WO2022045359A1 - Film - Google Patents

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Publication number
WO2022045359A1
WO2022045359A1 PCT/JP2021/031950 JP2021031950W WO2022045359A1 WO 2022045359 A1 WO2022045359 A1 WO 2022045359A1 JP 2021031950 W JP2021031950 W JP 2021031950W WO 2022045359 A1 WO2022045359 A1 WO 2022045359A1
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Prior art keywords
film
group
polymer
solvent
mass
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PCT/JP2021/031950
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English (en)
Japanese (ja)
Inventor
勇輔 小沼
宏司 西岡
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住友化学株式会社
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Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to KR1020237008113A priority Critical patent/KR20230059170A/ko
Priority to CN202180050813.XA priority patent/CN115884996A/zh
Publication of WO2022045359A1 publication Critical patent/WO2022045359A1/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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two condensed rings
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • 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
    • 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
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention relates to a film that can be used as a substrate material compatible with a printed circuit board for a high frequency band and an antenna substrate, and a composition capable of forming 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 of the resin layer serving as the transmission path, particularly the dielectric loss tangent and the relative permittivity, a film having a low dielectric loss tangent has been studied.
  • Patent Document 1 describes 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. However, even with the film formed from the low-dielectric resin composition described in Patent Document 1, the reduction of the dielectric loss tangent was not always sufficient.
  • a resin (A) such as a polyimide resin and a cyclic olefin (co) polymer (B)
  • the present inventors have studied the reduction of dielectric loss tangent, and found that the film formed from the low-dielectric resin composition described in Patent Document 1 may not have sufficient water absorption resistance.
  • an object of the present invention is to provide a film having excellent water absorption resistance and a composition capable of forming the film.
  • the present invention includes the following preferred embodiments.
  • the polymer (B) is at least one polymer selected from the group consisting of an olefin polymer, a polyimide polymer, a fluoropolymer, a silicone polymer, a liquid crystal polymer, an aramid polymer, a styrene polymer and an ether polymer.
  • the cycloolefin-based polymer has the formula (I):
  • m represents an integer of 0 or more
  • R 7 to R 18 represent hydrogen atoms, halogen atoms or hydrocarbon groups having 1 to 20 carbon atoms independently of each other
  • 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 and form a ring with the carbon atom to which they are bonded.
  • a composition comprising the first solvent and the second solvent, and the distance between the HSP values of the second solvent and the particulate polymer (B) is 8.5 or more.
  • the present invention it is possible to provide a film having excellent water absorption resistance and a composition capable of forming the film.
  • the film of the present invention contains a polyimide resin (A) and a particulate polymer (B), and when the haze is 75% or less, the brightness of the reflected light measured by the normal reflected light removal method L * (hereinafter, simply """Brightness") is 37 or less on both sides of the film, contains polyimide resin (A) and particulate polymer (B), and when the haze exceeds 75%, it is measured by the normal reflected light removal method.
  • the brightness L * of the reflected light is 80 or less on both sides of the film.
  • the present inventors have surprisingly found that the water absorption resistance of the film can change depending on the relationship between the haze and the lightness of the film. Therefore, the present inventors further study focusing on the brightness of the film, and when the brightness of the film having a haze of 75% or less is 37 or less on both sides of the film, a film having excellent water absorption resistance can be obtained. It was found that when the brightness of the film having a haze of more than 75% is 80 or less on both sides of the film, a film having excellent water absorption resistance can be obtained.
  • the brightness of the film having a haze of 75% or less is preferably 36.5 or less, more preferably 36 or less, still more preferably 34 or less, and particularly preferably 32 or less on both sides.
  • the brightness of the film is preferably 10 or more, more preferably 20 or more, still more preferably 25 or more on both sides.
  • the brightness is equal to or higher than the above lower limit, curling habits are less likely to occur when the film is stored in a roll form, for example.
  • the brightness of the reflected light measured by the specular light removal (SCE) of the present invention can be measured by using a spectrophotometer, for example, by the method described in Examples. Further, the haze of the film can be measured by using a haze meter based on JIS K7136, for example, by the method described in Examples.
  • the brightness of the film having a haze of more than 75% is preferably 78.5 or less, more preferably 78 or less, still more preferably 76 or less, still more preferably 73 or less, on both sides. Particularly preferably, it is 72 or less.
  • the brightness of the film is preferably 30 or more, more preferably 40 or more, still more preferably 48 or more, still more preferably 50 or more, and particularly preferably 55 or more on both sides.
  • the brightness is equal to or higher than the above lower limit, curling habits are less likely to occur when the film is stored in a roll form, for example.
  • the brightness of the film is determined by the composition of the film, for example, the types of the structural units constituting the polyimide resin (A) and / or the polymer (B) contained in the film, their composition ratios, their molecular weights, and the particulate polymer in the film. It can be adjusted by appropriately adjusting the content of (B), the particle size thereof, the production conditions of the film, and the like.
  • the brightness of the film is the type of the polymer (B) described as a preferred embodiment in the description below, the types of the constituent units constituting the polyimide resin (A) and / or the polymer (B), and their constituent ratios.
  • the lightness of the film may be adjusted to the above range by selecting the content of the particulate polymer (B), the particle size thereof, and the method for producing the film.
  • particle size is meant to include the average primary particle size and / or median size of the particulate polymer (B).
  • the polymer (B) is a polymer different from the polyimide resin (A).
  • the polymer (B) may be a polyimide-based resin having a different type from the polyimide-based resin (A), for example, a different type of monomer unit constituting the resin, its content, and the like.
  • the polymer (B) is not particularly limited, and examples thereof include olefin-based polymers, polyimide-based polymers, fluoropolymers, silicone-based polymers, liquid crystal polymers, aramid polymers, styrene-based polymers, and ether-based polymers.
  • the polymer (B) can be used alone or in combination of two or more. When these are used as the polymer (B), the particle size of the polymer (B) can be easily reduced and the dispersibility can be easily improved. Further, when these are used as the polymer (B), it is easy to reduce the brightness and linear expansion coefficient (hereinafter, may be referred to as CTE) of the obtained film, and it is easy to improve the dielectric properties and water absorption resistance of the film.
  • CTE brightness and linear expansion coefficient
  • At least one polymer selected from the group consisting of an olefin polymer, a polyimide polymer, a fluoropolymer, a liquid crystal polymer, a styrene polymer and an ether polymer is preferable, an olefin polymer is more preferable, and polyethylene and high At least one polymer selected from the group consisting of density polyethylene, polypropylene, polymethylpentene and cycloolefin-based polymers is more preferable, and cycloolefin-based polymers are particularly preferable.
  • the dielectric property means a property related to dielectric including dielectric loss, relative permittivity and dielectric loss tangent, and that the dielectric property is enhanced or improved is, for example, dielectric loss, relative permittivity and / or. It shows that the dielectric loss tangent is reduced.
  • the cycloolefin polymer is the formula (I).
  • m represents an integer of 0 or more
  • R 7 to R 18 represent hydrogen atoms, halogen atoms or hydrocarbon groups having 1 to 20 carbon atoms independently of each other, and when a plurality of R 11 to R 14 are present, they are independently and identical to each other. May be different, and R 16 and R 17 may be bonded to each other and form a ring with the carbon atom to which they are bonded.
  • the "particle size of the particulate polymer (B)" may be simply referred to as the "particle size”.
  • m is an integer of 0 or more. From the viewpoint that the particle size and CTE can be easily reduced, the water absorption resistance and heat resistance of the film can be easily increased, and the film can be easily obtained, 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.
  • Examples of the hydrocarbon group having 1 to 20 carbon atoms which is a member of the substituents of R 7 to R 18 , include alkyl such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group and a dodecyl group.
  • alkyl such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group and a dodecyl group.
  • Aryl group such as phenyl group, trill group, naphthyl group
  • Aralkyl group such as benzyl group and phenetyl group
  • Group in which a part of hydrogen atom of the above alkyl group, aryl group and aralkyl group is replaced with a halogen atom Can be mentioned.
  • R 7 to R 18 are preferably hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, preferably hydrogen atoms or. It is more preferably an alkyl group having 1 to 10 carbon atoms.
  • Examples of the cycloolefin represented by the 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 the raw material monomer, reduction of the particle size and CTE of the film, and improvement of the heat resistance of the film.
  • the cycloolefin represented by the formula (I) may be used alone or in combination of two or more.
  • the cycloolefin polymer preferably contains a two-chain structure of the monomer unit (I).
  • the heat resistance is likely to be improved as compared with a polymer having the same content of the monomer unit (I).
  • the presence or absence of the two-chain structure can be determined by 13 C-NMR spectrum analysis. For example, in the case of a tetracyclodecene-ethylene copolymer, signals derived from the ethylene-tetracyclodecene-ethylene chain, which is an isolated chain of tetracyclodecene, appear at around 54.7 ppm and around 51.1 ppm, and endo-exo bond.
  • Ethylene-tetracyclodecene-tetracyclodecene-ethylene chain-derived signals which are two chains of tetracyclodecene, are located near 51.5 ppm and around 50.8 ppm, and are exo-exo-bonded ethylene-tetracyclodecene-tetracyclo. Since the signal derived from the decene-ethylene chain appears at around 55.3 ppm and around 54.3 ppm, it can be determined by the signal pattern around 55 ppm and around 50 ppm.
  • 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 two chain represented by the following structural formula (III-2) is included.
  • the ratio of the meso-type two-chain to the racemo-type two-chain (hereinafter, may be referred to as meso-type two-chain / racemo-type two-chain) is preferably 0.50 or less, more preferably 0.40 or less, 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-type two-chain to the racemic-type two-chain is, for example, using 13 C-NMR in "RA Wendt, G.
  • the mechanical property means the mechanical property including the bending resistance and the elastic modulus, and when the mechanical property is enhanced or improved, for example, the bending resistance and / or the elastic modulus is increased. Show that.
  • the content of the monomer unit (I) in the cycloolefin polymer is preferably 60 mol% or more, more preferably 65 mol% or more, still more preferably 65 mol% or more, based on the total molar amount of the repeating units constituting the cycloolefin polymer.
  • the content of the monomer unit (I) is at least the above lower limit, it is easy to raise the glass transition temperature (hereinafter, may be referred to as Tg), so that it is easy to reduce the CTE of the film, and the brightness of the film is also easy to increase. It is easy to improve the water absorption resistance because it is easy to reduce. Further, it is easy to improve mechanical properties such as heat resistance and bending resistance of the film. When the content of the monomer unit (I) is not more than the above upper limit, it is easy to enhance mechanical properties such as bending resistance.
  • the content of the monomeric unit (I) is based on the attribution described in "RA Wendt, G. Fink, Macromol. Chem. Phys., 2001, 202, 3490" using 13 C-NMR. It can be calculated, for example, by the method described in Examples.
  • the cycloolefin-based polymer is ethylene, a linear ⁇ -olefin having 3 to 20 carbon atoms, and carbon from the viewpoint of easily reducing the CTE of the film and easily enhancing mechanical properties such as water absorption resistance and bending resistance. It preferably contains a monomer unit (II) derived from at least one selected from the group consisting of the aromatic vinyl compounds of the number 8 to 20, and preferably contains a monomer unit (II) derived from ethylene. More preferred.
  • linear ⁇ -olefin having 3 to 20 carbon atoms examples include propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene, 1-octene, 1-nonene, 1-decene and the like. Be done. Among these, propylene, 1-butene, 1-hexene or 1-octene is preferable, and propylene is preferable from the viewpoint of easily reducing the CTE of the film and easily enhancing the mechanical properties such as water absorption resistance and bending resistance. Is more preferable.
  • the linear ⁇ -olefin having 3 to 20 carbon atoms one type may be used alone, or two or more types may be used in combination.
  • the "linear ⁇ -olefin” refers to a linear olefin having a carbon-carbon unsaturated double bond at the ⁇ -position.
  • aromatic vinyl compound having 8 to 20 carbon atoms examples include styrene, methylstyrene, dimethylstyrene, ethylstyrene, tert-butylstyrene, vinylnaphthalene, vinylanthracene, diphenylethylene, isopropenylbenzene, isopropenyltoluene and isopropenyl.
  • Examples thereof include ethylbenzene, isopropenylpropylbenzene, isopropenylbutylbenzene, isopropenylpentylbenzene, isopropenylhexylbenzene, isopropenyloctylbenzene, isopropenylnaphthalene, isopropenylanthracene and the like.
  • styrene, methylstyrene or dimethylstyrene is preferable, and styrene is more preferable, from the viewpoints of easy availability of the raw material monomer, easy reduction of CTE of the film, and easy improvement of mechanical properties such as bending resistance. ..
  • the aromatic vinyl compound having 8 to 20 carbon atoms one kind may be used alone, or two or more kinds may be used in combination.
  • the cycloolefin polymer is made from ethylene, propylene and styrene from the viewpoints of easy availability of raw material monomers, easy reduction of CTE of the film, and easy improvement of mechanical properties such as bending resistance. It may contain a monomer unit (II) derived from at least one selected from the group consisting of ethylene and styrene, more preferably a monomer unit (II) derived from at least one selected from the group consisting of ethylene and styrene. preferable.
  • the content of the monomer unit (II) in the cycloolefin polymer is preferably 0 mol% or more, more preferably 0.01 mol% or more, based on the total molar amount of the repeating units constituting the cycloolefin polymer. It is 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, and particularly preferably 25 mol% or less.
  • the content of the monomer unit (II) is at least the above lower limit, it is easy to improve mechanical properties such as bending resistance of the film, processability and moldability.
  • the content of the monomer unit (II) is not more than the above upper limit, it is easy to reduce the CTE of the film and to improve the mechanical properties such as water absorption resistance, heat resistance and bending resistance.
  • the cycloolefin polymer is a cyclo-olefin polymer from the viewpoint of easily improving mechanical properties such as heat resistance, processability, bending resistance, and water absorption resistance, and easily reducing the particle size and CTE. It is preferably an olefin-based polymer, preferably a monomer unit (I) derived from cycloolefin represented by the formula (I) and ethylene, a linear ⁇ -olefin having 3 to 20 carbon atoms, and 8 to 20 carbon atoms.
  • a cycloolefin-based polymer containing a monomer unit (II) derived from at least one selected from the group consisting of aromatic vinyl compounds of the above, and a monomer unit (I) derived from norbornene.
  • Ethylene-norbornene copolymer containing and a monomer unit (II) derived from ethylene, or styrene containing a monomer unit (I) derived from norbornene and a monomer unit (II) derived from styrene.
  • -It is more preferably a norbornene copolymer.
  • the cycloolefin-based polymer may contain another monomer unit (III).
  • Other monomers constituting the other monomer unit (III) include, for example, conjugated diene such as butadiene or isoprene; non-conjugated diene 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; vinyl acetate and the like can be mentioned.
  • the other monomer unit (III) can be used alone or in combination of two or more.
  • the polymer (B) can be used alone or in combination of two or more.
  • examples of the olefin polymer other than the cycloolefin polymer include the monomer unit (II); the monomer unit (III); 3-methyl-1-butene and 3-methyl-.
  • At least one monomer unit selected from the group consisting of 1-pentene, 4-methyl-1-pentene and vinylcycloalkane; and polymers or copolymers containing derivatives thereof and the like include polyethylene, high density. Polyethylene, polypropylene or polymethylpentene is preferable, and polypropylene or polymethylpentene is more preferable from the viewpoint of increasing heat resistance.
  • examples of the polyimide-based polymer include a polyimide-based polymer soluble in a first solvent.
  • the fluoropolymer is a polymer of an olefin containing fluorine or a modified product thereof, and specifically, fluoroolefins such as tetrafluoroethylene, trifluoroethylene, and chlorotrifluoro.
  • fluoroolefins such as tetrafluoroethylene, trifluoroethylene, and chlorotrifluoro.
  • examples thereof include polymers and copolymers containing at least one monomer unit selected from the group consisting of ethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride and the like, and examples thereof include polytetrafluoroethylene (hereinafter referred to as PTFE).
  • the fluoropolymer is preferably a polymer having a constituent unit derived from tetrafluoroethylene, and more preferably, the molar ratio of the constituent units derived from tetrafluoroethylene to the total of all the constituent units is 0.
  • the molar ratio is 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 constituent unit of the fluoropolymer can be obtained by NMR measurement, and in calculating the molar ratio, for example, Eric B. Twum et al., “Multidimensional 19F NMR Analytics of Terpolymers from Vinylidene Fluoride (VDF)-Hexafluoropropylene). (HFP)-Tetrafluoroethylene (TFE) ”, Macromolecules, 2015, Vol. 48, No. 11, p.3563-3576. Further, from the viewpoint of enhancing the solubility in the first solvent, it may be a copolymer of at least one selected from the group consisting of vinyl ethers, vinyl esters and allyl ethers and the monomer unit.
  • examples of the liquid crystal polymer include a polymer having an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, an aromatic diol, an aliphatic diol, or the like as a repeating unit.
  • Specific examples of the monomer giving the aromatic hydroxycarboxylic acid repeating unit 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, These include alkyl, alkoxy or halogen substituents, as well as ester-forming derivatives thereof.
  • parahydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are preferable from the viewpoint of easily improving the water absorption resistance, mechanical properties and heat resistance of the film.
  • the monomer giving the aromatic dicarboxylic acid repeating unit include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,4. Included are aromatic dicarboxylic acids such as -naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, alkyl, alkoxy or halogen substituents thereof, and ester-forming derivatives thereof. Of these, terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid are preferable from the viewpoint of easily improving the water absorption resistance, mechanical properties, and heat resistance of the film.
  • the monomer giving the aromatic diol repeating unit include hydroquinone, resorcin, 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, 4,4'-dihydroxybiphenyl ether, alkyl, alkoxy or halogen substituents thereof, and these. Examples of the ester-forming derivative of. Of these, hydroquinone and 3,3'-dihydroxybiphenyl are preferable from the viewpoint of easily improving the water absorption resistance, mechanical properties and heat resistance of the film.
  • the monomer giving the aliphatic diol repeating unit include ethylene glycol, 1,4-butanediol, aliphatic diols such as 1,6-hexanediol, and acylated products thereof.
  • ethylene glycol is preferable from the viewpoint of easily improving the water absorption resistance, mechanical properties and heat resistance of the film.
  • the styrene-based polymer is a resin containing at least one styrene in a repeating structural unit, for example, polystyrene, ABS resin (acrylonitrile, butadiene, styrene copolymer), AS resin (acrylonitrile). -Styrene copolymer) and the like.
  • polystyrene is preferable from the viewpoint of easily improving the dielectric properties.
  • the ether-based polymer is a resin containing at least one repeating unit containing an ether group in the main chain, and is, for example, a polyetherimide, a polyphenylene ether, a polyether sulfone, a polyether ketone, and the like.
  • examples thereof include polyether ether ketones.
  • polyphenylene ether, polyether sulfone, and polyether ether ketone are preferable from the viewpoint of easily improving the water absorption resistance and dielectric properties of the film.
  • 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, still more preferably 20. 000 or more, even more preferably 30,000 or more, particularly preferably 50,000 or more, particularly more preferably 70,000 or more, particularly still more preferably 90,000 or more, preferably 2,000,000 or less, It is more preferably 1,000,000 or less, still more preferably 700,000 or less.
  • Mw is at least the above lower limit, it is easy to improve the water absorption resistance and heat resistance of the film, and it is easy to improve the strength.
  • Mw is not more than the above upper limit, it is easy to improve the water absorption resistance, mechanical properties and moldability of the film.
  • the ratio (Mw / Mn) of Mw of the polymer (B) to the number average molecular weight (hereinafter, the number average molecular weight may be abbreviated as Mn) is preferably 2. 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, still more preferably 1. It is 50 or more, more preferably 1.60 or more, and particularly preferably 1.65 or more.
  • Mw and Mn can be determined by gel permeation chromatography (hereinafter, may be abbreviated as GPC) measurement and converted to standard polystyrene, and can be determined, for example, by the method described in Examples.
  • the refractive index of the polymer (B) is preferably 1.600 or less, more preferably 1.570 or less, still more preferably 1. It is 550 or less, preferably 1.500 or more, and more preferably 1.520 or more.
  • the refractive index of the polymer (B) can be measured by a refractometer, for example, by the method described in Examples.
  • the CTE of the polymer (B) is preferably 110 ppm / K or less, more preferably 80 ppm / K or less, even more preferably 58 ppm / K or less, even more preferably 55 ppm / K or less, particularly preferably. It is 50 ppm / K or less, preferably 0 ppm / K or more, more preferably 0.01 ppm / K or more, still more preferably 1 ppm / K or more, still more preferably 5 ppm / K or more.
  • the CTE of the polymer (B) is not more than the above upper limit, it is easy to reduce the CTE of the obtained film.
  • the CTE of the film when a copper-clad laminate is produced by laminating with a copper foil, it is preferable to adjust the CTE of the film to around 20 ppm / K from the viewpoint of preventing the laminated film from peeling off.
  • the polymer (B) having the optimum CTE can be selected according to the CTE of the resin to be mixed.
  • the CTE can be measured by, for example, thermomechanical analysis (hereinafter, may be referred to as TMA), and can be obtained by the method described in Examples.
  • At least one of the glass transition temperature and the 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, still more preferably 180 ° C. or higher, particularly preferably 200 ° C. or higher, and particularly more preferably 220 ° C. or higher.
  • it is more preferably 240 ° C. or higher, most preferably 260 ° C. or higher, preferably 500 ° C. or lower, more preferably 400 ° C. or lower, still more preferably 350 ° C. or lower, still more preferably 320 ° C.
  • 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. or higher. ° C. or higher, particularly preferably 200 ° C. or higher, particularly more preferably 220 ° C. or higher, particularly still more preferably 240 ° C. or higher, most preferably 260 ° C. or higher, preferably 500 ° C. or lower, still more preferably 400 ° C. or lower, still more preferable. Is 350 ° C. or lower.
  • the CTE of the film is likely to be reduced, and mechanical properties such as water absorption resistance, heat resistance and bending resistance are likely to be further enhanced.
  • the mechanical properties of the film particularly the resistance to repeated bending, are likely to be enhanced.
  • the Tg of the polymer (B) is the softening temperature measured by TMA based on JIS K7196, and can be measured by, for example, the method described in Examples.
  • the method for adjusting the Tg and melting point of the polymer (B) is not particularly limited, but for example, a method for appropriately adjusting the content of the monomer unit (I), the Mw of the polymer (B), the degree of crystallinity, and the like can be used. Can be mentioned. The larger the content of the monomer unit (I), the Mw of the polymer (B), and at least one selected from the group consisting of the degree of crystallinity, the higher the Tg and melting point of the polymer (B) tend to be.
  • the melting point of the polymer (B) can be determined by measuring the melting peak temperature from the melting curve obtained by using, for example, a differential scanning calorimeter (DSC, manufactured by Hitachi High-Tech Science Corporation).
  • the average primary particle size of the particulate polymer (B) is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 5 ⁇ m or less, still more preferably 3 ⁇ m or less, and particularly preferably. It is 1 ⁇ m or less, more preferably 0.8 ⁇ m or less, particularly preferably 0.5 ⁇ m or less, preferably 0.01 ⁇ m or more, more preferably 0.03 ⁇ m or more, still more preferably 0.05 ⁇ m or more.
  • the average primary particle diameter of the particulate polymer (B) is at least the above lower limit, it is easy to enhance the mechanical properties of the film.
  • the average primary particle diameter of the particulate polymer (B) can be obtained by image analysis of an image taken with an electron microscope. For example, a cross-sectional observation of the film is performed using a scanning transmission electron microscope (STEM), the particle size of 50 or more particles is measured from the observed image, and the average value thereof is the average primary particle size of the particulate cycloolefin copolymer. Can be.
  • STEM scanning transmission electron microscope
  • the content of the particulate polymer (B) is usually 1% by mass or more, preferably 5% by mass or more, more preferably, with respect to the total mass of the polyimide resin (A) and the particulate polymer (B) contained in the film. Is 10% by mass or more, more preferably 15% by mass or more, particularly preferably 20% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less, and particularly preferably. It is 30% by mass or less.
  • the content of the particulate polymer (B) is at least the above lower limit, it is easy to increase the particle dispersibility in the film, so that it is easy to reduce the brightness of the film, and also water absorption resistance, surface smoothness and mechanical properties. Easy to increase.
  • the content of the particulate polymer (B) is not more than the above upper limit, the brightness of the film is easily reduced and the moldability is easily improved. If the dispersibility of the particles in the film is high, the thermal conductivity and the uniformity of CTE are high. Therefore, for example, when the film is used as the resin layer of CCL, it is easy to suppress the peeling of the film and the copper foil. Become.
  • the polymer (B) may be a commercially available product or may be produced by a conventional method.
  • the polymer (B) is preferably a cycloolefinic polymer.
  • the method for producing the cycloolefin-based polymer is not particularly limited, but for example, the cycloolefin-based polymer is simply formed in the presence of a catalyst using the transition metal complex ( ⁇ ) represented by the formula (IV) as one component.
  • At least one selected from the group consisting of a polymer for example, a cycloolefin represented by the 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 produced by polymerizing one monomer and optionally the other monomer.
  • a polymer for example, a cycloolefin represented by the 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 produced by polymerizing one monomer and optionally the other monomer.
  • the transition metal complex ( ⁇ ) represented by the formula (IV) is used, 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 Group 4 transition metal element in the Periodic Table of the Elements.
  • Cp represents a group having a cyclopentadienyl skeleton and represents A represents a group 16 atom in the periodic table of elements, T represents an atom of Group 14 in the periodic table of elements.
  • D 1 and D 2 are 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 6 to 20 carbon atoms. It represents an aryloxy group or a disubstituted amino group having 2 to 20 carbon atoms, which may be the same or different.
  • R 1 to R 6 are 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 an aryl having 6 to 20 carbon atoms.
  • M is a transition metal element of Group 4 of the Periodic Table of Elements (IUPAC Inorganic Chemistry Naming Method Revised Edition 1989), and examples thereof include a titanium atom, a zirconium atom, and a hafnium atom.
  • Cp is a group having a cyclopentadienyl skeleton, and examples thereof include 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 -A propylfluorenyl group, a phenylfluorenyl group, a dimethylfluorenyl group and the like can be mentioned.
  • a cyclopentadienyl group preferably a cyclopentadienyl group, a methylcyclopentadienyl group, a tetramethylcyclopentadienyl group, an n-butylcyclopentadienyl group, an isobutylcyclopentadienyl group, an indenyl group, a methylindenyl group.
  • a fluorenyl group may be mentioned.
  • A is an atom of Group 16 in the periodic table of elements, and examples thereof include 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 examples thereof include a carbon atom, a silicon atom, and a germanium atom. Among these, a carbon atom or a silicon atom is preferable.
  • D 1 and D 2 are independent of each other, 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 of carbon atoms. It is an aryloxy group of 6 to 20 or a disubstituted amino group having 2 to 20 carbon atoms, which may be the same or different. Among these, a halogen atom is preferable.
  • D 1 and D 2 are halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • D 1 and D 2 are hydrocarbon groups
  • the number of carbon atoms thereof is preferably 1 to 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.
  • examples thereof include a group, an n-octyl group, a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a naphthyl group, a benzyl group and the like.
  • D 1 and D 2 are halogenated hydrocarbon groups
  • D 1 and D 2 are halogenated hydrocarbon groups
  • D 1 and D 2 are halogenated hydrocarbon groups.
  • D 1 and D 2 are alkoxy groups
  • D 1 and D 2 are alkoxy groups
  • D 1 and D 2 are alkoxy groups
  • examples thereof include a pentoxy group, a neopentoxy group, an n-hexoxy group, an n-octoxy group and the like.
  • D 1 and D 2 are aryloxy groups
  • a phenoxy group a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a naphthyloxy group and the like.
  • the disubstituted amino group is an amino group in which two substituents are bonded.
  • Specific examples thereof include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, diisobutylamino group, di-sec-butylamino group and di-tert-butyl.
  • Examples thereof include an amino group, a di-n-hexyl amino group, a di-n-octyl amino group, and a diphenyl amino group.
  • R 1 to R 6 are independent of each other, 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 of carbon atoms. It represents an aryloxy group of 6 to 20, 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 they may be optional. They may be combined to form a ring. Among these, a hydrocarbon group having 1 to 20 carbon atoms is preferable.
  • R 1 to R 6 are hydrocarbon groups, the number of carbon atoms is preferably 1 to 10. Specific examples thereof 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 Groups, 2,3,4,6-tetramethylphenyl group, pentamethylphenyl group and the like can be mentioned.
  • R 1 to R 6 are a halogen atom, a halogenated hydrocarbon group, an alkoxy group, an aryloxy group, and a disubstituted amino group
  • D 1 and D 2 as a halogen atom and a halogenated hydrocarbon group.
  • an alkoxy group, an aryloxy group, and a disubstituted amino group those exemplified above can be mentioned.
  • R 1 to R 6 are silyl groups
  • a trimethylsilyl group a triethylsilyl group, a tri-n-propylsilyl group, a triisopropylsilyl group, a tri-n-butylsilyl group, a triisobutylsilyl group, and a tri.
  • examples thereof include -sec-butylsilyl group, tritert-butylsilyl group and triphenylsilyl group.
  • Such a compound represented by the formula (IV) include isopropanol (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride and isopropyridene (methylcyclo).
  • the compound in which titanium is changed to zirconium or hafnium in the above specific example, and the compound in which isopropridene is changed to dimethylsilylene, diphenylcilylene, and methylene including them can be similarly exemplified.
  • a compound in which dichloride is changed to dibromide, diiodide, dimethyl, dibenzyl, dimethoxydo, or diethoxyde can be similarly exemplified.
  • the transition metal complex ( ⁇ ) represented by the above formula (IV) can be used as a catalyst for producing the polymer (B) according to the embodiment of the present invention in combination with various co-catalysts.
  • the cocatalyst is a compound that interacts with the transition metal complex ( ⁇ ) to produce a 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), and these co-catalysts are used.
  • the structure of the polymerization active species produced by this is not clear.
  • Equation ( ⁇ 1) BQ 1 Q 2 Q 3 Equation ( ⁇ 2) J + (BQ 1 Q 2 Q 3 Q 4 ) - Equation ( ⁇ 3) (L—H) + (BQ 1 Q 2 Q 3 Q 4 ) - [In the formulas ( ⁇ 1) to ( ⁇ 3), B represents a boron atom in a trivalent valence state.
  • Q1 to Q4 are independent of each other, 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, and 1 to 20 carbon atoms.
  • J + represents an inorganic or organic cation
  • L represents a neutral Lewis base
  • (L—H) + represents a Bronsted acid.
  • organoaluminum compound ( ⁇ ) a known organoaluminum compound can be used. Specific examples thereof include organoaluminum compounds represented by the formula ( ⁇ 1), cyclic aluminoxane having a structure represented by the formula ( ⁇ 2), and linear aluminoxane having a structure represented by the formula ( ⁇ 3). , These can be used alone or in combination of two or more.
  • Equation ( ⁇ 1) E 1 a AlZ 3-a Equation ( ⁇ 2) ⁇ -Al (E 2 ) -O- ⁇ b Equation ( ⁇ 3) E 3 ⁇ -Al (E 3 ) -O- ⁇ c AlE 3 2
  • E1 , E2 and E3 represent hydrocarbon groups having 1 to 8 carbon atoms independently of each other , and all E1, all E2 and all.
  • E 3 may be the same or different
  • Z may represent hydrogen or halogen
  • all Z may be the same or different
  • a represents an integer of 0-3.
  • B represent an integer of 2 or more
  • 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, and the like.
  • Dialkylaluminum chloride such as dihexylaluminum chloride; alkylaluminum dichloride 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 hydride and the like. Among these, trialkylaluminum is preferable, and triethylaluminum or triisobutylaluminum is more preferable.
  • E 2 and E 3 in the formula ( ⁇ 2) and the formula ( ⁇ 3) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group and neopentyl.
  • Examples thereof include an alkyl group such as a group. Among these, a methyl group or an isobutyl group is preferable.
  • b is an integer of 2 or more, preferably an integer of 2 to 40.
  • c is an integer of 1 or more, preferably an integer of 1 to 40.
  • the above aluminoxane is made by various methods.
  • the method is not particularly limited, and it may be produced according to a known method.
  • a method for making a solution of trialkylaluminum, for example, trimethylaluminum, etc. in a suitable organic solvent, for example, benzene, an aliphatic hydrocarbon, etc. in contact with water, trialkylaluminum, for example, trimethylaluminum, etc.
  • An example is a method of making the solution by contacting it with a metal salt containing water of crystallization, for example, copper sulfate hydrate.
  • any of the boron compounds represented by the formula ( ⁇ 1), the formula ( ⁇ 2) or the formula ( ⁇ 3) can be used.
  • B represents a boron atom in a trivalent valence state
  • Q1 to Q3 are halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, and carbon atoms 1 to 20 independently of each other.
  • Q1 to Q3 are independent of each other, 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 the formula ( ⁇ 1) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, and tris (2,3,4,5-). Examples thereof include tetrafluorophenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, and the like, and tris is preferable. (Pentafluorophenyl) Borane can be mentioned.
  • B represents a boron atom in a trivalent valence state
  • Q1 to Q4 are the same as Q1 to Q3 in the above formula ( ⁇ 1).
  • J + represents an inorganic or organic cation.
  • Examples of the inorganic cation in J + include a ferrosenium cation, an alkyl-substituted ferrosenium cation, and a silver cation.
  • Examples of the organic cation in J + include triphenylmethyl cation and the like.
  • ferrosenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrosenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, and triphenylmethyl tetrakis.
  • Examples thereof include (pentafluorophenyl) borate, triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate, and preferably triphenylmethyltetrakis (pentafluorophenyl) borate.
  • B represents boron in a trivalent valence state
  • Q1 to Q4 are the same as Q1 to Q3 in the above formula ( ⁇ 1).
  • L represents a neutral Lewis base
  • (L—H) + represents a Bronsted acid.
  • examples of the Bronsted acid (L—H) + include trialkyl-substituted ammonium cations, N, N-dialkylanilinium cations, dialkylammonium cations, and triallylphosphonium cations.
  • (BQ 1 Q 2 Q 3 Q 4 ) - the same as described above can be mentioned.
  • organoaluminum compound ( ⁇ ) and compound ( ⁇ ) in combination.
  • the transition metal complex ( ⁇ ) represented by the formula (IV), the organoaluminum compound ( ⁇ ) and / or the compound ( ⁇ ) can be used in any order at the time of polymerization, but any compound thereof. You may use the reaction product obtained by contacting the combination of the above in advance.
  • the molar ratio of the co-catalyst / transition metal complex ( ⁇ ) is preferably 0.01 to 10,000, more preferably 0.5 to 2,000.
  • the concentration of the transition metal complex ( ⁇ ) is preferably 0.0001 to 5 mmol / L, more preferably 0.001 to 1 mmol / L.
  • the amount of the 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 the monomers used.
  • the polymerization method of the polymer (B) according to the embodiment of the present invention is not particularly limited, and for example, a batch type or continuous type gas phase polymerization method, a bulk polymerization method, or a solution weight using an appropriate solvent is used. Any method such as a legal method or a slurry polymerization method can be adopted.
  • a solvent When a solvent is used, various solvents can be used under the condition that the catalyst is not inactivated, and examples of such a solvent include hydrocarbon solvents such as benzene, toluene, pentane, hexane, heptane, and cyclohexane; Examples thereof include halogenated hydrocarbon solvents such as dichloromethane and ethylene dichloride.
  • hydrocarbon solvents such as benzene, toluene, pentane, hexane, heptane, and cyclohexane
  • 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.
  • the ethylene and hydrogen are put into the system, it is preferable to pressurize with the partial pressure of hydrogen and then pressurize with the partial pressure of ethylene. Further, after putting the solution of the cycloolefin represented by the formula (I) into the polymerization reaction tank, toluene may be further added.
  • the polymerization temperature is preferably 50 ° C. or higher, more preferably 50 to 150 ° C., and even more preferably 50 ° C. to 100 ° C.
  • a chain transfer agent such as hydrogen can also 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, may be referred to as a polyimide resin) and a resin containing a repeating structural unit containing both an imide group and an amide group (hereinafter referred to as a polyimide resin).
  • Polyamide-imide resin a resin containing a repeating structural unit containing both an imide group and an amide group
  • the precursor before producing the polyimide resin is a polyamic acid.
  • a "repeating structural unit” may be referred to as a "constituent unit”.
  • the "constituent unit derived from” may be simply referred to as "unit", and for example, the constituent unit derived from a compound may be referred to as a compound unit.
  • the polyimide resin (A) is represented by the formula (1):
  • X represents a divalent organic group
  • Y represents a tetravalent organic group
  • * represents a bond
  • X in the formula (1) represents a divalent organic group independently of each other, and preferably represents a divalent organic group having 2 to 100 carbon atoms.
  • the divalent organic group include a divalent aromatic group and a divalent aliphatic group
  • examples of the divalent aliphatic group include a divalent acyclic aliphatic group or a divalent aliphatic group.
  • Cyclic aliphatic groups can be mentioned. Among these, a divalent cyclic aliphatic group and a divalent aromatic group are preferable, and a divalent aromatic group is preferable from the viewpoint that the CTE of the film can be easily reduced and the heat resistance and mechanical properties can be easily improved. Is more preferable.
  • the 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 which case the carbon number of these groups is preferably 1.
  • the divalent aromatic group is a divalent organic group having an aromatic group, and an aliphatic group or another substituent may be contained in a part of the structure thereof.
  • the divalent aliphatic group is a divalent organic group having an aliphatic group, and a part of the structure thereof may contain other substituents, but does not contain an aromatic group.
  • the polyimide resin (A) may contain a plurality of types of X, and the plurality of types of X may be the same as each other or may be different from each other.
  • X in the formula (1) for example, the group (structure) represented by the formulas (2) to (8); the hydrogen atom in the group represented by the formulas (5) to (8) is a methyl group. , 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 substituted group and the like.
  • Ra and R b are independent of each other, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 6 to 12 carbon atoms.
  • the hydrogen atoms contained in Ra and R b may be substituted with halogen atoms independently of each other, and W is independent of each other, single -bonded, -O-, -CH 2- .
  • R c represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a hydrogen atom or a halogen atom, and n represents 0 to 0 to. 4 is an integer, t is an integer of 0 to 4, u is an integer of 0 to 4, and * represents a bond.
  • the 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-2).
  • S1 and S2 represent integers from 0 to 20 independently of each other
  • * represents a bond.
  • X in the formula (1) include, for example, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a propylene group, a 1,2-butanediyl group, and a 1,3-butanediyl group.
  • 1,12-Dodecandyl group, 2-methyl-1,2-propanediyl group, 2-methyl-1,3-propanediyl group and other linear or branched alkylene groups with divalent acyclic Examples include aliphatic groups.
  • the hydrogen atom in the divalent acyclic aliphatic group may be substituted with a halogen atom, and the carbon atom may be substituted with a hetero atom, for example, an oxygen atom, a nitrogen atom or the like.
  • the polyimide-based resin (A) in the present invention is in the formula (1) from the viewpoint of easily achieving high water absorption resistance, high dielectric property, low CTE, high heat resistance and high mechanical property of the film.
  • X preferably contains the structure represented by the formula (2) and / or the structure represented by the formula (3), and more preferably contains the structure represented by the formula (2).
  • each benzene ring or cyclohexane ring is at the ortho-position, meta-position or para-position, or ⁇ -position, ⁇ -position or ⁇ -position, respectively, based on ⁇ W—. It may be bonded to any of them, and from the viewpoint of easily reducing the CTE of the film and easily enhancing the water absorption resistance, heat resistance and mechanical properties, it is preferably in the meta-position or para-position, or ⁇ -position or ⁇ -position. It can preferably bind to the para position or the ⁇ position.
  • R a and R b 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.
  • the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group, and 2 -Methyl-butyl group, 3-methylbutyl group, 2-ethyl-propyl group, n-hexyl group and the like can be mentioned.
  • alkoxy group having 1 to 6 carbon atoms examples include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group and a cyclohexyloxy group.
  • aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a naphthyl group and a biphenyl group.
  • the hydrogen atom contained in Ra and R b may be substituted with a halogen atom independently of each other, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • Ra and R b are independent of each other and have an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms.
  • alkyl fluoride group having 1 to 6 carbon atoms is preferably an alkyl fluoride group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or an alkyl fluoride group having 1 to 3 carbon atoms, and it is a methyl group or a trifluoromethyl group. Is even more preferable.
  • t and u are integers of 0 to 4 independently of each other, which is preferable from the viewpoints that the CTE of the film can be easily reduced and the heat resistance and mechanical properties can be easily improved.
  • W is single-bonded independently of each other, -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 ) -reduces the CTE of the film.
  • R c represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a hydrogen atom or a halogen atom.
  • Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and an n-.
  • Etc. which may be substituted with a halogen atom.
  • Examples of the halogen atom include the same as above.
  • n is an integer of 0 to 4, and is preferably 0 from the viewpoint of easily reducing the CTE of the film and easily improving the water absorption resistance, heat resistance and mechanical properties.
  • n is 2 or more, the plurality of Ws, Ras, and ts may be the same or different from each other, and the positions of the bonds of each benzene ring with respect to ⁇ W— are also the same. It may or may not be different.
  • the polyimide-based resin (A) in the present invention contains both the structure represented by the formula (2) and the structure represented by the formula (3) as X in the formula (1), the formula (2) is used.
  • W, n, Ra, R b , t and u may be the same as or different from W, n, Ra , R b , t and u in the formula (3) independently of each other. ..
  • ring A represents a cycloalkane having 3 to 8 carbon atoms.
  • the cycloalkane include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and preferably cycloalkane having 4 to 6 carbon atoms.
  • the bonds may or may not be adjacent to each other.
  • the two bonds may be in the positional relationship of the ⁇ -position, the ⁇ -position, or the ⁇ -position, and may be preferably in the positional relationship of the ⁇ -position or the ⁇ -position.
  • R d in the 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 R7 to R18, and preferably represent an alkyl group having 1 to 10 carbon atoms.
  • r represents an integer of 0 or more and (number of carbon atoms of ring A-2) or less. r is 0 or more, preferably 4 or less.
  • S1 and S2 in the formula (4) represent integers of 0 to 20 independently of each other. S1 and S2 are independent of each other, preferably 0 or more, more preferably 2 or more, and preferably 15 or less.
  • the X in the formula (1) when X in the formula (1) includes a structure represented by the formula (2) and / or the formula (3), the X in the formula (1) is the formula (2). And / or the ratio of the structural unit represented by the formula (3) is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably, with respect to the total molar amount of the structural unit represented by the formula (1). Is 70 mol% or more, particularly preferably 90 mol% or more, and preferably 100 mol% or less. When the ratio of the structural unit represented by the formula (2) and / or the formula (3) is in the above range, X in the formula (1) can easily reduce the CTE of the film, and has water absorption resistance and heat resistance.
  • the ratio of the structural unit in which Y in the formula (1) is represented by the formula (2) and / or the formula (3) can be measured using, for example, 1 H-NMR, or calculated from the charging ratio of the raw materials. You can also do it.
  • Y represents a tetravalent organic group independently of each other, preferably a tetravalent organic group having 4 to 40 carbon atoms, and more preferably 4 having a cyclic structure and 4 to 40 carbon atoms.
  • the cyclic structure include an alicyclic ring, an aromatic ring, and a heterocyclic structure.
  • the 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 which case the carbon number of these groups is preferably 1 to 8. Is.
  • the polyimide-based resin (A) in the present invention may contain a plurality of types of Y, and the plurality of types of Y may be the same as or different from each other.
  • Y the group (structure) represented by the formulas (31) to (38); the hydrogen atom in the group represented by the formulas (34) to (38) is a methyl group, an ethyl group, or n-propyl.
  • R 19 to R 26 have a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 6 to 12 carbon atoms independently of each other. Hydrogen atoms representing an aryl group and contained in R 19 to R 26 may be substituted with halogen atoms independently of each other.
  • V 1 and V 2 are independent of each other, 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)
  • R 27 to R 30 represent hydrogen atoms or alkyl groups having 1 to 6 carbon atoms independently of each other, and Z is -C (CH 3 ) 2- or -C (CF 3 ) 2 .
  • Representing a hydrocarbon group, e and d represent an integer of 0 to 2 independently of each other, f represents an integer of 1 to 3, and g and h represent an integer of 0 to 4 independently of each other.
  • the polyimide-based resin in the present invention is represented by the formula (31) as Y in the formula (1) from the viewpoint of easily reducing the CTE of the film and easily improving the heat resistance and mechanical properties. It preferably contains at least one structure selected from the group consisting of a structure, a structure represented by the formula (32) or a structure represented by the formula (33), and preferably includes a structure represented by the formula (31). Is more preferable.
  • R 19 to R 26 are independent of each other, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl having 6 to 12 carbon atoms.
  • 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, the alkyl group having 1 to 6 carbon atoms and carbon having 1 to 6 carbon atoms in the formulas (2) and (3), respectively.
  • Examples of the alkoxy group having the number 1 to 6 and the aryl group having the number of carbons 6 to 12 are exemplified above.
  • R 19 to R 26 may be substituted with halogen atoms independently of each other, and examples of the halogen atoms include those mentioned above.
  • R 19 to R 26 are preferably hydrogen atoms or alkyl groups having 1 to 6 carbon atoms independently of each other, and hydrogen atoms or carbons. Alkyl groups of numbers 1 to 3 are more preferable, and hydrogen atoms are even more preferable.
  • V 1 and V 2 are single-bonded independently of each other, -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 )-, equation (a) or equation (b) ), Which is preferable from the viewpoint of easily reducing the CTE of the film and easily improving the water absorption resistance, heat resistance and mechanical properties, preferably single bond, —O—, ⁇ CH 2 ⁇ , ⁇ C (CH 3 ) 2 .
  • R j represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a hydrogen atom or a halogen atom. Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include those exemplified above.
  • f represents an integer of 1 to 3, and is preferably 1 or 2, more preferably 1, from the viewpoint of easily reducing the CTE of the film and easily increasing the heat resistance and mechanical properties.
  • R 27 to R 30 represent hydrogen atoms or alkyl groups having 1 to 6 carbon atoms independently of each other.
  • 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 more preferably hydrogen atoms or alkyl groups having 1 to 3 carbon atoms independently of each other. , Hydrogen atom is more preferable.
  • Z represents -C (CH 3 ) 2- or -C (CF 3 ) 2- .
  • i represents an integer of 1 to 3, and is preferably 1 or 2 from the viewpoint of easily reducing the CTE of the film and easily improving the water absorption resistance, heat resistance, and mechanical properties.
  • the plurality of Z and R 27 to R 30 may be the same as each other or may be different from each other.
  • Y in the formula (1) when Y in the formula (1) includes at least one selected from the group consisting of the structures represented by the formulas (31) to (33), the formula (1) is used.
  • Y is selected from the group consisting of the structures represented by the formulas (31) to (33), and the ratio of the constituent units represented by at least one is the total mole of the constituent units represented by the formula (1).
  • the amount it 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.
  • the film is formed. It is easy to reduce CTE and to improve water absorption resistance, heat resistance, dielectric property and mechanical property.
  • the ratio of the structural unit represented by at least one selected from the group consisting of the structures represented by the formulas (31) to (33) in the formula (1) is determined by using, for example, 1 H-NMR. It can be measured or calculated from the raw material charge ratio.
  • the polyimide resin (A) in the present invention has a structural unit represented by the formula (52), a structural unit represented by the formula (53), and a structural unit represented by the formula (53), in addition to the structural unit represented by the formula (1). It may contain at least one selected from the group consisting of the structural units represented by 54).
  • Y 1 represents a tetravalent organic group.
  • Y 2 represents a trivalent organic group X 1 and X 2 represent divalent organic groups independently of each other. * Represents a bond.
  • G and X represent divalent organic groups independently of each other. * Represents a bond.
  • Y 1 is synonymous with Y in formula (1)
  • X 1 and X 2 are synonymous with X in formula (1).
  • Y 2 in the formula (53) is a group in which any one of the bonds of Y in the formula (1) is replaced with a hydrogen atom.
  • Y 2 a group in which any one of the bonds of the groups (structures) represented by the formulas (31) to (38) is replaced with a hydrogen atom; a chain hydrocarbon having a trivalent carbon number of 1 to 8 is used.
  • the group etc. can be mentioned.
  • the polyimide-based resin may contain a plurality of types of Y 1 or Y 2 , and the plurality of types of Y 1 or Y 2 may be the same as or different from each other.
  • G is a divalent organic group independently of each other, preferably substituted with a hydrocarbon group having 1 to 8 carbon atoms or a fluorine-substituted hydrocarbon group having 1 to 8 carbon atoms. It may be a divalent organic group having 2 to 100 carbon atoms, more preferably substituted with a hydrocarbon group having 1 to 8 carbon atoms or a fluorine-substituted hydrocarbon group having 1 to 8 carbon atoms. It represents a good, divalent organic group having a cyclic structure and having 2 to 100 carbon atoms. Examples of the cyclic structure include an alicyclic ring, an aromatic ring, and a heterocyclic structure.
  • Examples of the organic group of G include a group in which two non-adjacent groups are replaced with hydrogen atoms and a divalent chain carbonization having 6 or less carbon atoms among the bonds of the groups represented by the formulas (31) to (38).
  • a hydrogen group can be mentioned, and preferably, among the bonds of the groups represented by the formulas (39) to (51), a group in which two non-adjacent groups are replaced with a hydrogen atom can be mentioned.
  • X in the formula (54) is synonymous with X in the formula (1), and when the polyimide resin contains a structural unit represented by the formula (1) and a structural unit represented by the formula (54), each X in the structural unit may be the same or different.
  • the polyimide-based resin may contain a plurality of types of X or G, and the plurality of types of X or G may be the same as or different from each other.
  • the polyimide resin (A) is represented by a structural unit represented by the formula (1), and in some cases, a structural unit represented by the formula (52) and the formula (53). It consists of at least one structural unit selected from the structural unit and the structural unit represented by the formula (54). Further, from the viewpoint of easily reducing the CTE of the film and easily improving the water absorption resistance, heat resistance and dielectric properties, the ratio of the structural unit represented by the formula (1) in the polyimide resin (A) is polyimide. All the structural units contained in the system resin, for example, the structural unit represented by the formula (1), and in some cases, the structural unit represented by the formula (52), the structural unit represented by the formula (53), and the formula (54).
  • the polyimide resin (A) Is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, based on the total molar amount of at least one structural unit selected from the structural units represented by).
  • the upper limit of the ratio of the structural unit represented by the formula (1) is 100 mol% or less. The above ratio can be measured using, for example, 1 H-NMR, or can be calculated from the charging ratio of raw materials.
  • the polyimide resin in the present invention is preferably a polyimide resin from the viewpoint of easily reducing the CTE of the film and easily improving the water absorption resistance, heat resistance and dielectric properties.
  • the polyimide-based resin (A) in the present invention may contain a halogen atom, preferably a fluorine atom, which can be introduced by, for example, the above-mentioned halogen-containing atom substituent or the like.
  • a halogen atom preferably a fluorine atom
  • Preferred fluorine-containing substituents for containing a fluorine atom in the polyimide-based resin (A) include, for example, a fluoro group and a trifluoromethyl group.
  • the content of the halogen atom in the polyimide resin (A) is preferably 0.1 to 40% by mass, more preferably 0.1 to 40% by mass, based on the mass of the polyimide resin. It is 1 to 35% by mass, more preferably 5 to 30% by mass.
  • the content of halogen atoms is at least the above lower limit, it is easy to improve the water absorption resistance, heat resistance and dielectric properties of the film.
  • the content of the halogen atom is not more than the above upper limit, the CTE of the film can be reduced and the synthesis becomes easy.
  • the imidization ratio 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 property, optical property and water absorption resistance of the film, the imidization rate is preferably at least the above lower limit.
  • the imidization ratio indicates the ratio of the molar amount of the imide bond in the polyimide-based resin to the value of twice the molar amount of the structural unit derived from the tetracarboxylic acid compound in the polyimide-based resin.
  • the value is twice the molar amount of the structural unit derived from the tetracarboxylic acid compound in the polyimide resin, and the structural unit derived from the tricarboxylic acid compound.
  • the ratio of the molar amount of the imide bond in the polyimide resin to the total amount of the molar amount of is shown.
  • the imidization rate can be determined by an IR method, an NMR method, or the like.
  • the 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 300 ° C. or higher, particularly preferably 350 ° C. or higher, and preferably 550 ° C. or higher. It is below ° C.
  • the Tg of the polyimide resin (A) is at least the above lower limit, the heat resistance of the obtained film can be easily increased and the CTE can be easily reduced.
  • the Tg of the polyimide resin (A) is not more than the above upper limit, the mechanical properties are likely to be enhanced.
  • the Tg of the polyimide resin (A) can be obtained, for example, by performing dynamic viscoelasticity measurement (hereinafter, may be abbreviated as DMA measurement), and can be measured by the method described in Examples.
  • DMA measurement dynamic viscoelasticity measurement
  • the 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, still more preferably 700,000 or less, still more preferably 500,000 or less, particularly preferably. Is 450,000 or less.
  • the Mw of the polyimide resin (A) is at least the above lower limit, it is easy to improve the water absorption resistance, heat resistance and mechanical properties of the obtained film, and it is easy to reduce the CTE.
  • the Mw of the polyimide resin (A) is not more than the above upper limit, the moldability is likely to be improved.
  • the Mw of the polyimide resin (A) can be obtained by, for example, GPC measurement and converted to standard polystyrene, and can be obtained by, for example, the method described in Examples.
  • the polyimide-based resin (A) in the present invention includes a precursor before imidization of the polyimide-based resin.
  • the polyimide resin (A) is a polyamic acid
  • the polyamic acid is the formula (1'): [In equation (1'), Y and X represent Y and X in equation (1), respectively] Includes building blocks represented by.
  • the method for producing the polyimide resin (A) is not particularly limited, and can be produced by a method including, for example, a step of reacting a diamine compound with a tetracarboxylic acid compound to obtain a polyamic acid, and a step of imidizing the polyamic acid. ..
  • the step of obtaining the polyamic acid may be carried out.
  • a dicarboxylic acid compound or a tricarboxylic acid compound may be reacted.
  • Examples of the tetracarboxylic acid compound used for the synthesis of the polyimide resin (A) include aromatic tetracarboxylic acid compounds such as aromatic tetracarboxylic dianhydride; and aliphatic tetracarboxylics such as aliphatic tetracarboxylic dianhydride. Acid compounds and the like can be mentioned.
  • the tetracarboxylic acid compound may be used alone or in combination of two or more.
  • the tetracarboxylic acid compound may be a tetracarboxylic acid compound analog such as an acid chloride compound in addition to the dianhydride.
  • tetracarboxylic acid compound examples include pyromellitic anhydride (hereinafter, may be abbreviated as PMDA), 4,4'-(4,4'-isopropylidene diphenoxy), and diphthalic anhydride (hereinafter, BPADA).
  • PMDA pyromellitic anhydride
  • BPADA diphthalic anhydride
  • 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride (hereinafter, may be abbreviated as BPDA), 4,4'-(Hexafluoroisopropylidene) diphthalic acid dianhydride (hereinafter, may be abbreviated as 6FDA), 4,4'-oxydiphthalic acid anhydride (hereinafter, may be abbreviated as ODPA), 2,2 ', 3,3'-, 2,3,3', 4'-or 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,3', 3,4'-biphenyltetracarboxylic Acid dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid dianhydride, 2,3', 3,4'-diphenyl ether t
  • PMDA BPDA
  • 6FDA BPADA
  • ODPA ODPA
  • HPMDA HPMDA
  • CBDA p-phenylene from the viewpoint of easily reducing the CTE of the film and easily enhancing the water absorption resistance, heat resistance, dielectric property, and mechanical property.
  • Bis (trimeritate anhydride) is preferred.
  • These tetracarboxylic acid compounds can be used alone or in combination of two or more.
  • diamine compound used for the synthesis of the polyimide resin (A) examples include aliphatic diamines, aromatic diamines and mixtures thereof.
  • aromatic diamine represents a diamine having an aromatic ring, and an aliphatic group or another substituent may be contained in a part of the structure thereof.
  • the aromatic ring may be a monocyclic ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring, but the aromatic ring is not limited thereto. Among these, a benzene ring is preferable.
  • the "aliphatic diamine” represents a diamine having an aliphatic group, and may contain other substituents as a part of its structure, but does not have an aromatic ring.
  • diamine compound examples include 1,4-diaminocyclohexane, 4,4'-diamino-2,2'-dimethylbiphenyl (hereinafter, may be referred to as m-TB), and 4,4'-diamino-.
  • 1,3-APB 3,3'-dimethylbiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl
  • TFMB 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl
  • 1,4-diaminodiphenyl ether 4,4'-diaminodiphenyl ether, 1,3 -Bis (3-aminophenoxy) benzene (hereinafter, may be abbreviated as 1,3-APB), 1,4-bis (4-aminophenoxy) benzene (hereinafter, may be abbreviated as 1,4-APB).
  • 1,4-diaminocyclohexane, 4,4'-diaminodiphenyl ether, TFMB, 4 from the viewpoint of easily reducing the CTE of the film and easily enhancing the water absorption resistance, heat resistance, dielectric property and mechanical property.
  • the polyimide resin (A) contains other tetracarboxylic acids, dicarboxylic acids, tricarboxylic acids, and their tricarboxylic acids in addition to the tetracarboxylic acid compounds used in the resin synthesis, as long as the various physical properties of the film are not impaired. Anhydrous and derivatives may be further reacted.
  • Examples of other tetracarboxylic acids include water adducts of the anhydrides of the above tetracarboxylic acid compounds.
  • dicarboxylic acid compound examples include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, acid chloride compounds related thereto, acid anhydrides and the like, and they may be used alone or in combination of two or more.
  • Specific examples include a dicarboxylic acid compound of terephthalic acid; isophthalic acid; naphthalenedicarboxylic acid; 4,4'-biphenyldicarboxylic acid; 3,3'-biphenyldicarboxylic acid; a chain hydrocarbon having 8 or less carbon atoms, and 2 Compounds in which one benzoic acid is linked by a single bond, -O-, -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -SO 2- or a phenylene group, and their compounds.
  • Examples include acid chloride compounds.
  • tricarboxylic acid compound examples include aromatic tricarboxylic acids, aliphatic tricarboxylic acids, acid chloride compounds related thereto, acid anhydrides, and the like, and they may be used alone or in combination of two or more. Specific examples include anhydrate of 1,2,4-benzenetricarboxylic acid; 2,3,6-naphthalentricarboxylic acid-2,3-anhydride; a single bond of phthalic anhydride and benzoic acid, -O-. , -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -SO 2- or compounds linked with a phenylene group.
  • the amount 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 ratio of each structural unit of the desired 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, particularly preferably 0.98 mol or more, relative to 1 mol of the tetracarboxylic acid compound.
  • 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 with respect to the tetracarboxylic acid compound is in the above range, the CTE of the obtained film can be easily reduced, and the water absorption resistance, heat resistance, dielectric property, mechanical property and optical property can be 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 30 minutes to 72 hours.
  • the reaction temperature is preferably 5-50 ° C, more preferably 10-40 ° C, and the reaction time is preferably 3-24 hours. With such a reaction temperature and reaction time, it is easy to reduce the CTE of the obtained film, and it is easy to improve the water absorption resistance, heat resistance, dielectric property, mechanical property and optical property.
  • 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, and is, for example, water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, and the like.
  • Alcohol-based solvent such as 2-butoxyethanol and propylene glycol monomethyl ether; phenol-based solvent such as phenol and cresol; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, ⁇ -butyrolactone (hereinafter, may be referred to as GBL).
  • ⁇ -Valerolactone propylene glycol methyl ether acetate, ethyl lactate and other ester solvents
  • acetone methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methylisobutylketone and other ketone solvents
  • pentane hexane, heptane and the like.
  • Alicyclic hydrocarbon solvent such as ethylcyclohexane; aromatic hydrocarbon solvent such as toluene and xylene; nitrile solvent such as acetonitrile; ether solvent such as tetrahydrofuran and dimethoxyethane; chloroform and chlorobenzene and the like.
  • Chlorine-containing solvent; amide-based solvent such as N, N-dimethylacetamide (hereinafter, may be referred to as DMAc), N, N-dimethylformamide (hereinafter, may be referred to as DMF); dimethylsulfone, dimethylsulfoxide.
  • Sulfur-containing solvent such as sulfolane
  • carbonate solvent such as ethylene carbonate and propylene carbonate
  • pyrrolidone solvent such as N-methylpyrrolidone (hereinafter, may be abbreviated as NMP); and combinations thereof.
  • NMP N-methylpyrrolidone
  • a phenol-based solvent, an amide-based solvent, and a pyrrolidone-based solvent can be preferably used from the viewpoint of solubility.
  • 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, if necessary.
  • the reaction may be carried out under an inert atmosphere such as a nitrogen atmosphere or an argon atmosphere.
  • an inert atmosphere such as a nitrogen atmosphere or an argon atmosphere.
  • imidization may be performed using an imidization catalyst, imidization may be performed by heating, or a combination thereof may be used.
  • the imidization catalyst used in the imidization step include aliphatic amines such as tripropylamine, dibutylpropylamine and ethyldibutylamine; N-ethylpiperidine, N-propylpiperidin, N-butylpyrolidin and N-butylpiperidine.
  • alicyclic amines such as N-propylhexahydroazepine (monocyclic); azabicyclo [2.2.1] heptane, azabicyclo [3.2.1] octane, azabicyclo [2.2.2] octane, and Alicyclic amines such as azabicyclo [3.2.2] nonane (polycyclic); as well as pyridine, 2-methylpyridine (2-picolin), 3-methylpyridine (3-picolin), 4-methylpyridine (4).
  • the imidization step by heating may be carried out in a solvent in which a polyamic acid is dissolved, or may be carried out in a filmed state as described later.
  • the reaction temperature is usually 20 to 250 ° C.
  • the reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours.
  • the polyimide-based resin (A) may be separated and purified by a conventional method, for example, a separation means such as filtration, concentration, extraction, crystallization, recrystallization, or column chromatography, or a separation means combining these. Often, in a preferred embodiment, a large amount of alcohol such as methanol is added to the reaction solution containing the resin to precipitate the resin, and the resin can be isolated by concentration, filtration, drying and the like.
  • a separation means such as filtration, concentration, extraction, crystallization, recrystallization, or column chromatography
  • a separation means such as filtration, concentration, extraction, crystallization, recrystallization, or column chromatography
  • the brightness is 80 or less on both sides of the film, so that it has excellent water absorption resistance.
  • the dielectric property of the film can be enhanced.
  • the film of the present invention is also excellent in the smoothness of the film surface. Therefore, the film of the present invention may have excellent water absorption resistance, dielectric properties, and surface smoothness.
  • the distance between the HSP values of the polyimide resin (A) and the polymer (B) is preferably 6 or more.
  • HSP is a Hansen solubility parameter ( ⁇ ), defined by a three-dimensional parameter of ( ⁇ D, ⁇ P, ⁇ H), and the formula (X) :.
  • ⁇ 2 ( ⁇ D) 2 + ( ⁇ P) 2 + ( ⁇ H) 2 ... (X)
  • ⁇ D represents the L
  • ⁇ P represents the molecular polarization term (dipole interpole force term)
  • ⁇ H represents the hydrogen bond term
  • HSP Hansen solubility parameters ⁇ D, ⁇ P, and ⁇ H can be calculated using HSPiP (Hansen S Cincinnatilubility Parameters in Practice), a program developed by Dr. Hansen's group who proposed the Hansen solubility parameter, for example, Ver. 4.1.07 and the like can be used.
  • HSPiP Haansen S Welubility Parameters in Practice
  • Dr. Hansen's group who proposed the Hansen solubility parameter, for example, Ver. 4.1.07 and the like can be used.
  • the details of the Hansen-dissolved sphere method will be described below.
  • the component of interest is dissolved in a solvent having a known HSP value, and the solubility of the component in a specific solvent is evaluated.
  • the solubility is evaluated by visually determining whether or not the target component is dissolved in the solvent. This is done for multiple solvents.
  • the type of the solvent it is preferable to use a solvent having a wide range of ⁇ t, more specifically, 10 kinds or more, more preferably 15 kinds or more, still more preferably 18 kinds or more.
  • the HSP having a composition targeting the center coordinates ( ⁇ d, ⁇ p, ⁇ h) of the Hansen sphere obtained by inputting the obtained solubility evaluation result into HSPiP is used.
  • HSP may be obtained from a structural formula using, for example, numerical values or literature values in a database of HSPiP, or HSPiP may be used.
  • the value of the Hansen solubility parameter is referred to as an HSP value, and the HSP value represents a 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 be obtained by any of the above methods, for example, by the method described in Examples. Desired.
  • the distance between the Hansen solubility parameters (hereinafter, may be abbreviated as HSP) of two substances is called the distance between HSP values.
  • the distance between HSPs (Ra) is an index showing the affinity between the two substances, and the smaller the value, the higher the affinity between the two substances. On the contrary, the larger the Ra value, the lower the affinity between the two substances, that is, the more difficult it is to be compatible.
  • the distance between the HSP values determines the Hansen solubility parameters ⁇ A and ⁇ B of the two substances A and B, respectively.
  • ⁇ A ( ⁇ DA, ⁇ PA, ⁇ HA)
  • ⁇ B ( ⁇ DB, ⁇ PB, ⁇ HB)
  • the distance between HSPs (Ra) is the equation (Y) :.
  • Ra [4 ⁇ ( ⁇ DA- ⁇ DB) 2 + ( ⁇ PA- ⁇ PB) 2 + ( ⁇ HA- ⁇ HB) 2 ] 0.5 ... (Y)
  • HSP value and the distance between the HSP values are as defined above, and can be obtained according to the above method.
  • the film of the present invention has water absorption resistance, heat resistance, bending resistance, etc. even when the distance between the HSP values of the polyimide resin (A) and the polymer (B) is relatively large. It has excellent mechanical and dielectric properties and can reduce CTE. Therefore, in the film of the present invention, the distance between the HSP values of the polyimide resin (A) and the polymer (B) is preferably 6.0 or more, more preferably 7.0 or more, still more preferably 8.0 or more. be.
  • the distance between the HSP values of the polyimide resin (A) and the polymer (B) is preferably 30 or less, more preferably 25 or less, still more preferably 20 or less, and even more, from the viewpoint of the affinity between the resin and the polymer. It is preferably 15 or less.
  • the total mass of the polyimide resin (A) and the particulate polymer (B) contained in the film is preferably 40% by mass or more, more preferably 60% by mass, based on the mass of the film. % Or more, 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 particulate polymer (B) contained in the film is at least the above lower limit, it is easy to improve the water absorption resistance, the dielectric property, and the surface smoothness of the film.
  • the film of the present invention is preferably a composite film in which the particulate polymer (B) is dispersed, preferably uniformly dispersed, with respect to the polyimide resin (A).
  • the composite film has a sea-island structure, the polyimide resin (A) is the sea, and the particulate polymer (B) is the island.
  • Such a composite film tends to enhance mechanical properties such as water absorption resistance, heat resistance, and bending resistance, and dielectric properties, and tends to reduce CTE.
  • the particulate polymer (B) can be easily dispersed uniformly in the film, and the film has excellent water absorption resistance. Can be obtained.
  • the film of the invention may have a low CTE.
  • the CTE of the film can be appropriately designed according to the application.
  • CCL is produced by laminating with a copper foil
  • the CTE of the film can be adjusted by the CTE of the polyimide resin (A) and the particulate polymer (B) to be mixed, the mixing amount, and the like. From the viewpoint of reducing CTE, it is preferable to mix the particulate polymer (B) having a high Tg.
  • the CTE can be measured by TMA, for example, by the method described in Examples.
  • the water absorption resistance of the film of the present invention can be evaluated by the water absorption rate of the film.
  • the water absorption rate of the film of the present invention is preferably 1% or less, more preferably 0.8% or less, still more preferably 0.6% or less, still more preferably 0.5% or less. Particularly preferably, it is 0.3% or less.
  • the water absorption rate of the film is not more than the above upper limit, it may have excellent water absorption resistance. Therefore, when the water absorption rate of the film is not more than the above upper limit, when the film of the present invention is used for the resin layer of CCL, it is easy to improve the dielectric property, and it is easy to suppress the dielectric loss and the transmission loss.
  • the water absorption rate of the film of the present invention may be usually 0.01% or more.
  • the water absorption rate of the film of the present invention can be determined by exposing the film to water vapor for a certain period of time and measuring the mass of the film before and after the exposure to water vapor, and can be measured by, for example, the method described in Examples.
  • the film of the present invention may have excellent surface smoothness.
  • the surface smoothness of the film can be evaluated by the standard deviation of the average thickness obtained in each of the 10 measurement regions obtained by dividing the region of the straight line 1 mm on the surface of the film into 10 equal parts.
  • the film of the invention has a standard deviation of average thickness of preferably 2.5 or less, more preferably 2.0 or less, even more preferably 1.70 or less, even more preferably 1. It is 50 or less, particularly preferably 1.0 or less, particularly more preferably 0.8 or less, and particularly preferably 0.5 or less.
  • the standard deviation of the average thickness is not more than the above upper limit, the surface smoothness of the film can be further improved.
  • the lower limit of the standard deviation of the average thickness is usually 0.01 or more, preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.2 or more.
  • the standard deviation of the average thickness is not more than the above lower limit, for example, when the copper foil is attached to the copper foil with an adhesive or the like, the adhesion is likely to be improved by the anchor effect.
  • a continuous straight 1 mm region on the film surface is arbitrarily selected, the region is divided into 10 equal parts to set 10 measurement regions, and then contact type or non-contact type.
  • the average thickness in each measurement area may be an average value calculated from a plurality of thicknesses measured at arbitrary points in the measurement area.
  • the film of the present invention may contain additives, if necessary.
  • Additives include, for example, antioxidants, flame retardants, cross-linking agents, surfactants, compatibilizers, imidization catalysts, weathering agents, lubricants, antiblocking agents, antistatic agents, antifogging agents, drip-free agents, pigments. , Fillers and the like. Additives can be used alone or in combination of two or more.
  • the film of the present invention has high water absorption resistance and low thermal conductivity because the particulate polymer (B) exhibits high particle dispersibility even if it does not contain a compatibilizer. It can exhibit variability, low CTE, high heat resistance, and high mechanical properties. Therefore, in the film of the present invention, the content of the compatibilizer is preferably 5 parts by mass or less, more preferably 1 part by mass or less, and further preferably 0.1 with respect to 100 parts by mass of the polyimide resin (A). It is not more than parts by mass, 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.
  • the polyimide resin (A) is a polyimide resin precursor such as polyamic acid and thermal imidization is required at the time of film production, inhibition of imidization by a compatibilizer or compatibilization by heating is required.
  • the content of the compatibilizer is preferably less than 0.1 part by mass within the above range.
  • the content of the compatibilizer may be based on 100 parts by mass of the total of the polyimide resin (A) and the particulate polymer (B) instead of 100 parts by mass of the polyimide resin (A). good.
  • the thickness of the film of the present invention can be appropriately selected depending on the intended use, 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, still more preferably. It is 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, and can be measured, for example, by the method described in Examples. When the film of the present invention is a multilayer film, the above thickness represents the average thickness of the single layer portion.
  • 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 include other layers (or other films). Even in such a case, the film of the present invention includes all the layers. Examples of the other layer include a functional layer and the like. Examples of the functional layer include a primer layer, a gas barrier layer, an adhesive layer, and a protective layer.
  • the functional layer can be used alone or in combination of two or more.
  • 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 usually industrially adopted.
  • the film according to one embodiment of the present invention is excellent in water absorption resistance and dielectric properties. Therefore, it can be suitably used as a substrate material compatible with a printed circuit board for a high frequency band and an antenna substrate.
  • CCL has a structure in which copper foils are laminated on both surfaces of a resin layer via an adhesive.
  • the film of the present invention When the film of the present invention is used as the resin layer, it has excellent water absorption resistance and a small dielectric loss, so that the transmission loss can be reduced.
  • the film of the present invention is used as the resin layer, the surface smoothness is high and the CTE is reduced, so that peeling between the copper foil and the resin layer can be effectively suppressed as compared with the conventional film.
  • the film of the present invention is also suitably used for other 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) Composition preparation step for preparing a composition containing a polyimide resin (A), a particulate polymer (B) and a solvent, It is produced by a method including (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. be able to.
  • the polyimide resin (A) is thermally imidized, a step of completing the imidization reaction may be included.
  • the composition comprises a polyimide resin (A), a particulate polymer (B) and a solvent, and optionally the additives.
  • the composition may be prepared or produced, for example, by mixing the polyimide resin (A), the particulate polymer (B) and the solvent, and optionally the additive, but the particulate polymer in the obtained film.
  • the dispersibility of (B) is improved, and when the haze is 75% or less, the brightness is easily adjusted to 37 or less on both sides of the film, and when the haze exceeds 75%, the brightness is reduced to 80 or less on both sides of the film.
  • the method for producing the composition in the present invention is: Step (1) of dissolving the polymer (B) in a first solvent to obtain a polymer (B) solution; After the polymer (B) solution is brought into contact with the second solvent, the first solvent is distilled off to provide a dispersion liquid containing the particulate polymer (B) (hereinafter, referred to as a particulate polymer (B) dispersion liquid). ); And the step of adding the polyimide resin (A) to the particulate polymer (B) dispersion (3). including.
  • the agglomeration of the particles of the polymer (B) can be suppressed, so that the particle size can be easily reduced and the dispersibility can be easily improved. Therefore, it is easy to obtain a film having high water absorption resistance, surface smoothness and high mechanical properties. Further, when such a manufacturing method is used, it is easy to reduce the brightness of the obtained film.
  • Step (1) is a step of dissolving the polymer (B) in the first solvent to obtain a polymer (B) solution.
  • the form of the polymer (B) to be dissolved in the first solvent is not particularly limited.
  • the first solvent is not particularly limited as long as the polymer (B) can be dissolved, and is, for example, a hydrocarbon solvent such as benzene, toluene, pentane, hexane, heptane, cyclohexane, xylene; a halogen such as dichloromethane and ethylene dichloride. Examples thereof include a hydrocarbon solvent. Of these, hydrocarbon solvents are preferred.
  • the first solvent contains a hydrocarbon solvent
  • the solubility of the polymer (B) and the first solvent is enhanced, so that the particle size of the particulate polymer (B) can be easily reduced and the dispersibility can be easily improved.
  • the first solvent can be used alone or in combination of two or more.
  • the first solvent is a solvent in which the polymer (B) is dissolved.
  • the evaluation of "dissolving” or “not dissolving” 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 the polymer (B) is preferably 4.0 or less, more preferably 3.0 or less, still more preferably 2.5 or less.
  • the distance between the HSP values is not more than the above upper limit, the solubility of the first solvent and the polymer (B) is increased, so that the particle size of the particulate polymer (B) can be easily reduced and the dispersibility is improved.
  • Cheap The lower limit of the distance between HSP values usually exceeds 0.
  • the distance between the HSP values of the first solvent and the polymer (B) is smaller than the interaction radius of the polymer (B).
  • the polymer (B) is easily dissolved in the first solvent, so that the particle size of the particulate polymer (B) can be easily reduced and the dispersibility can be easily improved.
  • the interaction radius is a plurality of solvents capable of dissolving a specific polymer, that is, when the Hansen solubility parameter of a good solvent is plotted in a three-dimensional HSP space, the plots of the good solvents are similar to each other.
  • the first solvent is preferably a solvent in which the polyimide resin (A) does not dissolve.
  • the particle size of the particulate polymer (B) can be easily reduced and the dispersibility can be easily improved.
  • the distance between the HSP values of the first solvent and the polyimide-based resin (A) is preferably 5.0 or more, more preferably 6.0 or more, still more preferably 7.0 or more, and further. It is more preferably 8.0 or more, and particularly preferably 9.0 or more.
  • the distance between the HSP values is not more than the above lower limit, the polyimide resin (A) is difficult to dissolve in the first solvent, so that it is easy to suppress the formation of aggregates of the particulate polymer (B), and the particle diameter is also high. Is easy to reduce, so it is easy to improve the dispersibility.
  • the upper limit of the distance between the HSP values of the first solvent and the polyimide resin (A) is preferably 30.0 or less, more preferably 27 or less, still more preferably 25 or less, still more preferably 23 or less, and particularly preferably 21 or less. Is.
  • the distance between the HSP values of the first solvent and the polyimide resin (A) is not more than the above upper limit, it is easy to suppress the aggregation of the particulate polymer (B), so that the dispersibility of the particles can be easily improved. It is easy to improve the particle dispersibility of the obtained film.
  • the distance between the HSP values of the first solvent and the polyimide resin (A) is larger than the interaction radius of the polyimide resin (A).
  • the solubility of the polymer (B) in the first solvent is preferably greater than the solubility of the polymer (B) in the second solvent. With such a relationship, it is easy to obtain a particulate polymer (B) having a small particle size and good dispersibility.
  • the solubility of the polymer (B) in the solvent can be measured by the following method. Add 1,000 mg of polymer (B) and 3 mL of solvent to the sample bottle, and stir at room temperature for 2 hours. Next, the solid phase and the liquid phase were separated by filtration, and the solid phase was dried at 80 ° C.
  • 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, still more preferably 0.1% by mass or more, still more preferably. It is 0.5% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.
  • the content of the polymer (B) in the solution is at least the above lower limit, the composition can be easily prepared. Further, when the content of the polymer (B) in the solution is not more than the above upper limit, it is easy to obtain a dispersion liquid and a film having a small particle size and high dispersibility.
  • the method for dissolving the polymer (B) in the first solvent is not particularly limited, but for example, the first solvent may be added to the polymer (B), or the polymer (B) may be added to the first solvent. It may be either or both. Further, it may be dissolved by heating or the like depending on the solubility of the first solvent in the polymer (B).
  • the step (2) is a step of contacting the polymer (B) solution with the second solvent and then distilling off the first solvent to obtain a particulate polymer (B) dispersion liquid.
  • the second solvent is not particularly limited as long as it is a solvent that can produce the particulate polymer (B) by contact with the polymer (B) solution, and is, for example, an amide solvent such as DMAc or DMF; GBL, ⁇ -valero.
  • lactone-based solvents such as lactones
  • sulfur-containing solvents such as dimethyl sulfoxide, dimethyl sulfoxide and sulfolane
  • carbonate-based solvents such as ethylene carbonate and propylene carbonate
  • pyrrolidone-based solvents such as N-methylpyrrolidone; and combinations thereof.
  • the particulate polymer (B) As a result of easily suppressing the aggregation of the particulate polymer (B) and having high particle dispersibility, it has low brightness, high water absorption resistance, smooth surface, low CTE, high heat resistance and high mechanical properties. From the viewpoint that a film can be easily obtained, it is preferably at least one selected from the group consisting of an amide-based solvent, a lactone-based solvent, and a pyrrolidone-based solvent. These solvents can be used alone or in combination of two or more. Further, the particulate polymer (B) dispersion liquid may contain water, an alcohol solvent, a ketone solvent, an acyclic ester solvent, an ether solvent and the like.
  • the distance between the HSP values of the second solvent and the polymer (B) is preferably 8.5 or more, more preferably 9.0 or more, still more preferably 10.0 or more, still more preferably. Is 11.0 or more.
  • the distance between the HSP values is at least the above lower limit, it is easy to suppress the aggregation of the particles of the polymer (B), and it is easy to reduce the particle size, so that the dispersibility of the particles is easy to be improved.
  • the upper limit of the distance between the HSP values of the second 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 second solvent and the polymer (B) is not more than the above upper limit, it is easy to suppress the aggregation of the particulate polymer (B), so that the dispersibility of the particles can be easily improved. It is easy to reduce the brightness of the film to be obtained and to improve the particle dispersibility.
  • the distance between the HSP values of the second solvent and the polymer (B) is larger than the interaction radius of the polymer (B).
  • the polymer (B) is difficult to dissolve in the second solvent, so that the particle size of the particulate polymer (B) in the particulate polymer (B) dispersion can be easily reduced and the dispersibility can be improved. Easy to improve.
  • the second solvent is preferably a solvent in which the polymer (B) does not dissolve.
  • a solvent it is easy to suppress the aggregation of the particulate polymer (B), so that it is easy to reduce the particle size and improve the dispersibility of the particles.
  • the second solvent is preferably a solvent in which the polyimide resin (A) is dissolved.
  • the particulate polymer (B) is likely to be dispersed in the obtained composition and film with a small particle size.
  • the film tends to form a sea-island structure.
  • the HSP value distance between the second solvent and the polyimide resin (A) is preferably 10.0 or less, more preferably 9.5 or less, still more preferably 9.0 or less, particularly preferably. Is 8.5 or less, preferably 0.01 or more, and more preferably 0.1 or more.
  • the distance between the HSP values is not more than the above upper limit, the affinity between the second solvent and the polyimide resin (A) can be improved. Therefore, in the obtained composition and film, a particulate polymer having a small particle size is used. (B) is dispersed, and it is easy to improve the particle dispersibility.
  • the distance between the HSP values of the second solvent and the polyimide resin (A) is preferably smaller than the interaction radius of the polyimide resin (A).
  • the method of contacting the polymer (B) solution with the second solvent is not particularly limited, and examples thereof include a method of mixing the polymer (B) solution and the second solvent. Specifically, a method of adding the polymer (B) solution to the second solvent and a method of adding the second solvent to the polymer (B) solution can be exemplified. By contacting in this way, the particulate polymer (B) having a small particle size can be precipitated or dispersed in the mixed solution of the second solvent and the first solvent. As long as the particulate polymer (B) does not aggregate, a small amount of the polyimide resin (A) or other additives may be added at any time during the step (2).
  • the amount of the polymer (B) solution to be brought into contact with the second solvent is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, still more preferably, with respect to 1 part by mass of the amount of the second 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, still more preferably 3 parts by mass or less, and particularly preferably 1.5 parts by mass. It is less than a part.
  • the amount of the polymer (B) solution to be brought into contact with the second solvent is within the above range, it is easy to suppress the aggregation of the particulate polymer (B), so that the particle size is easily reduced and the dispersibility of the particles is improved. It's easy to do.
  • step (2) the polymer (B) solution is brought into contact with the second solvent, and then the first solvent is distilled off. Distillation of the first solvent can enhance the dispersion stability of the particulate polymer (B). Further, the polymer (B) may be further precipitated by distilling off the first solvent. The first solvent may be distilled off or removed at least partially, and the first solvent may remain in the dispersion liquid containing the particulate polymer (B). From the viewpoint of easily suppressing the aggregation of the polymer (B) and easily preparing the dispersion liquid, it is preferable that the first solvent partially remains or is partially contained in the particulate polymer (B) dispersion liquid.
  • the method for distilling off the first solvent is not particularly limited, and a method for distilling off under reduced pressure using an evaporator or the like is exemplified.
  • the pressure and temperature at the time of distillation can be appropriately selected according to the characteristics such as the boiling points of the first solvent and the second solvent.
  • the boiling point of the first solvent is usually lower than the boiling point of the second solvent.
  • the content of the first solvent contained in the particulate polymer (B) dispersion obtained after distilling off the first solvent is preferably 120 parts by mass or less, more preferably 120 parts by mass with respect to 100 parts by mass of the content of the second solvent.
  • the content of the first solvent is not more than the above upper limit, it is easy to suppress the aggregation of the particulate polymer (B), so that it is easy to reduce the particle size and improve the dispersibility of the particles. As a result, it is easy to reduce the brightness of the obtained film, and it is easy to improve water absorption resistance, particle dispersibility, surface smoothness and mechanical properties. Further, when the content of the first solvent is at least the above lower limit, it is easy to prepare the dispersion liquid.
  • the content of the first solvent in the particulate polymer (B) dispersion can be measured by gas chromatography, for example, by the method described in Examples.
  • the content of the solvent contained in the particulate polymer (B) dispersion is preferably 50% by mass or more, more preferably 70% by mass or more, and further, with respect to the mass of the dispersion. It is 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 less, still more preferably 99% by mass or less, and particularly preferably 95% by mass. It is as follows. When the content of the solvent is in the above range, it is easy to suppress the aggregation of the particulate polymer (B), so that it is easy to reduce the particle size and improve the dispersibility of the particles. As a result, it is easy to improve the water absorption resistance, particle dispersibility, surface smoothness, mechanical properties and the like of the obtained film.
  • the solvent contained in the particulate polymer (B) dispersion may contain other solvents other than the first solvent and the second solvent as long as the effects of the present invention are not impaired. ..
  • the other solvent is not particularly limited, and a conventional solvent can be used.
  • the total mass of the first solvent and the second solvent is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably, with respect to the mass of the solvent contained in the dispersion liquid. Is 90% by mass or more, 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 in the above range, it is easy to suppress the aggregation of the particulate polymer (B), so that it is easy to reduce the particle size and improve the dispersibility of the particles. As a result, it is easy to improve the water absorption resistance, particle dispersibility, surface smoothness, mechanical properties and the like of the obtained film.
  • the content of the particulate polymer (B) contained in the particulate polymer (B) dispersion obtained after distilling off the first solvent is preferably 0.01 with respect to the mass of the particulate polymer (B) dispersion.
  • 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 or less, particularly preferably. It is 5% by mass or less.
  • the particulate polymer (B) dispersion liquid preferably contains a particulate polymer (B) having a median diameter of 0.01 to 15 ⁇ m.
  • the median diameter of the particulate polymer (B) is preferably 0.01 ⁇ m or more, more preferably 0.03 ⁇ m or more, still more preferably 0.05 ⁇ m or more, preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably. It is 5 ⁇ m or less, more preferably 3 ⁇ m or less, particularly preferably 1 ⁇ m or less, particularly more preferably 0.8 ⁇ m or less, and particularly preferably 0.5 ⁇ m or less.
  • the median diameter of the particulate polymer (B) in the dispersion is not more than the above lower limit, it is easy to improve the dielectric properties of the film formed from the composition, and it is easy to manufacture the film.
  • the median diameter of the particulate polymer (B) in the dispersion is not more than the above upper limit, the brightness of the film formed from the composition can be easily reduced, and the particle dispersibility, water absorption resistance, surface smoothness, and surface smoothness can be easily reduced. It is easy to improve mechanical properties such as bending resistance.
  • the median diameter of the particulate polymer (B) in the dispersion can be determined by a scattering type particle size distribution measurement using laser diffraction.
  • a dispersion liquid sample is prepared by diluting the particulate polymer (B) dispersion liquid with a solvent, and the obtained dispersion liquid sample is subjected to a laser diffraction / scattering type particle size distribution measuring device (Malvern Panasonic). It can be obtained by measuring using a company, model: Nan AlbanyZS, refractive index: 1.70-0.20i).
  • the median diameter is also referred to as D50, and indicates a value in which the number of particles of the particulate polymer (B) on the side smaller than the value is equal to the number of particles on the side larger than the value.
  • the step (3) is a step of adding the polyimide resin (A) to the particulate polymer (B) dispersion liquid.
  • the polyimide resin (A) to be added may be in the form of a solid, preferably powder, and the form of a varnish in which the polyimide resin (A) is dissolved in a predetermined solvent, for example, a second solvent. May be.
  • the polyimide resin or polyamic acid can be added in the form of a solid, preferably powder or varnish.
  • the content of the polyimide resin (A) in the varnish is preferably 0.1% by mass or more, more preferably 1 with respect to the mass of the varnish. It is mass% or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less.
  • the content of the polyimide resin (A) in the varnish is in the above range, film formation becomes easy, which is advantageous from the viewpoint of film production.
  • the polyimide-based resin (A) added in the step (3) is preferably 50% by mass or more with respect to the total mass of the polymer (B) and the polyimide-based resin (A) in the particulate polymer (B) dispersion. , More preferably 60% by mass or more, further preferably 65% by mass or more, preferably 95% by mass or less, more preferably 93% by mass or less, still more preferably 90% by mass or less.
  • the content of the polyimide resin (A) added in the step (3) is at least the above lower limit, film formation becomes easy, which is advantageous from the viewpoint of film production.
  • the content of the polyimide resin (A) added in the step (3) is not more than the above upper limit, the dispersibility of the particulate polymer (B) in the dispersion liquid and the composition is likely to be improved. It is easy to reduce variations in physical properties such as lightness, thermal conductivity, and thermal diffusion rate of the film, and it is easy to improve water absorption resistance, particle dispersibility, surface smoothness, mechanical properties, and the like.
  • the method of adding the polyimide resin (A) to the particulate polymer (B) dispersion is not particularly limited, and the polyimide resin (A) may be added at once, and a plurality of polyimide resins (A) may be added. It may be added in batches.
  • composition preparation step according to the embodiment of the present invention may include steps other than the steps (1) to (3) as long as the effects of the present invention are not impaired, and the polyimide resin (A) and the polymer may be included.
  • Polymers or additives other than (B), such as the additives exemplified above, may be used.
  • the polyimide resin (A) is added to the particulate polymer (B) dispersion, but the polymer (B) in the powder form is added to the varnish of the polyimide resin (A). You may.
  • the varnish of the polyimide-based resin (A) may be one in which the polyimide-based resin (A) is dissolved in a predetermined solvent, for example, a second solvent, or the polyimide-based resin. It may be a resin solution for synthesizing the precursor of (A), for example, a polyimide acid solution (at least a solution containing polyamic acid and a synthetic solvent).
  • the content of the particulate polymer (B) contained in the composition obtained in the composition preparation step is usually 1% by mass or more with respect to the total mass of the polyimide resin (A) and the particulate polymer (B). It is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, particularly preferably 20% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably. Is 35% by mass or less, particularly preferably 30% by mass or less.
  • the content of the particulate polymer (B) contained in the composition is at least the above lower limit, the dispersibility of the particulate polymer (B) is likely to be enhanced, so that the brightness of the obtained film is easily reduced and the resistance is high. It is easy to improve water absorption, particle dispersibility, surface smoothness, and mechanical properties. Further, when the content of the particulate polymer (B) contained in the composition is not more than the above upper limit, the brightness of the film can be easily reduced and the film can be easily formed, which is advantageous from the viewpoint of film production. be. If the dispersibility of the particles in the film is high, the thermal conductivity or thermal diffusivity and the uniformity of CTE are high.
  • the film when the film is used as the resin layer of CCL, the film and the copper foil are used. It becomes easier to suppress peeling.
  • the polyimide resin (A) is added to the particulate polymer (B) dispersion, but the polymer (B) in the powder form is added to the varnish of the polyimide resin (A). You may.
  • the total mass of the polyimide resin (A) and the particulate polymer (B) contained in the composition is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5. It is 5% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
  • the total mass of the polyimide resin (A) and the particulate polymer (B) contained in the composition is in the above range, the water absorption resistance, the dielectric property, and the surface smoothness of the film are likely to be improved.
  • the content of the first solvent contained in the composition obtained in the composition preparation step is preferably 100 parts by mass or less, more preferably 60 parts by mass or less, still more preferably 60 parts by mass, based on 100 parts by mass of the content of the second solvent. Is 45 parts by mass or less, more preferably 30 parts by mass or less, particularly preferably less than 30 parts by mass, particularly more preferably 25 parts by mass or less, preferably 0.01 parts by mass or more, and more preferably 0.05 parts by mass. More than parts, more preferably 0.1 parts by mass or more.
  • the content of the first solvent is not more than the above upper limit, the aggregation of the particulate polymer (B) is easily suppressed, and the particle size is easily reduced, so that the dispersibility is easily improved.
  • the content of the first solvent is not more than the above upper limit, it is easy to improve the uniformity of the thermal conductivity or the thermal diffusivity of the film, the surface smoothness and the mechanical properties. Further, when the content of the first solvent is at least the above lower limit, it is easy to prepare the composition.
  • the content of the solvent contained in the composition obtained in the composition preparation step is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, based on the mass of the composition. It is still 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, still more preferably 95% by mass or less.
  • the content of the solvent is within the above range, it is easy to suppress the aggregation of the particulate polymer (B), and it is easy to reduce the particle size, so that the dispersibility is easily improved. Therefore, it is easy to obtain a film having high water absorption resistance, surface smoothness and high mechanical properties.
  • the content of the solvent is at least the above lower limit, it is easy to knead the obtained composition, so that it is easy to improve the moldability of the film, and when it is at least the above upper limit, it is in the form of particles in the obtained composition. Since it is easy to suppress the sedimentation and floating of the polymer (B), it is easy to improve the dispersibility of the particulate polymer (B).
  • the solvent contained in the composition obtained in the composition preparation step may contain other solvents other than the first solvent and the second solvent as long as the effects of the present invention are not impaired.
  • the other solvent is not particularly limited, and a conventional solvent can be used.
  • the total mass of the first solvent and the second solvent is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably, with respect to the mass of the solvent contained in the composition. Is 90% by mass or more, 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, it is easy to suppress the aggregation of the particulate polymer (B), and it is easy to reduce the particle size, so that the dispersibility is easily improved. Therefore, it is easy to obtain a film having high water absorption resistance, surface smoothness and high mechanical properties.
  • the median diameter of the particulate polymer (B) in the composition obtained in the composition preparation step can be selected from the same range as the median diameter of the particulate polymer (B) in the above dispersion liquid.
  • the method for determining the median diameter of the particulate polymer (B) in the composition is not particularly limited, but can be determined by, for example, a centrifugal sedimentation type particle size distribution measuring device or an ultrasonic attenuation type particle size distribution measuring device.
  • the particle size in the dispersion can be measured and used as the particle size in the composition.
  • the composition obtained in the composition preparation step can contain the additives exemplified above, if necessary.
  • the particle size of the particulate polymer (B) is small and the particle size of the particulate polymer (B) is small even if it does not contain a compatibilizer. Excellent dispersibility. Therefore, in the composition of the present invention, the content of the compatibilizer is preferably 5 parts by mass or less, more preferably 1 part by mass or less, and further preferably 0.
  • the polyimide-based resin (A) is a polyimide-based resin precursor such as polyamic acid and thermal imidization is required at the time of film production, inhibition of imidization by a compatibilizer or a phase by heating is performed.
  • the content of the compatibilizer is preferably less than 0.1 part by mass within the above range.
  • the content of the compatibilizer may be based on 100 parts by mass of the total of the polyimide resin (A) and the polymer (B) instead of 100 parts by mass of the polyimide resin (A).
  • the coating step is a step of applying the compositions obtained in the above steps (1) to (3) to a substrate to form a coating film.
  • the composition is applied onto the substrate by a known coating method to form a coating film.
  • Known coating methods include, for example, wire bar coating method, reverse coating, roll coating method such as gravure coating, die coating method, comma coating method, lip coating method, spin coating method, screen printing coating method, fountain coating method, and dipping method. , Spray method, curtain coating method, slot coating method, hypersalivation forming method and the like.
  • the base material examples include a copper plate (including copper foil), a SUS plate (including SUS foil and SUS belt), a glass substrate, a PET film, a PEN film, another polyimide resin film, a polyamide resin film and the like.
  • copper plate, SUS plate, glass substrate, PET film, PEN film and the like are preferable from the viewpoint of excellent heat resistance, and copper plate, SUS plate, glass substrate and the like are more preferable from the viewpoint of adhesion to the film and cost.
  • a PET film or the like can be mentioned.
  • the film can be formed by drying the coating film and peeling it from the substrate.
  • the base material is a copper foil
  • a film is formed without peeling the coating film from the copper foil, and a laminate in which the film is laminated on the obtained copper foil is copper-clad. It can also be used for laminated boards.
  • a drying step of further drying the film may be performed after the peeling.
  • the coating film can be appropriately selected depending on the heat resistance of the polyimide resin (A) and the like, but in one embodiment of the present invention, the coating film may be dried at a temperature of 50 to 450 ° C, preferably 70 to 400 ° C.
  • the present invention can be carried out at a temperature of 50 to 350 ° C, preferably 70 to 300 ° C.
  • the composition can be dried uniformly, and the brightness of the obtained film can be easily reduced, so that the water absorption resistance can be easily improved and the Tg of the obtained film can be improved.
  • the drying or heating time is preferably 5 minutes to 10 hours, more preferably 10 minutes to 5 hours.
  • the coating film may be dried under inert atmosphere conditions such as in nitrogen or argon, under vacuum or reduced pressure conditions, and / or under ventilation.
  • the coating film may be continuously dried after the coating film is peeled off from the base material during the stepwise drying, and after all the drying is completed, the coating film is applied from the base material ( The film) may be peeled off.
  • the coating film may be peeled off from the substrate after the first step of drying to perform the second and subsequent drying steps, or the coating film (film) may be peeled off from the substrate after all the drying steps are completed. good.
  • the first step of drying may be pre-drying.
  • the film may be peeled off from the copper foil as the base material by etching and removing the copper foil with a ferric chloride solution or the like.
  • the composition when the polyimide-based resin (A) in the composition is a polyimide-based resin precursor, for example, a polyamic acid, and a polyimide-based resin is produced during film production, the composition is applied to a substrate. After that, it is preferable to heat 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 having excellent water absorption resistance and making it easy to obtain a smooth film, it is preferable to perform heating step by step.
  • the solvent may be removed by heating at a relatively low temperature of 50 to 150 ° C., and then gradually heated to a temperature in the range of 300 to 450 ° C.
  • the heating time can be selected from the same range as the above range, for example.
  • the film of the present invention is a multilayer film
  • it can be produced by, for example, a multilayer film forming method such as a coextrusion processing method, an extrusion laminating method, a thermal laminating method, or a dry laminating method.
  • the present invention includes a polyimide resin (A), a particulate polymer (B) and a solvent, the solvent containing a first solvent and a second solvent, and the HSP value of the second solvent and the particulate polymer (B). It also includes compositions having a distance of 8.5 or more.
  • the composition of the present invention is preferably the composition described in the above [Method for producing a film], and the polyimide resin (A) contained in the composition is in the form of particles.
  • the polymer (B) and the solvent are the same as those described in the sections [Film] and [Method for producing a film].
  • the composition of the present invention contains a polyimide resin (A), a particulate polymer (B) and a solvent, the solvent containing a first solvent and a second solvent, and a second solvent and a particulate polymer (B). Since the distance between the HSP values is 8.5 or more, the brightness is reduced, and as a result, a film having improved water absorption resistance can be formed. In addition, the composition of the present invention can form a film having a reduced CTE as compared with a conventional composite film. Furthermore, the composition of the present invention can form a film capable of exhibiting mechanical properties such as excellent bending resistance even though the Tg of the polymer (B) is large. Therefore, the composition of the present invention can form a film having both mechanical properties such as excellent water absorption resistance, surface smoothness, heat resistance and bending resistance, and reduced CTE.
  • NB content The content of the monomer unit derived from norbornene (also referred to as “NB content”) in the cycloolefin copolymer obtained in the production example was measured using 13 C-NMR. 13 C-NMR measurement conditions are as follows.
  • HSP Hansen solubility parameter
  • HSP solubility parameter
  • HSP of cycloolefin copolymer The solubility of the cycloolefin copolymer in various solvents was evaluated. For the evaluation of solubility, use a solvent with a known solubility parameter in a transparent container (refer to the HSPiP database, solvent used: methyl chloride, 1,4-dichlorobenzene, chloroform, toluene, p-xylene, GBL, DMAc, NMP. , Water, acetone, diiodomethane, butyl benzoate) 10 mL and 0.1 g of cycloolefin copolymer were added to prepare a mixed solution.
  • the obtained mixed solution was subjected to ultrasonic treatment for a total of 6 hours.
  • the appearance of the mixed solution after the ultrasonic treatment was visually observed, and the solubility of each resin in the solvent was evaluated based on the following evaluation criteria from the obtained observation results.
  • evaluation criteria 2 The appearance of the mixed solution is cloudy and precipitates at room temperature, but the appearance of the mixed solution becomes transparent by heating to 50 ° C. and stirring with a stirrer for 30 minutes.
  • 1 The appearance of the mixture is transparent at room temperature.
  • 0 The appearance of the mixed solution is cloudy and precipitates at room temperature, and the appearance of the mixed solution does not become transparent even when heated to 50 ° C. and stirred with a stirrer for 30 minutes.
  • the HSP value was calculated by the above-mentioned Hansen-dissolved sphere method using HSPiP.
  • HSP of polyimide resin The solubility of the polyimide resin in various solvents was evaluated. For evaluation of solubility, use a solvent with known solubility parameters in a transparent container (see HSPiP database, solvents used: acetone, toluene, ethanol, tetrahydrofuran, N, N-dimethylformamide, dimethyl sulfoxide, hexane, GBP, ethyl.
  • Acetate, methyl ethyl ketone, propylene glycol monomethyl ether, 1-butanol, N-methylformamide, 1-methylnaphthalene, bromobenzene, 1-methylimidazole, pyrazole, acetic acid) 10 mL and 0.1 g of polyimide resin are added to make a mixed solution.
  • the obtained mixed solution was subjected to ultrasonic treatment for a total of 6 hours. The appearance of the mixed solution after the ultrasonic treatment was visually observed, and the solubility of each resin in the solvent was evaluated based on the following evaluation criteria from the obtained observation results.
  • evaluation criteria 1 The appearance of the mixed solution is cloudy.
  • 0 The appearance of the mixed solution is transparent.
  • the HSP value was calculated by the above-mentioned Hansen-dissolved sphere method using HSPiP.
  • HSP of Fluoropolymer (PTFE)
  • PTFE Fluoropolymer
  • ⁇ Meso-type two-chain / Racemo-type two-chain> The ratio of the meso-type two-chain of the norbornene two-chain to the racemo-type two-chain (meso-type two-chain / racemo-type two-chain) of the cycloolefin copolymer obtained in the production example is the above-mentioned NB content using 13 C-NMR. It was measured under the same conditions as the measurement of.
  • the meso-type / racemo-type two-chain of the norbornene two-chain is based on 1,1,2,2-tetrachloroethane (74.24 ppm), and is described in “RAWendt, G.Fink, Macromol.Chem.
  • the meso-type two-chain / racemo-type two-chain has a signal integral value observed at a chemical shift value of 27.5-28.4 ppm in the spectrum chart measured using 13 C-NMR: IC5 .
  • the refractive index of the cycloolefin copolymer obtained in the production example was determined by measuring under the following conditions using a sheet-shaped sample formed to a thickness of 100 ⁇ m with a vacuum press.
  • the Tg of the cycloolefin copolymer obtained in the production example was determined 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 is measured under the following conditions, and the onset of displacement when the indenter sinks into the sample is defined as the softening temperature. did.
  • Tg of the polyimide resin obtained in the production example was determined by the following measurement. Using DMA Q800 manufactured by TA Instrument, measurement under the following samples and conditions was performed to obtain a tan ⁇ curve, which is the ratio of the loss modulus to the storage modulus, and then the peak of the tan ⁇ curve peaked. Tg was calculated from.
  • ⁇ Mw and Mn of cycloolefin copolymer> The polystyrene-equivalent Mw and Mn of the cycloolefin copolymer obtained in the production example were measured using GPC. The GPC measurement was performed under the following conditions, and the peak was specified by defining the baseline on the chromatogram based on the description of ISO16014-1.
  • GPC column TSKgel GMH6-HT 7.8 mm I. D. ⁇ 300 mm (manufactured by Tosoh Corporation) 3 connected mobile phase: Ortodichlorobenzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade) with 2,6-di-tert-butyl-4-methylphenol (hereinafter, BHT) was added at a concentration of 0.1 w / V, that is, 0.1 g / 100 mL.
  • BHT 2,6-di-tert-butyl-4-methylphenol
  • Example solution preparation conditions Solvent: BHT was added to orthodichlorobenzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade) at a concentration of 0.1 w / V, that is, 0.1 g / 100 mL.
  • Sample solution concentration 1 mg / mL
  • Automatic shaker for melting DF-8020 (manufactured by Tosoh Corporation)
  • Dissolution conditions A 5 mg 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, and 5 mL of orthodichlorobenzene having the same composition as the mobile phase is added to the test tube. The lid was covered with aluminum foil, the test tube was set in DF-8020, and the mixture was stirred at 140 ° C. for 120 minutes at a stirring rate of 60 reciprocating / min. GPC measurement was performed using the stirred solution as a sample.
  • ⁇ Mw of polyimide resin The polystyrene-equivalent Mw of the polyimide resin obtained in the production example was measured using GPC. GPC measurement was performed under the following conditions. GPC measurement (1) Pretreatment method Add DMF eluent (10 mmol / L lithium bromide-added DMF solution) to the sample to a concentration of 2 mg / mL, heat with stirring at 80 ° C. for 30 minutes, cool, and then cool. The solution filtered by a 0.45 ⁇ m membrane filter was used as a measurement solution.
  • DMF eluent 10 mmol / L lithium bromide-added DMF solution
  • the dispersion obtained in the example is placed in a glass cell having a capacity of 3.5 mL, and further diluted 1000-fold with GBL or DMAc (using the same solvent as the dispersion) to form a particulate cyclo.
  • a dispersion sample containing an olefin copolymer or PTFE was obtained.
  • the obtained dispersion sample was measured using a laser diffraction / scattering type particle size distribution measuring device (manufactured by Malvern Panasonic, model: Nan AlbanyZS, refractive index: 1.70-0.20i), and the particulate cycloolefin copolymer and The median diameter of the particulate PTFE was determined.
  • the polyimide resin was added to the dispersion in an amount within a range not affecting the particle size of the particulate cycloolefin copolymer and the particulate PTFE to form a composition, so that the composition was formed in the dispersion.
  • the median diameter of the particulate cycloolefin copolymer and the particulate PTFE was defined as the median diameter of the particulate cycloolefin copolymer and the particulate PTFE in the composition.
  • ⁇ Thickness of composite film> For the thickness of the composite film obtained in Examples and Comparative Examples, a Digimatic Indicator (ID-C112XBS, manufactured by Mitutoyo Co., Ltd.) was used to measure the thickness of any 5 or more points of the film, and the thickness thereof was measured. The average value was taken as the thickness of the composite film.
  • ID-C112XBS Digimatic Indicator
  • ⁇ CTE> CTE of composite film
  • the CTEs of the composite films obtained in Examples and Comparative Examples were measured by TMA. Specifically, the measurement was performed under the following conditions, and the CTE at 50 ° C to 100 ° C was calculated.
  • Specimen 40 mm ⁇ 10 mm ⁇ 50 ⁇ m rectangular parallelepiped
  • CTE of cycloolefin copolymer 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.
  • the lid of the metal plate is removed so that the surface of the composite film opposite to the surface in contact with the glass substrate at the time of film formation of the film becomes the surface in contact with steam.
  • the beaker was covered with a film and then covered with a metal plate, and the composite film was exposed to water vapor. After 5 minutes, the composite flume was taken out and the mass was measured to obtain the mass W1 after exposure to water vapor.
  • ⁇ Standard deviation of average thickness of composite film> The standard deviation of the average thickness of the composite films obtained in Examples and Comparative Examples was calculated as follows. On the surface of the film fixed so as to be in close contact with the glass substrate, a palpation type surface shape measuring instrument (Dektak XTE Co., Ltd.) is used, and the glass substrate is used as a reference surface in an arbitrary continuous straight line 1 mm region. A thickness profile (height profile) was obtained. The region was divided into 10 equal parts to set 10 measurement regions, and then the average thickness (average height) of each of the 10 measurement regions was determined. Then, the standard deviation of the average thickness of the composite film was calculated from the average thickness data of 10 points in each of the obtained measurement regions.
  • Triisobutylaluminum (hereinafter referred to as TIBA) manufactured by AGC Co., Ltd. and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (hereinafter referred to as AB) manufactured by AGC Co., Ltd. were used.
  • Toluene was dehydrated using Molecular Sieves 13X (manufactured by Union Showa Co., Ltd.) and activated alumina (manufactured by Sumitomo Chemical Co., Ltd., NKHD-24), and then nitrogen gas was blown into the toluene to remove dissolved oxygen. used.
  • NB solution A solution from which dissolved oxygen was removed was used (hereinafter referred to as NB solution).
  • NB solution A solution from which dissolved oxygen was removed was used (hereinafter referred to as NB solution).
  • the NB concentration in the NB solution was measured by using gas chromatography.
  • Isopropyridene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) Titanium dichloride (hereinafter referred to as a complex) is synthesized according to the method described in JP-A-9-183809. did.
  • the temperature in the system was kept at 60 ° C., and ethylene was continuously supplied to keep the pressure in the system at the starting value.
  • 5.0 mL of water was added to stop the polymerization, and the solution in the autoclave was withdrawn.
  • 1,500 g of toluene and 100 g of magnesium sulfate were added and stirred, and then 100 mL of water was added and stirred, and the solid was removed by filtration.
  • the obtained liquid was added dropwise to acetone, and the precipitated powder was isolated by filtration. The isolated powder was further washed with acetone and dried under reduced pressure at 120 ° C.
  • a cycloolefin copolymer In the obtained cycloolefin copolymer, the NB content is 84.1 mol%, Tg is 293 ° C., Mw is 521,000, Mw / Mn is 1.87, and CTE is 49.4 ppm /. It was K.
  • the cycloolefin copolymer has a ⁇ D of 17.7 MPa 0.5 , a ⁇ P of 2.1 MPa 0.5 , a ⁇ H of 3.9 MPa 0.5 , and a meso-type two-chain / racemo-type two-chain of 0. It was 19, and the refractive index was 1.538.
  • Table 2 shows the synthesis conditions of Production Example 1. This cycloolefin copolymer was dissolved in a toluene solution at a concentration of 2% by mass to obtain a cycloolefin copolymer solution 1.
  • cycloolefin copolymer In the obtained cycloolefin copolymer, the NB content was 92.3 mol%, Tg was 308 ° C., Mw was 852,000, and Mw / Mn was 1.81.
  • the ⁇ D of the cycloolefin copolymer was 17.7 MPa 0.5
  • the ⁇ P was 2.1 MPa 0.5
  • the ⁇ H was 3.9 MPa 0.5
  • the CTE was 44.5 ppm / K. ..
  • This cycloolefin copolymer was pulverized with a counter jet mill manufactured by Hosokawa Micron Co., Ltd. and classified by a filter to obtain a cycloolefin copolymer crushed powder having a median diameter of 2.6 ⁇ m.
  • the temperature in the system was kept at 80 ° C. during the polymerization. After 2 hours from the start of the polymerization, 3.0 mL of water was added to stop the polymerization, and the solution in the autoclave was withdrawn. The obtained liquid was added dropwise to acetone in the extracted solution, and the precipitated powder was isolated by filtration. The isolated powder was further washed with acetone and dried under reduced pressure at 150 ° C. for 2 hours to obtain 198.3 g of a cycloolefin copolymer. In the obtained cycloolefin copolymer, the NB content was 96.3 mol%, Mw was 79,000, Mw / Mn was 1.83, and Tg was more than 300 ° C.
  • the ⁇ D of the cycloolefin copolymer was 17.7 MPa 0.5
  • the ⁇ P was 2.1 MPa 0.5
  • the ⁇ H was 3.9 MPa 0.5
  • Table 3 shows the synthesis conditions of Production Example 3. This cycloolefin copolymer was dissolved in a toluene solution at a concentration of 2% by mass to obtain a cycloolefin copolymer solution 2.
  • the ⁇ D of the obtained polyimide resin was 18.1 MPa 0.5, the ⁇ P was 8.3 MPa 0.5 , and the ⁇ H was 9.3 MPa 0.5 .
  • the Mw of the polyimide resin was 334,300, and the Tg was 361 ° C.
  • Example 1 100.0 g of the cycloolefin copolymer solution 1 obtained in Production Example 1 and 98.0 g of GBL are mixed, and the pressure is reduced at 50 hPa and 80 ° C. so that the toluene content is 7 parts by mass with respect to 100 parts by mass of GBL. Toluene was distilled off to obtain a particulate cycloolefin copolymer dispersion. To 32.1 g (cycloolefin copolymer 1.9% by mass) of the obtained dispersion, 1.9 g of the polyimide resin obtained above was added to obtain a composition as a polyimide-cycloolefin copolymer mixed solution.
  • the median diameter of the particulate cycloolefin copolymer in the dispersion and composition measured by the above method was 0.15 ⁇ m. In the obtained composition, no aggregate of cycloolefin copolymer larger than 1 mm was confirmed.
  • the obtained composition was salivated on a glass substrate, and a coating film was formed at a linear velocity of 0.4 m / min. The coating film is heated at 70 ° C. for 60 minutes, the film is peeled off from the glass substrate, the film is fixed with a metal frame, and the film is further heated at 200 ° C. for 1 hour to obtain a polyimide-cycloolefin copolymer composite film having a thickness of 60 ⁇ m.
  • the content of the particulate cycloolefin copolymer in the obtained composite film was 24% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
  • the CTE of the obtained composite film was 44 ppm / K.
  • the standard deviation of the average thickness of the obtained composite film was 0.4, and the smoothness of the film surface was also excellent.
  • the haze of the obtained composite film was 44.8%.
  • the distance between the HSP values of the cycloolefin copolymer and the polyimide resin used in Example 1 is 8.3, the distance between the HSP values of the cycloolefin copolymer and toluene is 2.1, and the distance between the polyimide resin and toluene is 2.1.
  • the distance between HSP values was 10.0
  • the distance between HSP values between the cycloolefin copolymer and GBP was 14.9
  • the distance between HSP values between the polyimide resin and GBL was 8.5.
  • Example 2 Example 1 except that the toluene was distilled off under reduced pressure at 50 hPa and 80 ° C. to obtain a particulate cycloolefin copolymer dispersion so that the toluene content was 20 parts by mass with respect to 100 parts by mass of GBL. In the same manner as above, a particulate cycloolefin copolymer dispersion was obtained. To 35.9 g (cycloolefin copolymer 1.7% by mass) of the obtained particulate cycloolefin copolymer dispersion, 1.9 g of the polyimide resin obtained above is added to prepare a polyimide-cycloolefin copolymer mixed solution. I got something.
  • the median diameter of the particulate cycloolefin copolymer in the dispersion and the composition measured by the above method was 0.14 ⁇ m. In the obtained composition, no aggregate of cycloolefin copolymer larger than 1 mm was confirmed.
  • a polyimide-cycloolefin copolymer composite film having a thickness of 60 ⁇ m was obtained in the same manner as in Example 1 except that the obtained composition was used.
  • the content of the particulate cycloolefin copolymer in the obtained composite film was 24% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
  • the CTE of the obtained composite film was 44 ppm / K. Further, the standard deviation of the average thickness of the obtained composite film was 0.37, and the smoothness of the film surface was also excellent.
  • the haze of the obtained composite film was 50.5%.
  • Example 3 Example 1 except that the toluene was distilled off under reduced pressure at 50 hPa and 80 ° C. to obtain a particulate cycloolefin copolymer dispersion so that the toluene content was 30 parts by mass with respect to 100 parts by mass of GBL. In the same manner as above, a particulate cycloolefin copolymer dispersion was obtained. To 38.8 g (1.5% by mass) of the obtained particulate cycloolefin copolymer dispersion liquid, 1.9 g of the polyimide resin obtained above was added to prepare a polyimide-cycloolefin copolymer mixed solution. I got something.
  • the median diameter of the particulate cycloolefin copolymer in the dispersion and the composition measured by the above method was 0.13 ⁇ m. In the obtained composition, no aggregate of cycloolefin copolymer larger than 1 mm was confirmed.
  • a polyimide-cycloolefin copolymer composite film having a thickness of 60 ⁇ m was obtained in the same manner as in Example 1 except that the obtained composition was used.
  • the content of the particulate cycloolefin copolymer in the obtained composite film was 24% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
  • the CTE of the obtained composite film was 45 ppm / K, and the smoothness of the film surface was also excellent.
  • the haze of the obtained composite film was 65.7%.
  • Example 4 2.73 g of crushed cycloolefin copolymer powder and 52.03 g of DMAc were mixed and stirred to obtain a dispersion liquid. The toluene content of the obtained dispersion was 1.3 parts by mass with respect to 100 parts by mass of DMAc. To the obtained dispersion, 100 g of a polyamic acid solution (15% by mass of polyamic acid) was added to obtain a composition as a polyamic acid-cycloolefin copolymer mixed solution. The median diameter of the particulate cycloolefin copolymer in the dispersion and the composition measured by the above method was 2.6 ⁇ m.
  • the obtained composition no aggregate of cycloolefin copolymer larger than 1 mm was confirmed.
  • the obtained composition was subjected to salivation molding on a glass substrate to prepare a coating film at a linear 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 film was further heated at 360 ° C. for 15 minutes under a nitrogen atmosphere.
  • the polyamic acid was imidized to obtain a polyimide-cycloolefin copolymer composite film having a thickness of 50 ⁇ m.
  • the content of the particulate cycloolefin copolymer was 15.4% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
  • the CTE of the obtained composite film was 19 ppm / K, and the smoothness of the film surface was also excellent.
  • the haze of the obtained composite film was 98.9%.
  • the distance between the HSP values of the cycloolefin copolymer and the polyamic acid used in Example 4 was 6.0 or more, and the distance between the HSP values of the cycloolefin copolymer and the DMAc was 11.5.
  • the distance between the HSP values of the cycloolefin copolymer used in Example 4 and the polyimide resin obtained by imidizing the polyamic acid was 6.0 or more.
  • the cycloolefin copolymer used in Example 4 was dissolved in toluene and not in DMAc. Further, the polyamic acid was dissolved in DMAc and not in toluene.
  • Example 5 A dispersion was obtained by mixing 5.69 g of particulate PTFE (manufactured by P Cincinnatilysciences Inc., melting point; 320 ° C., Mw: 20,000), 41.9 g of DMAc, and 0.2 g of toluene, and stirring the mixture.
  • the toluene content of the obtained dispersion was 0.5 parts by mass with respect to 100 parts by mass of DMAc.
  • 100 g of a polyamic acid solution (15% by mass of polyamic acid) was added to the obtained dispersion to obtain a composition as a polyamic acid-PTFE mixed solution.
  • the median diameter of the particulate PTFE in the dispersion and the composition measured by the above method was 3 ⁇ m.
  • the obtained composition no aggregate of PTFE exceeding 1 mm was confirmed.
  • the obtained composition was subjected to salivation molding on a glass substrate to prepare a coating film at a linear speed of 0.4 m / min.
  • the coating film is heated at 50 ° C. for 80 minutes, the polyamic acid-PTFE composite film is peeled off from the glass substrate, the film is fixed with a metal frame, and the polyamic acid is gradually increased to 360 ° C. in 30 minutes under a nitrogen atmosphere.
  • the polyamic acid was imidized to obtain a polyimide-PTFE composite film having a thickness of 50 ⁇ m.
  • the content of particulate PTFE was 27.5% by mass with respect to the total mass of the polyimide resin and PTFE.
  • the CTE of the obtained composite film was 17 ppm / K, and the smoothness of the film surface was also excellent.
  • the haze of the obtained composite film was 88.0%.
  • the distance between the HSP values of PTFE and the polyamic acid used in Example 5 was 6.0 or more, and the distance between the HSP values of PTFE and DMAc was 9.5. Further, the distance between the HSP values of the PTFE used in Example 5 and the polyimide resin obtained by imidizing the polyamic acid was 6.0 or more.
  • Example 6 100.0 g of the obtained cycloolefin copolymer solution 2 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. for 2 hours. Toluene was distilled off under reduced pressure to obtain a particulate cycloolefin copolymer dispersion. The median diameter of the particulate cycloolefin copolymer in the particulate cycloolefin copolymer dispersion measured by the above method was 0.13 ⁇ m.
  • a composition as a polyamic acid-cycloolefin copolymer mixed solution was prepared. Obtained. In the obtained composition, no aggregate of cycloolefin copolymer larger than 1 mm was confirmed.
  • the obtained composition was subjected to salivation molding on a glass substrate to prepare a coating film at a linear speed of 0.4 m / min. The coating film is heated at 70 ° C.
  • the polyamic acid-cycloolefin copolymer composite film is peeled off from the glass substrate, the film is fixed with a metal frame, and the polyamic acid is gradually increased to 360 ° C. in 30 minutes under a nitrogen atmosphere.
  • the polyamic acid was imidized to obtain a polyimide-cycloolefin copolymer composite film having a thickness of 30 ⁇ m.
  • the content of the particulate cycloolefin copolymer was 15.4% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
  • the CTE of the obtained composite film was 18 ppm / K, and the smoothness of the surface of the obtained composite film was also excellent.
  • the haze of the obtained composite film was 96.6%.
  • the distance between the HSP values of the cycloolefin copolymer and the polyamic acid used in Example 6 is 6.0 or more, and the distance between the HSP values of the cycloolefin copolymer and toluene is 2.1.
  • the distance between the HSP values with DMAc was 11.5.
  • the distance between the HSP values of the cycloolefin copolymer used in Example 6 and the polyimide resin obtained by imidizing the polyamic acid was 6.0 or more.
  • the cycloolefin copolymer used in Example 6 was dissolved in toluene and not in DMAc.
  • the polyamic acid used in Example 6 was soluble in DMAc and not in toluene.
  • the content of the particulate cycloolefin copolymer in the obtained composite film was 24% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
  • the CTE of the obtained composite film was 44 ppm / K.
  • the standard deviation of the average thickness of the obtained composite film was 1.77.
  • the haze of the obtained composite film was 69.3%.
  • the haze, brightness, and water absorption of the polyimide-cycloolefin copolymer composite film and the polyimide-PTFE composite film obtained in Examples and Comparative Examples were measured according to the above method.
  • the obtained results are shown in Table 4.
  • the brightness of the composite film is measured on both sides of the film, and the brightness of the surface in contact with the glass substrate at the time of forming the film is shown as L1 and the brightness of the opposite surface is shown as L2.
  • Table 4 also shows the toluene content of the particulate cycloolefin copolymer dispersion and the particulate PTFE dispersion with respect to 100 parts by mass of GBL or DMAc in Examples and Comparative Examples.
  • the films obtained in Examples 1 to 6 had a low water absorption rate and were excellent in water absorption resistance as compared with Comparative Example 1.

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Abstract

L'invention concerne un film excellent en termes de résistance à l'absorption d'eau, ainsi qu'une composition permettant de former un tel film. Plus spécifiquement, l'invention concerne un film contenant: (A) une résine polyimide et (B) un polymère sous forme de particules. Ce film présente un voile inférieur ou égal à 75%, et la luminosité L* telle que mesurée à l'aide d'un procédé de composante spéculaire exclue est inférieure ou égale à 37 sur les deux faces du film.
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06162856A (ja) * 1992-11-20 1994-06-10 Nippon Zeon Co Ltd 熱硬化性樹脂成形材料、成形品、及び熱可塑性ノルボルネン系樹脂粒子
JPH08334607A (ja) * 1995-06-07 1996-12-17 Fuji Photo Film Co Ltd 光学用透明プラスチックフイルム
JP2009031763A (ja) * 2007-06-12 2009-02-12 Eternal Chemical Co Ltd 光学フィルム
JP2010195891A (ja) * 2009-02-24 2010-09-09 Sanyo Chem Ind Ltd 多層構造球状粒子
JP2012185393A (ja) * 2011-03-07 2012-09-27 Fuji Xerox Co Ltd 円筒状成形体及びその製造方法、円筒状成形体ユニット、画像形成装置用部材、並びに画像形成装置
JP2014058620A (ja) * 2012-09-18 2014-04-03 Du Pont-Toray Co Ltd タブレット端末向けｃｏｆ用基板
JP2015052107A (ja) * 2013-08-08 2015-03-19 東京応化工業株式会社 多孔質ポリイミド膜の製造方法、多孔質ポリイミド膜、多孔質ポリイミド膜からなるセパレータ、及びワニス
JP2016183333A (ja) * 2015-03-26 2016-10-20 富士ゼロックス株式会社 樹脂粒子分散ポリイミド前駆体溶液の製造方法、樹脂粒子分散ポリイミド前駆体溶液、樹脂粒子含有ポリイミドフィルム、多孔質ポリイミドフィルムの製造方法、及び多孔質ポリイミドフィルム
JP2020111713A (ja) * 2019-01-16 2020-07-27 旭化成株式会社 ポリイミドワニス及びポリイミドフィルム、並びにこれらの製造方法
JP2021116372A (ja) * 2020-01-28 2021-08-10 富士フイルムビジネスイノベーション株式会社 ポリイミド前駆体溶液及び多孔質ポリイミドフィルムの製造方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3470578B2 (ja) * 1997-01-14 2003-11-25 住友化学工業株式会社 オレフィン（共）重合体の製造方法
JPH10279630A (ja) * 1997-04-04 1998-10-20 Sumitomo Chem Co Ltd オレフィン系重合体の製造方法
JP3940119B2 (ja) * 2002-12-27 2007-07-04 株式会社アイ．エス．テイ ポリイミド前駆体液組成物及びポリイミド被膜
JP2008248067A (ja) * 2007-03-30 2008-10-16 Du Pont Toray Co Ltd ポリイミドフィルムおよびフレキシブル回路基板
JP5936437B2 (ja) * 2011-06-13 2016-06-22 ポリプラスチックス株式会社 環状オレフィン系樹脂
EP2551865A3 (fr) * 2011-07-29 2016-05-25 Konica Minolta Business Technologies, Inc. Élément de conversion photoélectrique et cellule solaire
JP5860240B2 (ja) * 2011-08-02 2016-02-16 日東電工株式会社 樹脂部材の接合方法
JP6829029B2 (ja) * 2016-08-31 2021-02-10 三井化学株式会社 硬化性樹脂組成物、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
JP6899636B2 (ja) 2016-08-31 2021-07-07 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
JP2018185471A (ja) * 2017-04-27 2018-11-22 キヤノン株式会社 トナー

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06162856A (ja) * 1992-11-20 1994-06-10 Nippon Zeon Co Ltd 熱硬化性樹脂成形材料、成形品、及び熱可塑性ノルボルネン系樹脂粒子
JPH08334607A (ja) * 1995-06-07 1996-12-17 Fuji Photo Film Co Ltd 光学用透明プラスチックフイルム
JP2009031763A (ja) * 2007-06-12 2009-02-12 Eternal Chemical Co Ltd 光学フィルム
JP2010195891A (ja) * 2009-02-24 2010-09-09 Sanyo Chem Ind Ltd 多層構造球状粒子
JP2012185393A (ja) * 2011-03-07 2012-09-27 Fuji Xerox Co Ltd 円筒状成形体及びその製造方法、円筒状成形体ユニット、画像形成装置用部材、並びに画像形成装置
JP2014058620A (ja) * 2012-09-18 2014-04-03 Du Pont-Toray Co Ltd タブレット端末向けｃｏｆ用基板
JP2015052107A (ja) * 2013-08-08 2015-03-19 東京応化工業株式会社 多孔質ポリイミド膜の製造方法、多孔質ポリイミド膜、多孔質ポリイミド膜からなるセパレータ、及びワニス
JP2016183333A (ja) * 2015-03-26 2016-10-20 富士ゼロックス株式会社 樹脂粒子分散ポリイミド前駆体溶液の製造方法、樹脂粒子分散ポリイミド前駆体溶液、樹脂粒子含有ポリイミドフィルム、多孔質ポリイミドフィルムの製造方法、及び多孔質ポリイミドフィルム
JP2020111713A (ja) * 2019-01-16 2020-07-27 旭化成株式会社 ポリイミドワニス及びポリイミドフィルム、並びにこれらの製造方法
JP2021116372A (ja) * 2020-01-28 2021-08-10 富士フイルムビジネスイノベーション株式会社 ポリイミド前駆体溶液及び多孔質ポリイミドフィルムの製造方法

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