film are easily improved.
  • the upper limit of the distance between the HSP values of the phenolic antioxidant and the solvent is preferably 30 or less, more preferably 25 or less, still more preferably 20 or less.
  • the phenolic antioxidant tends to disperse in the solvent, so that oxidation of the polymer (B) can be easily suppressed.
  • the Hansen Solubility Parameters ⁇ D, ⁇ P, and ⁇ H can be calculated using HSPiP (Hansen Solubility Parameters in Practice), a program developed by Dr. Hansen's group who proposed the Hansen Solubility Parameters, according to the Hansen Solubility Sphere Method. For example, Ver. 4.1.07 and the like can be used. Details of the Hansen melting ball method are described below. A component of interest is dissolved in a solvent with a known HSP value, and the solubility of the component in a specific solvent is evaluated. Solubility evaluation is performed by visually judging whether or not each target component is dissolved in the solvent. This is done for multiple solvents.
  • the HSP of the target component As for the types of solvents, it is preferable to use solvents having a wide range of different ⁇ t.
  • the center coordinates ( ⁇ d, ⁇ p, ⁇ h) of the Hansen sphere obtained by inputting the obtained solubility evaluation results into HSPiP are used as the HSP of the target component.
  • the HSP may be obtained by using, for example, numerical values in the HSPiP database or literature values, or may be determined from the structural formula using HSPiP.
  • the value of the Hansen solubility parameter is referred to as the HSP value
  • the HSP value represents the value at 25°C.
  • the HSP value of the polyimide resin (A), the HSP value of the polymer (B), and the HSP value of the solvent may each be determined by any of the methods described above, for example, by the methods described in the Examples.
  • the distance between the Hansen solubility parameters (hereinafter sometimes abbreviated as HSP) of two substances is called the distance between HSP values.
  • the inter-HSP distance (Ra) is an index representing the affinity between both substances, and the smaller the value, the higher the affinity between the two substances. Conversely, the larger the Ra value, the lower the affinity between the two substances, that is, the less compatible they are.
  • ⁇ A ( ⁇ DA, ⁇ PA, ⁇ HA)
  • ⁇ B ( ⁇ DB, ⁇ PB, ⁇ HB)
  • Ra [4 ⁇ ( ⁇ DA ⁇ DB) 2 +( ⁇ PA ⁇ PB) 2 +( ⁇ HA ⁇ HB) 2 ] 0.5
  • Y can be calculated by
  • the HSP value and the distance between HSP values are as defined above, and can be obtained according to the above method.
  • the phenolic antioxidant preferably has a distance between the HSP values of the structure S and the solvent of 10.0 or more, more preferably 12.3 or more, and even more preferably 12.5. 12.7 or more, particularly preferably 13.0 or more, particularly more preferably 13.5 or more, even more preferably 14.0 or more, extremely preferably 15.0 or more, extremely more preferably 16.0 or higher, and very preferably 17.0 or higher.
  • the distance between the HSP values is at least the above lower limit, the phenolic antioxidant is difficult to dissolve and disperse in the solvent and easily covers the polymer (B). It is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
  • the upper limit of the distance between the HSP values of Structure S and the solvent is preferably 30.0 or less, more preferably 25.0 or less, and even more preferably 20.0 or less.
  • the distance between the HSP values is equal to or less than the above upper limit, the phenolic antioxidant is prevented from aggregating in the composition, and the surroundings of the polymer (B) are easily covered, so oxidation of the polymer (B) is easily suppressed. .
  • a solvent having an HSP value distance of 12.0 or more with a phenolic antioxidant (hereinafter sometimes referred to as a "first solvent”) is not particularly limited, and for example, N,N-dimethylacetamide (hereinafter , sometimes referred to as DMAc), amide solvents such as NN-dimethylformamide (hereinafter sometimes referred to as DMF); ⁇ -butyrolactone (hereinafter sometimes referred to as GBL), ⁇ - lactone solvents such as valerolactone; sulfur-containing solvents such as dimethylsulfone, dimethylsulfoxide and sulfolane; carbonate solvents such as ethylene carbonate and propylene carbonate; pyrrolidone solvents such as N-methylpyrrolidone; .
  • DMAc N,N-dimethylacetamide
  • DMF amide solvents
  • GBL ⁇ -butyrolactone
  • ⁇ - lactone solvents such as valerolactone
  • sulfur-containing solvents
  • amide-based solvents lactone-based solvents, and pyrrolidone-based solvents are preferred.
  • the affinity between the phenolic antioxidant and the polymer (B) is relatively increased, the phenolic antioxidant is easily adsorbed to the polymer (B), and the polymer (B) Aggregation of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily improved, so that the moisture absorption resistance and heat resistance of the obtained film can be easily improved.
  • the dispersibility of the polymer (B) in the composition increases, so the moisture absorption resistance, surface smoothness, dielectric properties and mechanical properties of the film tend to increase, and the film physical properties, such as variation in thermal conductivity of the film, coefficient of linear expansion (hereinafter referred to as CTE), and surface roughness of the film.
  • CTE coefficient of linear expansion
  • mechanical properties refer to mechanical properties including bending resistance and elastic modulus, and increasing or improving mechanical properties means, for example, increasing bending resistance and/or elastic modulus. show.
  • a solvent can be used individually or in combination of 2 or more types.
  • the distance between the HSP values of the first solvent and the polymer (B) is preferably 8.0 or more, more preferably 8.5 or more, even more preferably 9.0 or more, and particularly preferably is 10.0 or more, and more preferably 11.0 or more.
  • the distance between the HSP values is at least the above lower limit, the affinity between the phenolic antioxidant and the polymer (B) is relatively increased, and the phenolic antioxidant is easily adsorbed to the polymer (B), and , when the polymer (B) is particulate, the dispersibility of the polymer (B) is likely to be enhanced.
  • the upper limit of the distance between the HSP values between the first solvent and the polymer (B) is preferably 30.0 or less, more preferably 25.0 or less, still more preferably 20.0 or less.
  • the distance between the HSP values of the first solvent and the polymer (B) is equal to or less than the above upper limit, aggregation of the polymer (B) is likely to be suppressed, and dispersibility of the polymer (B) is likely to be enhanced. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
  • the first solvent is preferably a solvent in which the polymer (B) does not dissolve.
  • a solvent in which the polymer (B) does not dissolve.
  • an interface is easily formed, so the phenolic antioxidant is easily adsorbed to the polymer (B), and aggregation of the polymer (B) is easily suppressed, and the dispersibility of the polymer (B) is improved.
  • Cheap it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
  • the evaluation of whether “dissolves” or “does not dissolve” can be performed according to the method described in ⁇ Evaluation of Solubility> in Examples.
  • the distance between the HSP values of the first solvent and polymer (B) is preferably larger than the interaction radius of polymer (B).
  • the polymer (B) is less likely to be dissolved in the first solvent, so aggregation of the polymer (B) is easily suppressed and the dispersibility of the polymer (B) is easily improved.
  • the interaction radius means a plurality of solvents capable of dissolving a specific polymer, that is, when the Hansen solubility parameters of good solvents are plotted in a three-dimensional HSP space, the plots of each good solvent are similar to each other.
  • a solute with a large interaction radius is soluble in many solvents
  • a solute with a small interaction radius is soluble in a small number of solvents, and is difficult to dissolve in a large number of solvents.
  • a solubility test is conducted to determine whether various solvents are good solvents or poor solvents. A radius is calculated.
  • the "interaction radius" is as defined above and can be determined according to the above method.
  • the distance between the HSP values of the first solvent and the polyimide resin (A) is preferably 11.0 or less, more preferably 10.0 or less, still more preferably 9.5 or less, and more preferably 9.0 or less, particularly preferably 8.5 or less, preferably 0.01 or more, more preferably 0.1 or more, still more preferably 1.0 or more, still more preferably 3.0 or more, Especially preferably, it is 5.0 or more.
  • the distance between the HSP values is the above upper limit or less, the affinity between the first solvent and the polyimide resin (A) can be improved, so that the dispersibility of the polymer (B) can be easily increased, and the resulting film It is easy to improve the moisture absorption resistance and heat resistance of
  • the first solvent is preferably a solvent in which the polyimide resin (A) dissolves.
  • a solvent facilitates dispersion of the polymer (B) in the resulting composition and film.
  • the film tends to form a sea-island structure.
  • the distance between the HSP values of the first solvent and the polyimide resin (A) is preferably smaller than the interaction radius of the polyimide resin (A).
  • the content of the first solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more, relative to the mass of the composition of the present invention. Even more preferably 80% by mass or more, particularly preferably 90% by mass or more, preferably 99% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less.
  • the content of the first solvent is within the above range, an interface is easily formed, so the phenolic antioxidant is easily adsorbed to the polymer (B), and aggregation of the polymer (B) is easily suppressed.
  • the composition of the present invention may contain a second solvent in addition to the first solvent whose HSP value distance to the phenolic antioxidant is 12.0 or more.
  • the composition contains the second solvent in addition to the first solvent, it is easy to prepare a composition containing the particulate polymer (B) with a reduced particle size.
  • the second solvent examples include hydrocarbon solvents such as benzene, toluene, pentane, hexane, heptane, cyclohexane, and xylene; halogenated hydrocarbon solvents such as dichloromethane and ethylene dichloride; acetone, methyl ethyl ketone, cyclopentanone, and cyclohexanone. , 2-heptanone, and ketone solvents such as methyl isobutyl ketone.
  • hydrocarbon-based solvents and/or ketone-based solvents are preferable, and hydrocarbon-based solvents are more preferable.
  • a 2nd solvent can be used individually or in combination of 2 or more types.
  • the distance between the HSP values of the second solvent and the phenolic antioxidant is preferably 0.5 or more, more preferably 0.8 or more, still more preferably 1.0 or more, and even more preferably Preferably it is 1.5 or more.
  • the upper limit of the distance between the HSP values of the second solvent and the phenolic antioxidant is usually 15 or less, preferably 10 or less, more preferably 8.0 or less, even more preferably 5.0 or less, and even more preferably 2.5 or less, particularly preferably 2.0 or less.
  • the phenolic antioxidant is likely to be adsorbed to the polymer (B), and the hygroscopic resistance and heat resistance of the resulting film are likely to be improved.
  • the distance between the HSP values of the second solvent and the polymer (B) is preferably 8.0 or less, more preferably 7.0 or less, even more preferably 6.0 or less, even more preferably is 5.0 or less, particularly preferably 4.0 or less, particularly more preferably 3.0 or less, and even more preferably 2.5 or less.
  • the distance between the HSP values is equal to or less than the above upper limit, the solubility of the polymer (B) in the second solvent is increased, so that the dispersibility of the polymer (B) is likely to be increased.
  • the phenolic antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
  • the lower limit of the distance between HSP values is usually greater than zero.
  • the second solvent is preferably a solvent in which the polymer (B) dissolves.
  • a solvent tends to improve the dispersibility of the polymer (B).
  • the phenolic antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
  • the distance between the HSP values of the second solvent and the polymer (B) is preferably smaller than the interaction radius of the polymer (B). Such a relationship facilitates dissolution of the polymer (B) in the second solvent, thereby enhancing the dispersibility of the polymer (B). In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
  • the distance between the HSP values of the second solvent and the polyimide resin (A) is preferably 4.0 or more, more preferably 5.0 or more, still more preferably 6.0 or more, and further It is more preferably 7.0 or higher, particularly preferably 8.0 or higher, and particularly preferably 9.0 or higher.
  • the distance between the HSP values is at least the above lower limit, the polyimide resin (A) is difficult to dissolve in the second solvent, so the formation of aggregates of the polymer (B) is easily suppressed, and the polymer (B) is dispersed. easy to enhance. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
  • the upper limit of the distance between the HSP values of the second solvent and the polyimide resin (A) is preferably 30.0 or less, more preferably 27.0 or less, still more preferably 25.0 or less, and even more preferably 23.0 or less. , and particularly preferably 21.0 or less.
  • the distance between the HSP values of the second solvent and the polyimide resin (A) is the above upper limit or less, aggregation of the polymer (B) is easily suppressed, so the dispersibility of the polymer (B) is easily increased, and It is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
  • the second solvent is preferably a solvent in which the polyimide resin (A) does not dissolve.
  • a solvent tends to enhance the dispersibility of the polymer (B).
  • the phenolic antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
  • the distance between the HSP values of the second solvent and the polyimide resin (A) is preferably larger than the interaction radius of the polyimide resin (A).
  • the polyimide resin (A) is less likely to be dissolved in the second solvent, so the formation of aggregates of the polymer (B) is easily suppressed, and the dispersibility of the polymer (B) is easily enhanced.
  • the phenolic antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
  • the solubility of polymer (B) in the second solvent is preferably greater than the solubility of polymer (B) in the first solvent.
  • Such a relationship tends to suppress the formation of aggregates of the polymer (B), and tends to increase the dispersibility of the polymer (B).
  • the phenolic antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
  • the solubility of the polymer (B) in solvents can be measured by the following method. 1000 mg of polymer (B) and 3 mL of solvent are added to a sample bottle and stirred at room temperature for 2 hours.
  • the solubility in the second solvent is clearly is large, it is not necessary to measure the solubility.
  • the content of the second solvent that can be contained in the composition of the present invention is preferably 120 parts by mass or less, more preferably 100 parts by mass with respect to 100 parts by mass of the content of the first solvent. parts or less, more preferably 60 parts by mass or less, even more preferably 45 parts by mass or less, particularly preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, even more preferably 30 parts by mass or less, and even more preferably is less than 30 parts by mass, extremely preferably 25 parts by mass or less, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and still more preferably 0.1 parts by mass or more.
  • the content of the second solvent is equal to or less than the above upper limit, the formation of aggregates of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily enhanced. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film. It is easy to prepare a composition as content of a 2nd solvent is more than said minimum.
  • the composition of the present invention may contain a solvent other than the first solvent and the second solvent within a range that does not impair the effects of the present invention.
  • solvents are not particularly limited, and commonly used solvents can be used.
  • the total content of the first solvent, the second solvent and other solvents that can be contained in the composition of the present invention is preferably 50% by mass or more, based on the mass of the composition. More preferably 60% by mass or more, still more preferably 70% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, preferably 99% by mass or less, more preferably 97% by mass or less, More preferably, it is 95% by mass or less.
  • the total content is within the above range, the formation of aggregates of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily improved. Furthermore, it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
  • the total weight of the first solvent and the second solvent is preferably 50% by weight based on the total weight of the first solvent, the second solvent and other solvents that may be included in the composition. Above, more preferably 70% by mass or more, still more preferably 90% by mass or more, even more preferably 95% by mass or more, and preferably 100% by mass or less.
  • the total mass of the first solvent and the second solvent is within the above range, the formation of aggregates of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily improved. Furthermore, it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
  • the composition of the present invention preferably further contains a secondary antioxidant.
  • a secondary antioxidant By including the secondary antioxidant in addition to the phenolic antioxidant which is the primary antioxidant, it is easy to suppress oxidation of the polymer (B) and improve the hygroscopic resistance and heat resistance of the resulting film.
  • Secondary antioxidants include phosphorus antioxidants, sulfur antioxidants, and the like, and these secondary antioxidants can be used alone or in combination of two or more.
  • phosphorus-based antioxidants include, for example, tris(2,4-di-tert-butylphenyl)phosphite, triphenylphosphite, tris(nonylphenyl)phosphite, trilaurylphosphite.
  • trioctadecyl phosphite distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-Butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl) ) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4′-diphenylenediphosphonite, 2,2′-methylene
  • sulfur-based antioxidants include, for example, dilauryl 3,3'-thiodipropionate, tridecyl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl stearyl 3,3'-thiodipropionate, neopentanetetrayl tetrakis(3-laurylthiopropionate) and the like.
  • sulfur antioxidants can be used alone or in combination of two or more.
  • the content of the secondary antioxidant that can be contained in the composition of the present invention is preferably 0.002 parts by mass or more, more preferably 100 parts by mass of the polymer (B) 0.01 parts by mass or more, more preferably 0.04 parts by mass or more, still more preferably 0.1 parts by mass or more, and particularly preferably 1 part by mass or more.
  • the content of the secondary antioxidant is at least the above lower limit, the oxidation of the polymer (B) can be sufficiently suppressed, and the hygroscopic resistance and heat resistance of the film can be easily improved.
  • the content of the secondary antioxidant is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and still more preferably 7 parts by mass with respect to 100 parts by mass of the polymer (B). parts or less, particularly preferably 5 parts by mass or less.
  • the content of the secondary antioxidant is equal to or less than the above upper limit, the dielectric properties of the film are likely to be enhanced.
  • the content of the secondary antioxidant that can be contained in the composition of the present invention is preferably 5 parts by mass or more, more preferably 10 parts by mass with respect to 100 parts by mass of the phenolic antioxidant. It is at least 15 parts by mass, more preferably at least 20 parts by mass, particularly preferably at least 30 parts by mass.
  • the content of the secondary antioxidant is at least the above lower limit, the oxidation of the polymer (B) can be sufficiently suppressed, and the hygroscopic resistance and heat resistance of the film can be easily improved.
  • the content of the secondary antioxidant is preferably 1000 parts by mass or less, more preferably 700 parts by mass or less, still more preferably 600 parts by mass or less, still more preferably 500 parts by mass or less, relative to 100 parts by mass of the phenolic antioxidant. Part by mass or less, particularly preferably 200 parts by mass or less, particularly more preferably 150 parts by mass or less, and even more preferably 100 parts by mass or less.
  • the content of the secondary antioxidant is equal to or less than the above upper limit, the dielectric properties of the film are likely to be enhanced.
  • the composition of the present invention may contain additives as necessary within a range that does not impair the effects of the present invention.
  • additives include flame retardants, cross-linking agents, surfactants, compatibilizers, imidization catalysts, weathering agents, lubricants, anti-blocking agents, antistatic agents, anti-fogging agents, anti-drip agents, pigments, fillers, etc. is mentioned.
  • Additives can be used alone or in combination of two or more.
  • the composition of the present invention effectively suppresses the formation of aggregates of the polymer (B) even without containing a compatibilizer, and the polymer (B) exhibits high dispersibility.
  • the content of the compatibilizing agent is preferably 5 parts by mass or less, more preferably 1 part by mass or less, further preferably 0.1 part by mass or less, with respect to 100 parts by mass of the polyimide resin (A). 1 part by mass or less, still more preferably less than 0.1 part by mass, particularly preferably 0.05 part by mass or less, particularly more preferably 0.01 part by mass or less, and even more preferably 0.001 part by mass or less, Even more preferably, it may be 0 parts by mass.
  • the polyimide resin (A) is a polyimide resin precursor such as polyamic acid and thermal imidization is required during film production, inhibition of imidization by a compatibilizing agent or compatibilization by heating
  • the content of the compatibilizing agent is preferably less than 0.1 parts by mass within the above range from the viewpoint of preventing deterioration of the properties of the film due to deterioration of the agent.
  • the content of the compatibilizer may be based on 100 parts by mass of the polyimide resin (A) and the polymer (B) in place of 100 parts by mass of the polyimide resin (A).
  • the total mass of the polyimide resin (A) and polymer (B) contained in the composition is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass. It is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less.
  • the total mass of the polyimide resin (A) and the polymer (B) contained in the composition is within the above range, it is easy to suppress the formation of aggregates of the polymer (B), and the dispersibility of the polymer (B) is increased. Cheap.
  • the phenol-based antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
  • the method for producing the composition of the present invention is not particularly limited, for example, polyimide resin (A), polymer (B), phenolic antioxidant, and optionally solvent, secondary antioxidant, and additives etc., but in one preferred embodiment of the invention in which the polymer (B) is particulate, the following steps: Step (I) of preparing a dispersion containing particulate polymer (B) (hereinafter sometimes referred to as particulate polymer (B) dispersion); ) Step (II) of adding and preferably produced by a method of adding a phenolic antioxidant in the step (I) and/or the step (II).
  • Step (I) is a step of preparing a dispersion containing particulate polymer (B).
  • step (I) comprises, for example, the following steps: Step (1) of dissolving polymer (B) in a second solvent to obtain a polymer (B) solution; and after contacting the polymer (B) solution with the first solvent, distilling off the second solvent, Step (2) of obtaining a particulate polymer (B) dispersion
  • Step (1) of dissolving polymer (B) in a second solvent to obtain a polymer (B) solution
  • Step (2) of obtaining a particulate polymer (B) dispersion It is preferable that the step of preparing a particulate polymer (B) dispersion is performed by a method comprising: When such a step is included, aggregation of the particles of the polymer (B) can be suppressed, so that the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
  • Step (1) is a step of dissolving polymer (B) in a second solvent to obtain a polymer (B) solution.
  • the form of the polymer (B) dissolved in the second solvent is not particularly limited, and may be, for example, particulate, fibrous, sheet-like, or pellet-like.
  • the polymer (B) solution preferably contains 0.01 to 20% by mass of polymer (B) relative to the mass of the solution.
  • the content of the polymer (B) in the polymer (B) solution is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass, relative to the mass of the solution. % or more, more preferably 0.5 mass % or more, preferably 20 mass % or less, more preferably 10 mass % or less, and even more preferably 5 mass % or less.
  • the content of the polymer (B) in the solution is at least the above lower limit, it is easy to adjust the composition.
  • the content of the polymer (B) in the solution is equal to or less than the above upper limit, the formation of aggregates of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
  • the method of dissolving the polymer (B) in the second solvent is not particularly limited.
  • the second solvent may be added to the polymer (B), or the polymer (B) may be added to the second solvent. or both. Also, depending on the solubility of the second solvent in the polymer (B), it may be dissolved by heating or the like.
  • the step (2) is a step of bringing the polymer (B) solution into contact with the first solvent and then distilling off the second solvent to obtain a dispersion containing the particulate polymer (B).
  • the method of bringing the polymer (B) solution into contact with the first solvent is not particularly limited, but an example thereof includes a method of mixing the polymer (B) solution and the first solvent. Specifically, a method of adding the polymer (B) solution to the first solvent and a method of adding the first solvent to the polymer (B) solution can be exemplified. By such contact, the particulate polymer (B) having a small particle size can be precipitated or dispersed in the mixture of the first solvent and the second solvent. A small amount of the resin (A) and other additives may be added at any timing during the step (2) as long as the particulate polymer (B) does not aggregate.
  • the amount of the polymer (B) solution to be brought into contact with the first solvent is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably 1 part by mass of the first solvent used. is 0.3 parts by mass or more, particularly preferably 0.7 parts by mass or more, preferably 100 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 3 parts by mass or less, particularly preferably 1.5 parts by mass It is below the department.
  • the amount of the polymer (B) solution to be brought into contact with the first solvent is within the above range, the formation of aggregates of the polymer (B) is easily suppressed, and the particle size is easily reduced, so the dispersibility is enhanced. Cheap.
  • step (2) after the polymer (B) solution is brought into contact with the first solvent, the second solvent is distilled off.
  • the second solvent By distilling off the second solvent, the dispersion stability of the particulate polymer (B) can be enhanced. Further, the polymer (B) may be further precipitated by distilling off the second solvent.
  • the second solvent may be at least partially distilled or removed, and the second solvent may remain in the particulate polymer (B) dispersion. From the standpoints of facilitating the suppression of aggregation of the polymer (B) and the facilitating preparation of the dispersion, it is preferred that the second solvent partially remain or partly be contained in the dispersion of the particulate polymer (B).
  • step (2) the method of distilling off the second solvent is not particularly limited, and a method of distilling off under reduced pressure using an evaporator or the like is exemplified.
  • the pressure and temperature during distillation can be appropriately selected according to the characteristics such as the boiling points of the second solvent and the first solvent.
  • the second solvent is distilled off from the mixture of the second solvent and the first solvent, so the boiling point of the second solvent is usually lower than that of the first solvent. In this way, a particulate polymer (B) dispersion in which the polymer (B) is dispersed without containing aggregates of the polymer (B) can be obtained.
  • the content of the second solvent contained in the particulate polymer (B) dispersion obtained after distilling off the second solvent is preferably 120 parts by mass or less, more preferably 120 parts by mass or less with respect to 100 parts by mass of the first solvent.
  • the content of the second solvent is equal to or less than the above upper limit, the formation of aggregates of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film. Moreover, when the content of the second solvent is at least the above lower limit, it is easy to prepare a dispersion.
  • step (I) is, for example, the following steps: Step (1′) of mixing particulate polymer (B) and solvent It may be a step of preparing a particulate polymer (B) dispersion by a method comprising When such a step is included, aggregation of the particles of the polymer (B) can be suppressed, so that the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
  • the step (1') is a step of mixing the particulate polymer (B) and a solvent to obtain a particulate polymer (B) dispersion.
  • the particulate polymer (B) used in step (1′) can be obtained, for example, by pulverizing the polymer (B) with a pulverizer, and if necessary, using a classifier, the particulate polymer (B ) may be adjusted within a desired range.
  • the particulate polymer (B) taken out from the particulate polymer (B) dispersion obtained by the steps (1) and (2) may be used.
  • the median diameter of the particulate polymer (B) used in step (1′) is preferably 0.01 ⁇ m or more, more preferably 0.03 ⁇ m or more, still more preferably 0.05 ⁇ m or more, and preferably 15 ⁇ m or less. It is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
  • the median diameter of the particulate polymer (B) to be added is at least the above lower limit, the dielectric properties of the film formed from the composition are likely to be enhanced, and the film is easily produced.
  • the median diameter of the particulate polymer (B) is equal to or less than the above upper limit, the hygroscopic resistance and heat resistance of the film formed from the composition are likely to be improved.
  • the solvent to be mixed with the particulate polymer (B) is preferably a solvent containing the first solvent, from the viewpoint that the phenolic antioxidant easily adsorbs to the particulate polymer (B), More preferably, it is the first solvent.
  • the particulate polymer (B) dispersion obtained in step (I) contains a solvent other than the first solvent and the second solvent within a range that does not impair the effects of the present invention.
  • solvents are not particularly limited, and commonly used solvents can be used.
  • the total content of the first solvent, the second solvent and other solvents that can be contained in the particulate polymer (B) dispersion obtained in step (I) is On the other hand, it is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, particularly preferably 95% by mass or more, preferably 99.99% by mass or less, more preferably 99.9% by mass or more. It is 9% by mass or less, more preferably 99% by mass or less, and particularly preferably 95% by mass or less.
  • the content of the solvent is within the above range, aggregation of the polymer (B) is likely to be suppressed, and dispersibility of the polymer (B) is likely to be enhanced. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
  • the total mass of the first solvent and the second solvent is the first solvent, the second solvent and other
  • the total mass of the solvent is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and preferably 100% by mass or less.
  • the total mass of the second solvent and the first solvent is within the above range, aggregation of the polymer (B) is likely to be suppressed, and dispersibility of the polymer (B) is likely to be improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
  • the content of the particulate polymer (B) contained in the particulate polymer (B) dispersion obtained in step (I) is, relative to the mass of the polymer (B) dispersion, Preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 1% by mass or more, preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 10% by mass Below, it is 5 mass % or less especially preferably.
  • the content of the particulate polymer (B) is within the above range, aggregation of the polymer (B) is likely to be suppressed, and dispersibility of the polymer (B) is likely to be enhanced. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
  • the polyimide resin (A) to be added when added in the form of varnish in step (II) described later, it is contained in the particulate polymer (B) dispersion obtained in step (I).
  • the content of the particulate polymer (B) is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass or more, relative to the mass of the polymer (B) dispersion, It is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 15% by mass or less.
  • the median diameter of the particulate polymer (B) contained in the particulate polymer (B) dispersion can be selected from the same range as the median diameter of the particulate polymer (B) in the composition of the present invention.
  • the median diameter of the particulate polymer (B) in the dispersion is at least the above lower limit, the dielectric properties of the film formed from the composition are likely to be enhanced, and the film is easily produced.
  • the median diameter of the particulate polymer (B) in the dispersion is equal to or less than the above upper limit, it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
  • the median diameter of the particulate polymer (B) contained in the particulate polymer (B) dispersion can be determined by scattering particle size distribution measurement using laser diffraction, for example, by the method described in Examples. be able to.
  • Step (II) is a step of adding the polyimide resin (A) to the particulate polymer (B) dispersion.
  • the polyimide resin (A) to be added may be in the form of a solid, preferably powder, or in the form of a varnish obtained by dissolving the polyimide resin (A) in a predetermined solvent, such as the first solvent.
  • a predetermined solvent such as the first solvent.
  • the polyimide resin or polyamic acid can be added in solid, preferably powder form or in varnish form.
  • the amount of the polyimide resin (A) added in the varnish is preferably 0.1% by mass or more, more preferably 1% by mass, based on the mass of the varnish.
  • the polyimide resin (A) added in step (II) is preferably 50% by mass or more, more preferably 60% by mass or more, based on the total mass of the polyimide resin (A) and the polymer (B). It is preferably 65% by mass or more, preferably 95% by mass or less, more preferably 93% by mass or less, and even more preferably 90% by mass or less.
  • the content of the polyimide-based resin (A) to be added is at least the above lower limit, film formation is facilitated, which is advantageous from the viewpoint of film production.
  • the content of the polyimide resin (A) is equal to or less than the above upper limit, it is easy to improve the moisture absorption resistance and heat resistance of the obtained film, and it is easy to improve the dielectric properties of the film.
  • the method of adding the polyimide resin (A) to the particulate polymer (B) dispersion is not particularly limited. It may be added in batches.
  • the composition of the present invention can be produced by adding a phenolic antioxidant in the step (I) and/or the step (II). Addition of the phenolic antioxidant may be performed in either step (I) or step (II), or may be performed in both step (I) and step (II).
  • the method of adding the phenolic antioxidant is not particularly limited, and the phenolic antioxidant may be added at once or may be added in multiple portions.
  • step (I) when the step (I) is a step including the step (1) and the step (2), the phenolic antioxidant is easily dispersed, and the polymer (B) is easily adsorbed uniformly. Therefore, it is preferable to add the phenolic antioxidant in step (I). Further, in one embodiment of the present invention, when the step (I) is a step including the step (1 '), the phenolic antioxidant is easily dispersed and uniformly adsorbed on the polymer (B). Addition of the phenolic antioxidant is preferably carried out in step (I).
  • step (I) When adding a phenolic antioxidant in step (I), it may be performed in any of steps (1), (2), and step (1′), but the phenolic antioxidant is dispersed. It is preferable to carry out in step (2) or step (1′), particularly step (1′), from the viewpoint of easy and uniform adsorption on the polymer (B).
  • the order of addition of the phenolic antioxidant and the polyimide resin (A) is not particularly limited, and the polyimide resin ( A) may be added, or the phenolic antioxidant may be added after adding the polyimide resin (A).
  • the phenolic antioxidant is easily dispersed and uniformly adsorbed on the polymer (B)
  • the phenolic antioxidant added in step (I) and/or step (II) is preferably 0.01 part per 100 parts by mass of the polymer (B) in the particulate polymer (B) dispersion or composition. Part by mass or more, more preferably 0.05 part by mass or more, still more preferably 0.1 part by mass or more, still more preferably 0.2 part by mass or more, particularly preferably 1 part by mass or more, particularly more preferably 2 parts by mass That's it.
  • the amount of the phenolic antioxidant added is at least the above lower limit, the polymer (B) is easily covered with the phenolic antioxidant, and the oxidation of the polymer (B) is easily suppressed. Easy to improve heat resistance.
  • the content of the phenolic antioxidant is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and still more preferably 7 parts by mass with respect to 100 parts by mass of the polymer (B). parts or less, particularly preferably 5 parts by mass or less.
  • the content of the phenolic antioxidant is equal to or less than the above upper limit, the dielectric properties of the film are likely to be enhanced.
  • the above production method in the present invention may include steps other than steps (I) and (II) within a range that does not impair the effects of the present invention, other than the above-described polyimide resin (A) and polymer (B) polymers, secondary antioxidants or additives may be added.
  • Additives include those described above.
  • the polyimide resin (A) is added to the polymer (B) dispersion. good too.
  • the varnish of the polyimide resin (A) may be obtained by dissolving the polyimide resin (A) in a predetermined solvent, for example, the first solvent, or the polyimide resin It may be a resin solution used when synthesizing the precursor of (A), such as a polyamic acid solution (a solution containing at least polyamic acid and a synthesis solvent).
  • the present invention comprises a polyimide resin (A), a polymer (B) and a phenolic antioxidant, wherein the phenolic antioxidant has the formula (P): [In the formula (P), R p , R q , R r and R s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms, and * represents a bond]
  • the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom includes a film having an aromatic ring which may have a substituent.
  • the aromatic ring is an aromatic ring different from the substituent P.
  • the film of the present invention has excellent moisture absorption resistance and heat resistance, when the film of the present invention is used for the resin layer of the CCL, it is easy to improve the dielectric properties and suppress the dielectric loss and transmission loss.
  • the polymer (B) contained in the film of the present invention is preferably particulate.
  • the dispersibility of the polymer (B) is likely to be enhanced, and the hygroscopic resistance and heat resistance of the film are likely to be improved.
  • the average primary particle size of the particulate polymer (B) is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less. , still more preferably 3 ⁇ m or less, particularly preferably 1 ⁇ m or less, particularly more preferably 0.8 ⁇ m or less, even more preferably 0.5 ⁇ m or less, preferably 0.01 ⁇ m or more, more preferably 0.03 ⁇ m or more, and further It is preferably 0.05 ⁇ m or more.
  • the average primary particle size of the particulate polymer (B) is at least the above lower limit, the mechanical properties of the film are likely to be enhanced.
  • the average primary particle size of the particulate polymer (B) can be determined by image analysis of images taken with an electron microscope. For example, the cross section of the film is observed using a scanning transmission electron microscope (STEM), the particle diameters of 50 or more particles are measured from the observed image, and the average value thereof is the average primary particle diameter of the particulate cycloolefin copolymer. and can be measured, for example, by the method described in Examples.
  • STEM scanning transmission electron microscope
  • the film of the present invention is preferably a composite film in which the polymer (B) is dispersed, preferably uniformly dispersed, in the polyimide resin (A).
  • the composite film preferably has a sea-island structure, wherein the polyimide resin (A) is the sea and the polymer (B) is the islands.
  • Such a composite film tends to improve moisture absorption resistance and heat resistance.
  • the film of the present invention is preferably formed from the composition of the present invention. Since such a film is preferably formed by removing the solvent from the composition of the present invention, components contained in the film of the present invention, such as polyimide resin (A), polymer (B), phenolic antioxidant The descriptions regarding the agent, secondary antioxidant, etc. are the same as those described in the section [Composition].
  • the film of the present invention contains a solvent, the type of the solvent and the distance between the HSP values between each component contained in the film of the present invention and the solvent are described in [Composition Item].
  • the total mass of the polyimide resin (A) and polymer (B) contained in the film is preferably 40% by mass or more, more preferably 60% by mass or more, relative to the mass of the film. , more preferably 80% by mass or more, particularly preferably 90% by mass or more, and preferably 100% by mass or less.
  • the total mass of the polyimide resin (A) and the polymer (B) contained in the film is at least the above lower limit, the dispersibility of the polymer (B) is easily increased, and the hygroscopic resistance and heat resistance of the film are easily improved. .
  • the thickness of the film of the present invention can be appropriately selected depending on the application, and is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, still more preferably 20 ⁇ m or more, preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, and still more preferably. 100 ⁇ m or less, particularly preferably 80 ⁇ m or less.
  • the thickness of the film can be measured using a film thickness meter or the like, for example, by the method described in Examples.
  • the above thickness represents the average thickness of the single layer portion.
  • the moisture absorption rate of the film is preferably 0.64% by mass or less, more preferably 0.60% by mass or less, even more preferably 0.57% by mass or less, and even more preferably 0.54% by mass. % by mass or less, particularly preferably 0.52 mass % or less, particularly preferably 0.50 mass % or less.
  • the moisture absorption rate is equal to or less than the above upper limit, excellent moisture absorption resistance can be exhibited. Therefore, when the film of the present invention is used for the resin layer of CCL, it is easy to improve the dielectric properties and to suppress dielectric loss and transmission loss.
  • the moisture absorption rate of the film of the present invention may generally be 0.01% by mass or more.
  • the moisture absorption rate of the film of the present invention can be determined by exposing the film to an environment with a temperature of 23° C. and a humidity of 50% for a certain period of time and measuring the moisture content of the film after the exposure with a moisture meter. It can be measured by the method described in .
  • the heat resistance of the film of the present invention may be evaluated by the IR peak retention rate of polymer (B) before and after the heat deterioration test.
  • the retention rate of the IR peak is derived from the cycloolefin-based polymer when annealed at 360° C. for 5 minutes in air (that is, before and after the heat deterioration test). It may be a peak retention rate in the range of 2500 to 3500 cm ⁇ 1 , preferably 2900 to 3000 cm ⁇ 1 .
  • IR peak retention rate [(peak intensity of cycloolefin polymer after deterioration test) / (peak intensity of polyimide resin after deterioration test)] ⁇ [(peak intensity of cycloolefin polymer before deterioration test) / (degradation test Peak intensity of the previous polyimide resin)]
  • the cycloolefin polymer peak intensity is 2500 to 3500 cm -1 , preferably 2900 to 3000 cm -1 peak top intensity
  • the polyimide resin peak intensity is 1450 to 1550 cm -1 , preferably 1480 to 1520 cm shows a peak top intensity of -1
  • the peak top intensity of 2500 to 3500 cm -1 indicates the stretching vibration of C-H contained in the cycloolefin-based polymer
  • the peak top intensity of 1450 to 1550 cm -1 is benzen
  • the IR peak retention rate of the polymer (B) is preferably 50% or higher, more preferably 60% or higher, even more preferably 70% or higher, still more preferably 80% or higher, particularly preferably 85% or more, particularly preferably 90% or more.
  • the upper limit of the IR peak retention rate is not particularly limited, and is usually 100% or less.
  • the film of the present invention may be a single layer film or a multilayer film containing at least one layer made of the film of the present invention.
  • the multilayer film can contain other layers (or other films). Even in such a case, the film including all layers is referred to as the film of the present invention.
  • Other layers include, for example, functional layers. Examples of the functional layer include a primer layer, a gas barrier layer, an adhesive layer, and a protective layer.
  • a functional layer can be used individually or in combination of 2 or more types.
  • the film of the present invention may be subjected to surface treatment such as corona discharge treatment, flame treatment, plasma treatment, ozone treatment, etc., by a method commonly employed industrially.
  • composition and film of the present invention are not limited to the above embodiments, and various modifications are possible without departing from the gist of the present invention.
  • the configurations, methods, etc. of the embodiments other than the above may be arbitrarily adopted and combined, and the configurations, methods, etc. according to the above one embodiment are applied to the configurations, methods, etc. according to the above other embodiments. You may
  • a film according to an embodiment of the present invention has excellent moisture absorption resistance and dielectric properties. Therefore, it can be suitably used as a substrate material compatible with printed circuit boards and antenna substrates for high frequency bands.
  • CCL has a structure in which copper foils are laminated on both surfaces of a resin layer via an adhesive.
  • transmission loss can be reduced because of its excellent moisture absorption resistance and low dielectric loss.
  • the film of the present invention is used as the resin layer, it has excellent heat resistance, so that it can maintain excellent dielectric properties even when exposed to a high-temperature environment.
  • the film of the present invention is used as the resin layer, the surface smoothness is high, and the variation in physical properties and CTE are reduced.
  • the film of the present invention is also suitably used for industrial materials such as automobile parts and electric/electronic parts; optical materials such as lenses, prisms, optical fibers, and recording media.
  • the method for producing the film of the present invention is not particularly limited, but for example the following steps: (a) a composition preparation step of preparing a composition comprising a polyimide resin (A), a polymer (B), a phenolic antioxidant and optionally a solvent; (b) a coating step of applying the composition to a substrate to form a coating film; and (c) a film forming step of drying the applied liquid (coating film) to form a film.
  • a step of completing the imidization reaction may be included.
  • composition preparation step for example, the composition may be prepared by mixing the polyimide resin (A), the polymer (B), the phenolic antioxidant, optionally the solvent, and the additives. It is preferred to use the composition of the invention, in particular the composition obtained by using the above-described process for producing the composition of the invention.
  • the composition of the present invention By using the composition of the present invention, a film having excellent dispersibility of the polymer (B) in the film, moisture absorption resistance and heat resistance can be formed.
  • the application step is a step of applying the composition obtained in the composition preparation step to a substrate to form a coating film.
  • a coating film is formed by coating the composition on the substrate by a known coating method.
  • Known coating methods include, for example, wire bar coating, reverse coating, roll coating such as gravure coating, die coating, comma coating, lip coating, spin coating, screen coating, fountain coating, dipping, A spray method, a curtain coating method, a slot coating method, a casting method, and the like can be mentioned.
  • base materials include copper plates (including copper foil), SUS plates (including SUS foil and SUS belts), glass substrates, PET films, PEN films, other polyimide resin films, and polyamide resin films.
  • SUS plate, glass substrate, PET film, PEN film, etc. are preferable from the viewpoint of excellent heat resistance, and SUS plate, glass substrate, PET film, etc. are more preferable from the viewpoint of adhesion to the film and cost. is mentioned.
  • the coating can be dried and optionally peeled from the substrate to form a film.
  • the base material is a copper foil
  • a film is formed without peeling the coating film from the copper foil, and the obtained laminate is a copper-clad laminate in which the film is laminated on the copper foil. It can also be used for laminates.
  • a drying process for further drying the film may be performed after peeling.
  • the composition is applied to a substrate to form a film, the surface of the coating film on the substrate side is almost flat, but the surface opposite to the substrate side (hereinafter also referred to as the air surface).
  • the thickness may vary and the surface smoothness of the film may be impaired.
  • the use of the composition of the present invention effectively suppresses the formation of such surface roughness. Therefore, a film having excellent surface smoothness can be formed.
  • Drying of the coating film can be appropriately selected depending on the heat resistance of the polyimide resin (A), etc., and is usually carried out at a temperature of 50 to 450°C, preferably 55 to 400°C, more preferably 70 to 380°C. can be carried out, and in another embodiment of the invention, it can be carried out at a temperature of 50-400°C, preferably 70-360°C. In a preferred embodiment of the invention, the drying is preferably done in stages.
  • the composition can be dried uniformly, and the moisture absorption resistance and heat resistance of the resulting film can be easily improved.
  • it may be heated to 200 to 450°C, preferably 200 to 400°C, more preferably 200 to 350°C.
  • the drying or heating time is preferably 5 minutes to 10 hours, more preferably 10 minutes to 5 hours. Heating from a low temperature to a high temperature stepwise within such a range tends to improve the hygroscopic resistance, heat resistance, uniformity of thermal conductivity or thermal diffusivity, optical properties, and Tg of the resulting film.
  • the coating film may be dried under inert atmosphere conditions such as nitrogen or argon, under vacuum or reduced pressure conditions, and/or under ventilation.
  • inert atmosphere conditions such as nitrogen or argon, under vacuum or reduced pressure conditions, and/or under ventilation.
  • drying of the coating film may be continued, and after all drying is completed, the coating film ( film) may be peeled off.
  • the coating film may be peeled off from the substrate and the second and subsequent drying stages may be performed, or after all the drying stages are completed, the coating film (film) may be peeled off from the substrate. good. Note that the drying in the first stage may be pre-drying.
  • the film may be peeled off from the copper foil as the base material by etching away the copper foil with a ferric chloride solution or the like.
  • the composition when the polyimide resin (A) in the composition is a polyimide resin precursor, such as polyamic acid, and the polyimide resin is produced during film production, the composition is applied to the substrate. After that, it is preferable to thermally imidize by heating. By the heating, drying for removing the solvent and thermal imidization can be performed at the same time.
  • the drying and imidization temperature is usually in the range of 50 to 450° C., and from the viewpoint of easily obtaining a smooth film having excellent moisture absorption resistance, it is preferable to carry out heating in stages. For example, after removing the solvent by heating at a relatively low temperature of 50 to 150°C, it may be heated stepwise to a temperature in the range of 300 to 450°C.
  • the heating time can be selected, for example, from the same range as the above range.
  • the film of the present invention is a multilayer film
  • it can be produced by a multilayer film forming method such as coextrusion processing, extrusion lamination, heat lamination, and dry lamination.
  • HSP Hansen solubility parameter
  • HSP Hansen solubility parameter
  • the Hansen Solubility Parameters (HSP) of the phenolic antioxidant, solvent, cycloolefin copolymer, polyimide resin and fluoropolymer, and the distance between the HSP values were obtained as follows.
  • HSP Heansen Solubility Parameter
  • the HSP value of the structure S of the phenolic antioxidant was calculated from the structural formula using HSPiP .
  • Structure S of Sumilizer GA80 had ⁇ D of 16.7 MPa 0.5 , ⁇ P of 5.0 MPa 0.5 and ⁇ H of 4.5 MPa 0.5 .
  • the HSP value of the solvent is 18.0 MPa 0.5 for GBL, 16.6 MPa 0.5 for ⁇ P, 7.4 MPa 0.5 for ⁇ H , and 16 for DMAc. 8 MPa 0.5 , ⁇ P is 11.5 MPa 0.5 , ⁇ H is 9.4 MPa 0.5 and toluene has ⁇ D of 18.0 MPa 0.5 , ⁇ P of 1.4 MPa 0.5 , ⁇ H of 2.0 MPa 0.5 .
  • Acetone had a ⁇ D of 15.5 MPa 0.5 , a ⁇ P of 10.4 MPa 0.5 and a ⁇ H of 7.0 MPa 0.5 .
  • HSP of cycloolefin copolymer The solubility of cycloolefin copolymers in various solvents was evaluated. Solubility evaluation was carried out using solvents with known solubility parameters in a transparent container (see HSPiP database, solvents used: 2-(1-cyclohexenyl)cyclohexanone, 6-tert-butyl-2,4-xylenol, Methyl chloride, 1,4-dioxane, 1,4-dichlorobenzene, chloroform, toluene, 1-phenyloctane, p-xylene, styrene, ethanol, 1-butanol, N,N-dimethylformamide, dimethylsulfoxide, GBL, N -methylformamide, acetic acid) and 0.1 g of a cycloolefin copolymer were added to prepare a mixed solution.
  • the resulting mixture was subjected to ultrasonic treatment for a total of 6 hours.
  • the appearance of the mixed solution after ultrasonic treatment was visually observed, and the solubility of each resin in the solvent was evaluated based on the following evaluation criteria based on the obtained observation results.
  • evaluation criteria 2 At room temperature, the appearance of the mixed solution is cloudy and precipitation occurs, but when heated to 50° C. and stirred with a stirrer for 30 minutes, the appearance of the mixed solution becomes transparent.
  • 1 Appearance of mixture is transparent at room temperature.
  • 0 At room temperature, the appearance of the mixture is cloudy and precipitation occurs, and even after heating to 50° C. and stirring with a stirrer for 30 minutes, the appearance of the mixture does not become clear.
  • the HSP value was calculated by the above-mentioned Hansen dissolving sphere method using HSPiP.
  • HSP of polyimide resin The solubility of the polyimide resin in various solvents was evaluated. Solubility evaluation was carried out using solvents with known solubility parameters in a transparent container (see HSPiP database, solvents used acetone, toluene, ethanol, tetrahydrofuran, N,N-dimethylformamide, dimethylsulfoxide, hexane, GBL, ethyl acetate , methyl ethyl ketone, propylene glycol monomethyl ether, 1-butanol, N-methylformamide, 1-methylnaphthalene, bromobenzene, 1-methylimidazole, pyrazole, acetic acid) and 0.1 g of polyimide resin were added to prepare a mixed solution.
  • HSPiP Hansen dissolving sphere method from the evaluation results of the solubility of the obtained polyimide resin in the solvent.
  • HSP of fluoropolymer 1 THV221AZ
  • THV solubility of fluoropolymer 1 in various solvents
  • Solubility evaluation was carried out using solvents with known solubility parameters in a transparent container (see HSPiP database, solvents used: acetone, tetrahydrofuran, N,N-dimethylformamide, dimethylsulfoxide, GBL, methyl ethyl ketone, 1-butanol, acetic acid Butyl, DMAc, methanol, hexyl acetate, ethyl acetoacetate, 2-propanol) (10 mL) and 0.1 g of fluoropolymer were added to prepare a mixed solution.
  • the HSP value was calculated by the above-mentioned Hansen dissolving sphere method using HSPiP.
  • HSP of fluoropolymer 2 (PTFE)
  • PTFE fluoropolymer 2
  • ⁇ D was 17.1 MPa 0.5
  • ⁇ P was 8.1 MPa 0.5
  • ⁇ h was 1.3 MPa 0.5 .
  • NB content The content of norbornene-derived monomer units (also referred to as “NB content”) in the cycloolefin copolymer was measured using 13 C-NMR.
  • the 13 C-NMR measurement conditions are as follows.
  • Apparatus Bruker AVANCE600, 10 mm cryoprobe Measurement temperature: 135°C Measurement method: proton decoupling method Concentration: 100 mg/mL Number of times of integration: 1024 times Pulse width: 45 degrees Pulse repetition time: 4 seconds Chemical shift value standard: Tetramethylsilane Solvent: 1,2-dichlorobenzene-d4 and 1,1,2,2 - tetrachloroethane - d2 The NB content in the cycloolefin copolymer is based on 1,2-dichlorobenzene (127.68 ppm) and is calculated according to RA Wendt, G. Fink, Macromol. , 2001, 202, 3490”.
  • ⁇ Meso type double chain/racemo type double chain The ratio of the meso-type double chain and the racemo-type double chain of the norbornene double chain of the cycloolefin copolymer (meso-type double chain/racemo-type double chain) is measured using 13 C-NMR under the same conditions as the measurement of the NB content. Measured at The meso-type double chain/racemo-type double chain of the norbornene double chain is based on 1,1,2,2-tetrachloroethane (74.24 ppm), and is described in RA Wendt, G. Fink, Macromol. Chem.
  • meso-type two-chain/racemo-type two chains are observed at chemical shift values of 27.5-28.4 ppm in a spectrum chart measured using 13 C-NMR: signal integral value: IC5 , C6 -m (derived from carbon atoms at positions 5 and 6 of the norbornene ring of the meso-type double chain), signal integral values observed at chemical shift values 28.4-29.6 ppm: I C5, C6 -r (racemo type derived from carbon atoms at positions 5 and 6 of a double-chained norbornene ring), it was obtained from the following formula.
  • Meso-type bilinkage/racemo-type bilinkage I C5,C6 ⁇ m/I C5,C6 ⁇ r
  • the refractive index of the cycloolefin copolymer was obtained by measuring under the following conditions using a sheet-like sample molded to a thickness of 100 ⁇ m with a vacuum press.
  • ⁇ CTE> The CTE of the cycloolefin copolymer was measured using TMA under the following conditions, and the CTE at 50°C to 100°C was calculated.
  • Apparatus TMA/SS6200 manufactured by Hitachi High-Tech Science Co., Ltd. Indenter (probe) diameter: 3.5 mm Load: 38.5 mN
  • Temperature program Temperature rise from 20°C to 130°C at a rate of 5°C/min Test piece: 10 mm x 10 mm x 1 mm rectangular parallelepiped
  • Tg of cycloolefin copolymer The Tg of the cycloolefin copolymer was obtained by measuring the softening temperature by TMA based on JIS K 7196. Specifically, a sample (thickness: 1.0 mm) obtained by molding a cycloolefin copolymer into a sheet with a vacuum press was measured under the following conditions, and the softening temperature was defined as the onset of the displacement when the indenter sinks into the sample. did. Apparatus: "TMA/SS6200" manufactured by Hitachi High-Tech Science Co., Ltd. Indenter diameter: 1mm Load: 780mN Temperature program: Temperature rise from 20°C to 380°C at a rate of 5°C/min
  • Tg of polyimide resin The Tg of the polyimide resin was determined by the following measurements. Using TA Instrument Co., Ltd., "DMA Q800", measured under the following samples and conditions to obtain a tan ⁇ curve, which is the ratio of the values of loss modulus and storage modulus, and then the peak of the tan ⁇ curve. Tg was calculated from the highest peak.
  • ⁇ Mw and Mn of cycloolefin copolymer> The polystyrene equivalent Mw and Mn of the cycloolefin copolymer were measured using GPC. GPC measurement was performed under the following conditions, and peaks were designated by defining a baseline on the chromatogram based on the description of ISO16014-1.
  • GPC column TSKgel GMH6-HT inner diameter 7.8 mm ⁇ length 300 mm (manufactured by Tosoh Corporation) 3 columns connected Mobile phase: ortho-dichlorobenzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade) with 0.1 g of BHT /100 mL was added for use.
  • Sample solution concentration 1 mg/mL
  • Automatic shaker for dissolution DF-8020 (manufactured by Tosoh Corporation)
  • Dissolution conditions 5 mg of sample is enclosed in a 1,000 mesh SUS wire mesh bag, the wire mesh bag containing the sample is placed in a test tube, 5 mL of orthodichlorobenzene having the same composition as the mobile phase is added, and the test tube is The test tube was covered with aluminum foil, set in DF-8020, and stirred at 140° C. for 120 minutes at a stirring rate of 60 reciprocations/minute. GPC measurement was performed using the stirred solution as a sample.
  • ⁇ Mw of polyimide resin and polyamic acid The polystyrene equivalent Mw of the polyimide resin and polyamic acid was measured using GPC. GPC measurement was performed under the following conditions. GPC measurement (1) Pretreatment method A DMF eluent (10 mmol/L lithium bromide-added DMF solution) was added to the sample to a concentration of 2 mg/mL, heated at 80°C for 30 minutes with stirring, and cooled. A measurement solution was obtained by filtration through a 0.45 ⁇ m membrane filter.
  • ⁇ Particle size of particulate cycloolefin copolymer and particulate fluoropolymer in dispersion and composition> (The particle size of the particulate cycloolefin copolymer in the particulate cycloolefin copolymer dispersion obtained using the cycloolefin copolymer solutions obtained in Production Examples 1 and 3, and the particle size in the particulate fluoropolymer dispersion Particle size of fluoropolymer)
  • the median diameter of the particulate cycloolefin copolymers in the dispersions of the particulate cycloolefin copolymers obtained in Examples 1, 3, 5, 9, 10, 12 and Comparative Examples 1 and 3, and the median sizes obtained in Examples 7 and 8 The median diameter of the particulate fluoropolymer in the obtained particulate fluoropolymer dispersion was determined by scattering particle size distribution measurement using laser diffraction.
  • the particulate cycloolefin copolymer dispersion obtained in Examples 1, 3, 5, 9, 10, 12 and Comparative Examples 1 and 3, or Example 7 was placed in a glass cell having a capacity of 3.5 mL.
  • add the particulate fluoropolymer dispersion obtained in 8 further add GBL or DMAc (using the same solvent as the dispersion) to dilute 1000 times, and contain particulate cycloolefin copolymer or particulate fluoropolymer A dispersion sample was obtained.
  • Each dispersion sample obtained was measured using a laser diffraction/scattering particle size distribution analyzer (manufactured by Malvern Panalytical, model: NanoZS, refractive index: 1.70-0.20i), and the particulate cycloolefin copolymer and the median diameter of the particulate fluoropolymer were determined.
  • the polyimide resin was used in an amount within a range not affecting the particle size of the particulate cycloolefin copolymer or the particulate fluoropolymer.
  • the median size of the particulate cycloolefin copolymer in the dispersion and the median size of the particulate fluoropolymer in the dispersion were used.
  • the particulate cycloolefin copolymer obtained in Production Examples 2 and 4 was dispersed in isopropanol to obtain a dispersion liquid sample containing the particulate cycloolefin copolymer.
  • Each dispersion sample obtained was measured using a laser diffraction/scattering particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., model: MT3300EX II) to determine the median diameter of each particulate cycloolefin copolymer.
  • polyamic acid was added to the dispersion in an amount within a range not affecting the particle size of the particulate cycloolefin copolymer to form the composition. did. Also, particulate cycloolefin copolymers are not soluble in isopropanol, DMAc and GBL. Therefore, the median diameter of the particulate cycloolefin copolymer in the dispersion sample was used as the median diameter of the particulate cycloolefin copolymer in the composition.
  • ⁇ Thickness of composite film> The thickness of the composite films obtained in Examples and Comparative Examples was measured using a digimatic indicator (manufactured by Mitutoyo Co., Ltd., "ID-C112XBS"), and measuring the thickness at five or more arbitrary points of the film. Their average value was taken as the thickness of the composite film.
  • ⁇ Moisture absorption rate of composite film> The moisture absorption of the composite films obtained in Examples 1, 2, 5 to 9 and Comparative Examples 1 and 2 was measured with a Karl Fischer moisture meter (evaporation type). Specifically, a film cut into a size of 20 mm ⁇ 20 mm is put in a vial bottle for a moisture vaporizer, and the temperature is 23 ° C. and the humidity is 50% (hereinafter also referred to as “23 ° C. 50%”) for 24 hours. more exposed. After that, the vial was sealed in the same environment, and the water content in the film was measured under the conditions shown below.
  • Moisture absorption rate [(moisture content in film) - (moisture content in blank measurement)] ⁇ (film mass after exposure for 24 hours or more at 23 ° C. 50% environment) ⁇ 100
  • ⁇ ATR unit Specac silver gate ATR evolution (germanium flat plate)
  • ⁇ Measurement surface The surface on the glass substrate side when the composite film was peeled from the glass substrate
  • ⁇ Measurement conditions 32 integration times, wave number resolution 4 cm ⁇ 1 , scan speed 5 kHz
  • Calculation of IR peak retention rate Calculated from the following formula.
  • Toluene is dehydrated using molecular sieves 13X (manufactured by Union Showa Co., Ltd.) and activated alumina ("NKHD-24" manufactured by Sumitomo Chemical Co., Ltd.), and then nitrogen gas is blown to remove dissolved oxygen. It was used.
  • NB is dissolved in toluene, dehydrated using molecular sieves 13X (manufactured by Union Showa Co., Ltd.) and activated alumina ("NKHD-24" manufactured by Sumitomo Chemical Co., Ltd.), and then nitrogen gas is blown. (hereinafter referred to as "NB solution”).
  • NB solution The NB concentration in the NB solution was measured using gas chromatography.
  • the NB content is 82.5 mol%
  • the Tg is 297°C
  • the Mw is 343,000
  • the Mw/Mn is 1.79
  • the CTE is 47.0 ppm/ was K.
  • the cycloolefin copolymer had a ⁇ D of 17.4 MPa 0.5 , a ⁇ P of 1.6 MPa 0.5 , a ⁇ H of 3.8 MPa 0.5 and a meso/racemo bilink of 0.5 . 11 and the refractive index was 1.54.
  • Table 2 shows the synthesis conditions of Synthesis Example 1.
  • the cycloolefin copolymer had a ⁇ D of 17.4 MPa 0.5, a ⁇ P of 1.6 MPa 0.5 and a ⁇ H of 3.8 MPa 0.5 .
  • Table 3 shows the synthesis conditions of Synthesis Example 2.
  • cycloolefin copolymer solution 1 Production of cycloolefin copolymer solution 1> A cycloolefin copolymer solution 1 was obtained by dissolving the cycloolefin copolymer obtained in Synthesis Example 1 in toluene at a concentration of 2% by mass.
  • ⁇ Production Example 2 Production of crushed cycloolefin copolymer powder 1>
  • the cycloolefin copolymer obtained in Synthesis Example 1 was pulverized with a counter jet mill manufactured by Kitamura Co., Ltd. and classified by a filter to obtain crushed cycloolefin copolymer powder 1 having a median diameter of 2.6 ⁇ m. .
  • cycloolefin copolymer solution 2 was obtained by dissolving the cycloolefin copolymer obtained in Synthesis Example 2 in toluene at a concentration of 2% by mass.
  • ⁇ Production Example 4 Production of crushed cycloolefin copolymer powder 2>
  • the cycloolefin copolymer obtained in Synthesis Example 2 was pulverized with a counter jet mill manufactured by Kitamura Co., Ltd. and classified by a filter to obtain crushed cycloolefin copolymer powder 2 having a median diameter of 2.7 ⁇ m. rice field.
  • the resulting polyimide resin had a ⁇ D of 18.1 MPa 0.5, a ⁇ P of 8.3 MPa 0.5 , and a ⁇ H of 9.3 MPa 0.5 .
  • the polyimide resin had an Mw of 334,300 and a Tg of 361°C.
  • the distance between the HSP values of the polyimide resin and the cycloolefin copolymer obtained in Production Example 1 was 8.8.
  • a reactor was prepared by attaching a silica gel tube, a stirrer and a thermometer to a separable flask. After creating a nitrogen atmosphere in the flask using dry nitrogen, 399.20 g of DMAc and 16.00 g (0.148 mol) of p-PDA were added, followed by stirring at room temperature to dissolve p-PDA in DMAc. rice field. To this was added 21.2869 g (0.0724 mol) of BPDA and 33.1603 g (0.0724 mol) of TAHQ while stirring at 400 rpm. After that, the mixture was stirred at room temperature for 3 hours to obtain a polyamic acid solution.
  • Example 1 100.0 g of the cycloolefin copolymer solution 1 obtained in Production Example 1 and 98.0 g of GBL were mixed and distilled under reduced pressure at 50 hPa and 80° C. so that the toluene content was 7 parts by mass with respect to 100 parts by mass of GBL. toluene was distilled off to obtain a particulate cycloolefin copolymer dispersion.
  • the median diameter of the particulate cycloolefin copolymer in the dispersion and composition measured by the above method was 0.14 ⁇ m.
  • Adekastab AO-330 manufactured by ADEKA Corporation; (1,3,5-tris(3,5-di-tert-butyl-4 -Hydroxyphenylmethyl)-2,4,6-trimethylbenzene) 0.0487 g was added and stirred, and then 2.0 g of the polyimide resin obtained above was added to obtain a polyimide-cycloolefin copolymer mixture, A composition was obtained.
  • the content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer.
  • the resulting composition was cast on a glass substrate to form a coating film at a line speed of 0.4 m/min. After heating the coating film at 70 ° C. for 60 minutes and peeling the film from the glass substrate, the film was fixed with a metal frame and further heated at 360 ° C. for 15 minutes in the atmosphere to obtain a polyimide-cycloolefin having a thickness of 50 ⁇ m. A copolymer composite film was obtained.
  • the content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
  • the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.16 ⁇ m.
  • the distance between the HSP values between the cycloolefin copolymer and the polyimide resin used in Example 1 is 8.8, the distance between the HSP values between the cycloolefin copolymer and toluene is 2.2, and the distance between the polyimide resin and toluene is 8.8.
  • the distance between HSP values is 10.0, the distance between HSP values between the cycloolefin copolymer and GBL is 15.5, the distance between HSP values between polyimide resin and GBL is 8.5, and AO-330
  • the distance between HSP values between and GBL is 17.7, the distance between HSP values between structure S of AO-330 and GBL is 17.6, and the distance between HSP values between AO-330 and cycloolefin copolymer is 3.4, and the distance between the HSP values of structure S of AO-330 and the cycloolefin copolymer was 2.8.
  • the distance between the HSP values between AO-330 and the polyimide resin is 11.7
  • the distance between the HSP values between the structure S of AO-330 and the polyimide resin is 11.5
  • the distance between AO-330 and toluene was 1.7.
  • the cycloolefin copolymer used in Example 1 dissolved in toluene but did not dissolve in GBL.
  • the polyimide resin dissolved in GBL but did not dissolve in toluene.
  • Example 2 7.31 g of crushed cycloolefin copolymer powder 1, 52.03 g of DMAc and 0.365 g of AO-330 were mixed and stirred to obtain a dispersion. 100 g of polyamic acid solution (15% by mass of polyamic acid) was added to the resulting dispersion to obtain a composition as a polyamic acid-cycloolefin copolymer mixed solution. The content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer. The resulting composition was cast on a glass substrate to form a coating film at a line speed of 0.4 m/min. After heating the coating film at 50° C.
  • the film was fixed with a metal frame and further heated at 360° C. for 15 minutes in the atmosphere to obtain a polyamic film.
  • the acid was imidized to obtain a 50 ⁇ m thick polyimide-cycloolefin copolymer composite film.
  • the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer.
  • the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 ⁇ m.
  • the distance between the HSP values between the cycloolefin copolymer and the polyamic acid used in Example 2 is 6.0 or more, the distance between the HSP values between the cycloolefin copolymer and DMAc is 11.4, and AO-330 and DMAc
  • the distance between HSP values of AO-330 is 14.4, the distance between HSP values between Structure S of AO-330 and DMAc is 14.0, and the distance between HSP values between AO-330 and cycloolefin copolymer is 3.4. and the distance between the HSP values of structure S of AO-330 and the cycloolefin copolymer was 2.8.
  • the distance between the HSP values of the cycloolefin copolymer used in Example 2 and the polyimide resin obtained by imidating the polyamic acid was 6.0 or more. According to the above solubility evaluation method, the polyamic acid used in Example 2 dissolved in DMAc but did not dissolve in toluene.
  • the content of the particulate cycloolefin copolymer was 32.8% by weight based on the total weight of the polyimide resin and the particulate cycloolefin copolymer.
  • the average primary particle size was 0.16 ⁇ m.
  • the distance between the HSP values between the cycloolefin copolymer and the polyimide resin used in Comparative Example 1 was 8.8, the distance between the HSP values between the cycloolefin copolymer and toluene was 2.2, and the cycloolefin copolymer and GBL
  • the distance between HSP values is 15.5, the distance between HSP values between polyimide resin and toluene is 10.0, the distance between HSP values between polyimide resin and GBL is 8.5, and Sumilizer GA80 and
  • the distance between HSP values with GBL is 15.3, the distance between HSP values between Structure S of Sumilizer GA80 and GBL is 12.2, and the distance between HSP values between Sumilizer GA80 and cycloolefin copolymer is 2.0.
  • the distance between the HSP values of Structure S of Sumilizer GA80 and the cycloolefin copolymer was 3.7. Further, the distance between the HSP values between Sumilizer GA80 and the polyimide resin is 8.1, the distance between the HSP values between the structure S of Sumilizer GA80 and the polyimide resin is 6.5, and the distance between the HSP values between Sumilizer GA80 and toluene The distance was 2.8.
  • Example 2 A composition as a polyamic acid-cycloolefin copolymer mixture and a thickness of 50 ⁇ m were prepared in the same manner as in Example 2, except that 0.365 g of Sumilizer GA80 manufactured by Sumitomo Chemical Co., Ltd. was added instead of AO-330. A polyimide-cycloolefin copolymer composite film was obtained. The content of Sumilizer GA80 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer.
  • the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer.
  • the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 ⁇ m.
  • the distance between the HSP values between the cycloolefin copolymer used in Comparative Example 2 and DMAc was 11.4, the distance between the HSP values between Sumilizer GA80 and DMAc was 11.4, and the distance between Structure S of Sumilizer GA80 and DMAc was 11.4.
  • the HSP value distance is 8.1, the HSP value distance between Sumilizer GA80 and the cycloolefin copolymer is 2.0, and the HSP value distance between Structure S of Sumilizer GA80 and the cycloolefin copolymer is 3.7. there were.
  • Example 3 A composition prepared in the same manner as in Example 1 was cast on a glass substrate to form a coating film at a line speed of 0.4 m/min. After heating the coating film at 70 ° C. for 60 minutes, peeling the film from the glass substrate, fixing the film with a metal frame, and further heating at 200 ° C. for 60 minutes in a nitrogen atmosphere, a 50 ⁇ m thick polyimide- A cycloolefin copolymer composite film was obtained. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.16 ⁇ m.
  • Example 4 A coating film was prepared from the composition prepared in the same manner as in Example 2 by casting on a glass substrate at a line speed of 0.4 m/min. The coating film was heated at 50°C for 80 minutes, the polyamic acid-cycloolefin copolymer composite film was peeled off from the glass substrate, the film was fixed with a metal frame, and the temperature was increased stepwise to 360°C in a nitrogen atmosphere. The polyamic acid was imidized by heating at 360° C. for 5 minutes to obtain a polyimide-cycloolefin copolymer composite film having a thickness of 50 ⁇ m.
  • the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer.
  • the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 ⁇ m.
  • Example 3 A polyimide-cycloolefin copolymer composite film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 3, except that the composition prepared in the same manner as in Comparative Example 1 was used.
  • the content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
  • the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.16 ⁇ m.
  • Example 4 A polyimide-cycloolefin copolymer composite film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 4 except that the composition prepared in the same manner as in Comparative Example 2 was used.
  • the content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
  • the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 ⁇ m.
  • Example 5 100.0 g of the cycloolefin copolymer solution 2 obtained in Production Example 3 and 98.0 g of DMAc were mixed, and the toluene content was 0.6 parts by mass with respect to 100 parts by mass of DMAc at 50 hPa and 80 ° C. Toluene was distilled off under reduced pressure to obtain a particulate cycloolefin copolymer dispersion. The median diameter of the particulate cycloolefin copolymer in the dispersion and composition measured by the above method was 0.13 ⁇ m.
  • Adekastab AO-330 manufactured by ADEKA Corporation; (1,3,5-tris(3,5-di-tert-butyl-4 -Hydroxyphenylmethyl)-2,4,6-trimethylbenzene) 0.03 g was added and stirred, and then 8.0 g of the polyamic acid solution obtained above (polyamic acid 15% by mass) was added to obtain a polyamic.
  • a composition was obtained as an acid-cycloolefin copolymer mixed solution.
  • the content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer.
  • a polyimide-cycloolefin copolymer composite film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 4, except that the composition obtained above was used.
  • the content of the particulate cycloolefin copolymer was 33.3% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer.
  • the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.15 ⁇ m.
  • the distance between the HSP values between the cycloolefin copolymer and polyamic acid used in Example 5 is 6.0 or more, the distance between the HSP values between the cycloolefin copolymer and toluene is 2.2, and the cycloolefin copolymer and DMAc
  • the distance between HSP values is 11.4, the distance between HSP values between AO-330 and DMAc is 14.4, and the distance between HSP values between structure S of AO-330 and DMAc is 14.0.
  • the distance between the HSP values of AO-330 and the cycloolefin copolymer was 3.4, and the distance between the HSP values of structure S of AO-330 and the cycloolefin copolymer was 2.8. Further, the distance between the HSP values of the cycloolefin copolymer used in Example 9 and the polyimide resin obtained by imidating the polyamic acid was 6.0 or more. According to the above solubility evaluation method, the cycloolefin copolymer used in Example 5 dissolved in toluene but did not dissolve in DMAc. Polyamic acid dissolved in DMAc but did not dissolve in toluene.
  • Example 6 A composition as a polyamic acid-cycloolefin copolymer mixed solution was prepared in the same manner as in Example 2 except that the cycloolefin copolymer crushed powder 2 obtained in Production Example 4 was added instead of the cycloolefin copolymer crushed powder 1. and a polyimide-cycloolefin copolymer composite film with a thickness of 50 ⁇ m.
  • the content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer.
  • the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer.
  • the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 ⁇ m.
  • the distance between the HSP values between the cycloolefin copolymer and the polyamic acid used in Example 6 is 6.0 or more, the distance between the HSP values between the cycloolefin copolymer and DMAc is 11.4, and AO-330 and DMAc
  • the distance between HSP values of AO-330 is 14.4, the distance between HSP values between Structure S of AO-330 and DMAc is 14.0, and the distance between HSP values between AO-330 and cycloolefin copolymer is 3.4. and the distance between the HSP values of structure S of AO-330 and the cycloolefin copolymer was 2.8.
  • the distance between the HSP values of the cycloolefin copolymer used in Example 6 and the polyimide resin obtained by imidating the polyamic acid was 6.0 or more. According to the solubility evaluation method described above, the cycloolefin copolymer used in Example 10 dissolved in toluene but did not dissolve in DMAc. Polyamic acid dissolved in DMAc but did not dissolve in toluene.
  • Example 7 Fluorine polymer (manufactured by 3M, THV221AZ (tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, molar ratio of tetrafluoroethylene structural units: 0.35, Mw: 384,000, melting point: 120° C.)) 2 g and 98 g of acetone were mixed to obtain a fluoropolymer solution. 100 g of the obtained fluoropolymer solution and 98.0 g of GBL were mixed and distilled under reduced pressure at 50 hPa and 40° C. for 2 hours to remove acetone and obtain a particulate fluoropolymer dispersion.
  • the acetone content of the resulting dispersion was 0.6 parts by weight per 100 parts by weight of GBL.
  • the median diameter of the fluoropolymer in the particulate fluoropolymer dispersion measured by the above method was 0.11 ⁇ m.
  • Adekastab AO-330 manufactured by ADEKA Corporation; (1,3,5-tris(3,5-di-tert -Butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene) 0.03 g was added and stirred, and then 1.2 g of the polyimide resin obtained above was added to obtain a polyimide-fluoropolymer.
  • a composition was obtained as a mixed solution.
  • the content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the fluoropolymer. No fluoropolymer aggregates larger than 1 mm were observed in the resulting composition.
  • the resulting composition was cast on a glass substrate to form a coating film at a line speed of 0.4 m/min. After heating the coating film at 70 ° C. for 60 minutes, peeling the film from the glass substrate, fixing the film with a metal frame, and further heating at 360 ° C. for 15 minutes in the atmosphere, a polyimide-fluoropolymer having a thickness of 50 ⁇ m. A composite film was obtained.
  • the content of the particulate fluoropolymer in the obtained composite film was 33.3% by mass with respect to the total mass of the polyimide resin and the particulate fluoropolymer.
  • the average primary particle size of the particulate fluoropolymer in the obtained composite film was 0.13 ⁇ m.
  • the HSP value distance between the fluoropolymer and polyimide used in Example 7 was 11.2, the HSP value distance between the fluoropolymer and acetone was 5.2, and the HSP value between the fluoropolymer and GBL.
  • the inter-HSP value distance between AO-330 and acetone is 12.9, and the inter-HSP value distance between AO-330 and fluoropolymer is 15.9.
  • the distance between HSP values between structure S and fluoropolymer is 15.3, the distance between HSP values between polyimide resin and acetone is 6.1, and the distance between HSP values between polyimide resin and GBL is 8.5. there were.
  • the fluoropolymer used in Example 7 dissolved in acetone, but did not dissolve in GBL.
  • the polyimide used in Example 7 was dissolved in GBL and acetone.
  • Example 8 5.69 g of particulate PTFE (manufactured by Polysciences Inc., melting point: 320° C., Mw: 20,000) and 42.1 g of DMAc were mixed and stirred to obtain a particulate PTFE dispersion.
  • Adekastab AO-330 manufactured by ADEKA Corporation; (1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6- After adding 0.2845 g of trimethylbenzene and stirring, 100 g of the polyamic acid solution obtained above (15% by mass of polyamic acid) was added to obtain a composition as a polyamic acid-PTFE mixed solution.
  • the content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the fluoropolymer. No fluoropolymer aggregates larger than 1 mm were observed in the resulting composition.
  • a polyimide-PTFE composite film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 4, except that the composition obtained above was used.
  • the content of particulate PTFE was 27.5% by mass with respect to the total mass of the polyimide resin and PTFE.
  • the average primary particle size of the particulate PTFE in the obtained composite film was 3 ⁇ m.
  • the distance between the HSP values between PTFE and polyamic acid used in Example 8 is 6.0 or more, the distance between the HSP values between PTFE and DMAc is 8.8, and the distance between the HSP values between AO-330 and PTFE The distance was 8.2, and the distance between the HSP values of Structure S of AO-330 and PTFE was 8.0. Further, the distance between the HSP values of the PTFE used in Example 8 and the polyimide resin obtained by imidizing the polyamic acid was 6.0 or more.
  • the PTFE used in Example 8 did not dissolve in DMAc by the above solubility evaluation method. Polyamic acid dissolved in DMAc but did not dissolve in toluene.
  • Example 9 100.0 g of the cycloolefin copolymer solution 1 obtained in Production Example 1 and 98.0 g of DMAc were mixed and distilled under reduced pressure at 50 hPa and 80° C. so that the toluene content was 7 parts by mass with respect to 100 parts by mass of DMAc. toluene was distilled off to obtain a particulate cycloolefin copolymer dispersion.
  • the median diameter of the particulate cycloolefin copolymer in the dispersion and composition measured by the above method was 0.13 ⁇ m.
  • a polyimide-cycloolefin copolymer composite film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 1, except that the particulate cycloolefin copolymer dispersion prepared above was used.
  • the content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
  • the average primary particle size of the particulate cycloolefin copolymer in the obtained composite film was 0.14 ⁇ m.
  • the distance between the HSP values between the cycloolefin copolymer used in Example 9 and toluene was 2.2, the distance between the HSP values between the cycloolefin copolymer and DMAc was 11.4, and the distance between AO-330 and DMAc was The inter-HSP value distance was 14.4, and the inter-HSP value distance between structure S of AO-330 and DMAc was 14.0.
  • the cycloolefin copolymer used in Example 9 dissolved in toluene but did not dissolve in DMAc.
  • the polyimide resin dissolved in DMAc but did not dissolve in toluene.
  • Example 10 A polyimide-cycloolefin copolymer composite film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 4, except that the composition prepared in the same manner as in Example 5 was used.
  • the content of the particulate cycloolefin copolymer in the resulting composite film was 33.3% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
  • the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.15 ⁇ m.
  • Example 11 A polyimide-cycloolefin copolymer composite film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 4 except that a composition prepared in the same manner as in Example 6 was used.
  • the content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
  • the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 ⁇ m.
  • Example 12 A polyimide-cycloolefin copolymer composite film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 3 except that a composition prepared in the same manner as in Example 9 was used.
  • the content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
  • the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.15 ⁇ m.
  • the moisture absorption rate of the polyimide-cycloolefin copolymer composite films obtained in Examples 1, 2, 5 to 9 and Comparative Examples 1 and 2 was measured according to the above method. The results obtained are shown in Table 43.
  • the IR peak retention rate of the polyimide-cycloolefin copolymer composite films obtained in Examples 3, 4, 10 to 12 and Comparative Examples 3 and 4 was measured according to the above method. The results obtained are shown in Table 54.
  • the films obtained in Examples 1, 2, 5 to 9 had lower moisture absorption rates and superior water absorption resistance than Comparative Examples 1 and 2.
  • the films obtained in Examples 3, 4, and 10 to 12 had higher COC IR peak retention rates and superior heat resistance than Comparative Examples 3 and 4.

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Abstract

L'invention concerne une composition comprenant une résine à base de polyimide (A), un polymère (B) et un antioxydant phénolique, l'antioxydant phénolique contenant un substituant P représenté par la formule (P) [dans laquelle Rp, Rq, Rr et Rs représentent chacun indépendamment un atome d'hydrogène, un groupe alkyle en C1-C12 ou un groupe cycloalkyle C5-C12 et * indique une liaison] et une structure S formée en remplaçant le substituant P de l'antioxydant phénolique par un atome d'hydrogène comprend un cycle aromatique éventuellement substitué.
PCT/JP2022/023930 2021-06-21 2022-06-15 Composition WO2022270375A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006152173A (ja) * 2004-11-30 2006-06-15 Sumitomo Bakelite Co Ltd 樹脂組成物、樹脂層、樹脂層付きキャリア材料および回路基板
JP2009185242A (ja) * 2008-02-08 2009-08-20 Hitachi Chem Co Ltd 樹脂組成物及びそれを含む被膜形成材料
JP2013127597A (ja) * 2011-11-16 2013-06-27 Jsr Corp 液晶配向剤、液晶配向膜及び液晶表示素子
JP2017125176A (ja) * 2016-08-31 2017-07-20 三井化学株式会社 低誘電性樹脂組成物、硬化物、ドライフィルム、フィルム、プリプレグ、金属張積層板、プリント配線基板および電子機器
WO2020189481A1 (fr) * 2019-03-19 2020-09-24 富士フイルム株式会社 Composition de résine durcissable, film durci, corps multicouche, procédé de production de film durci et dispositif à semi-conducteur

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006152173A (ja) * 2004-11-30 2006-06-15 Sumitomo Bakelite Co Ltd 樹脂組成物、樹脂層、樹脂層付きキャリア材料および回路基板
JP2009185242A (ja) * 2008-02-08 2009-08-20 Hitachi Chem Co Ltd 樹脂組成物及びそれを含む被膜形成材料
JP2013127597A (ja) * 2011-11-16 2013-06-27 Jsr Corp 液晶配向剤、液晶配向膜及び液晶表示素子
JP2017125176A (ja) * 2016-08-31 2017-07-20 三井化学株式会社 低誘電性樹脂組成物、硬化物、ドライフィルム、フィルム、プリプレグ、金属張積層板、プリント配線基板および電子機器
WO2020189481A1 (fr) * 2019-03-19 2020-09-24 富士フイルム株式会社 Composition de résine durcissable, film durci, corps multicouche, procédé de production de film durci et dispositif à semi-conducteur

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