[go: up one dir, main page]

WO2018181436A1 - Film de polyimide - Google Patents

Film de polyimide Download PDF

Info

Publication number
WO2018181436A1
WO2018181436A1 PCT/JP2018/012667 JP2018012667W WO2018181436A1 WO 2018181436 A1 WO2018181436 A1 WO 2018181436A1 JP 2018012667 W JP2018012667 W JP 2018012667W WO 2018181436 A1 WO2018181436 A1 WO 2018181436A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyimide film
film
component
less
fluorine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/012667
Other languages
English (en)
Japanese (ja)
Inventor
池田　圭
孔一 澤崎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Du Pont Toray Co Ltd
Original Assignee
Du Pont Toray Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Du Pont Toray Co Ltd filed Critical Du Pont Toray Co Ltd
Publication of WO2018181436A1 publication Critical patent/WO2018181436A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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 polyimide film and the like.
  • the transmission speed of a semiconductor element is limited mainly by the occurrence of a delay between metal wires carrying signals.
  • an insulating layer having a low dielectric constant is disposed between the wires, thereby reducing the capacitive coupling between the wires, thereby increasing the operation speed and reducing the noise disturbance.
  • the insulating layer can block the flow of current, and when the dielectric constant is low, the transmission speed is improved.
  • the dielectric loss tangent is low, the transmission loss can be reduced. That is, the high-frequency circuit board must have a low coefficient of thermal expansion (CTE, linear expansion coefficient), and a dielectric constant (Dk) and dielectric loss tangent (Tan ⁇ ) that are stable and low.
  • CTE coefficient of thermal expansion
  • Dk dielectric constant
  • Tan ⁇ dielectric loss tangent
  • Patent Document 1 describes a laminated film in which a fluorine resin is laminated on both sides or one side of a polyimide film.
  • both surfaces were discharged on both surfaces or one surface of an aromatic polyimide film having a main acid skeleton derived from biphenyltetracarboxylic acid, which was discharged on both surfaces.
  • a laminated film in which a fluororesin film is laminated is described.
  • An object of the present invention is to provide a novel polyimide film.
  • a laminated film of a fluororesin film and a polyimide film is used for an insulating layer such as FPC.
  • the combination of the two resin films as described above is considered in consideration of the balance of various physical properties. For example, while communication speed may not be sufficient for polyimide film, strength and dimensional stability may not be sufficient for fluororesin film, but it is assumed that these defects can be reduced by combining these. Is done.
  • the present inventors examined whether a film that can be used for FPC or the like could be formed by using a single layer film of polyimide instead of laminating different resins.
  • a film that can be used for FPC or the like could be formed by using a single layer film of polyimide instead of laminating different resins.
  • polyimide single-layer film sufficient low dielectric properties and low water absorption performance may not be obtained, and there are cases where dimensional accuracy is not sufficient, etc. Extremely difficult.
  • the present inventors have conducted extensive research, and as a result, by selecting the aspect of the gel film that is the raw material of polyimide or the precursor of the film, even if it is a single-layer film of polyimide, the above-mentioned The inventors have found that such characteristics can be satisfied, and have further studied to complete the present invention.
  • this invention relates to the following polyimide films etc.
  • the polyimide film as described in [1] whose relative dielectric constant is 3.3 or less.
  • the metal laminate according to [10] which is a copper-clad laminate using a polyimide film as a base film.
  • a novel polyimide film can be provided.
  • a polyimide film has characteristics such as low dielectric constant and low water absorption (and consequently low water vapor and gas permeability). Therefore, for example, it can be suitably used as an FPC film (base film, coverlay, etc.), and can be suitably used particularly for high-frequency compatible substrates.
  • the polyimide film of the present invention often has a relatively low CTE (linear expansion coefficient). For this reason, even when laminated on a metal layer, the dimensional stability is high, which is suitable for FPC applications.
  • the polyimide film of the present invention satisfies a specific range in dielectric properties and water absorption.
  • the polyimide film of this invention should just satisfy at least one among the dielectric characteristics of such a specific range, and the water absorption rate of a specific range, and may satisfy either one or both. Good.
  • the dielectric loss tangent of the polyimide film of the present invention can be selected from a range of about 0.015 or less (for example, 0.012 or less), for example, 0.01 or less (for example, 0.0095 or less), preferably 0.009 or less. (For example, 0.0085 or less), more preferably 0.008 or less (for example, 0.0075 or less), particularly 0.007 or less (for example, 0.0065 or less), particularly preferably 0.006 or less (for example, 0 .0058 or less), 0.0055 or less, 0.0050 or less, or the like.
  • the lower limit value of the dielectric loss tangent is not particularly limited, and may be, for example, 0.001, 0.0015, 0.002, 0.0025, 0.0030, 0.0035, and the like.
  • the relative dielectric constant of the polyimide film can be selected from a range of about 3.5 or less (for example, 3.4 or less), for example, less than 3.4 (for example, 3.37 or less), preferably 3.35 or less (for example, 3.32 or less), more preferably 3.3 or less (eg 3.25 or less), 3.2 or less (eg 3.15 or less), 3.1 or less (eg 3.15 or less). 05 or less), 3.0 or less (for example, 2.95 or less), or the like.
  • the lower limit value of the relative dielectric constant is not particularly limited, but may be, for example, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, or the like.
  • the measuring method of a dielectric loss tangent and a dielectric constant is not specifically limited, You may follow a conventionally well-known method.
  • the measurement frequency of dielectric loss tangent and dielectric constant may be, for example, 2.54 GHz, 5.8 GHz, or the like.
  • the polyimide film satisfying a specific range of dielectric characteristics may satisfy the above range in at least one of dielectric loss tangent and relative dielectric constant among the dielectric characteristics.
  • the above range may be satisfied at least in the dielectric loss tangent, and more preferably, the above range may be satisfied in both the dielectric loss tangent and the relative dielectric constant.
  • the water absorption of the polyimide film can be selected from a range of about 2% or less (for example, 1.5% or less), for example, 1.2% or less (for example, 1.1% or less), preferably 1.0% or less. (For example, 0.95% or less), more preferably 0.9% or less (for example, 0.85% or less), particularly 0.8% or less (for example, 0.75% or less), particularly preferably 0.7 % Or less (for example, 0.65% or less), 0.6% or less (for example, 0.55% or less), 0.5% or less (for example, 0.45% or less), 0.4 % Or less (for example, 0.35% or less).
  • the lower limit of the water absorption rate is not particularly limited. For example, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0 0.08%, 0.09%, 0.10%, etc. may be sufficient.
  • the measuring method of a water absorption rate is not specifically limited, For example, you may follow JIS K 7209 etc., and you may measure a water absorption rate by the method as described in the Example mentioned later.
  • the polyimide film may have a specific linear expansion coefficient.
  • the linear expansion coefficient (absolute value of the linear expansion coefficient) of the polyimide film can be selected from a range of about 40 ppm / ° C. or less (eg, 37 ppm / ° C. or less), for example, 35 ppm / ° C. or less (eg, 33 ppm / ° C. or less), Preferably it is 32 ppm / ° C. or less (eg, 31 ppm / ° C. or less), more preferably 30 ppm / ° C. or less (eg, 28 ppm / ° C. or less), particularly 25 ppm / ° C.
  • the lower limit value of the linear expansion coefficient is not particularly limited and can be selected according to the use and the like, 0 ppm / ° C., 2 ppm / ° C., 3 ppm / ° C., 5 ppm / ° C., 8 ppm / ° C., 10 ppm It may be / ° C.
  • the linear expansion coefficient of the polyimide film may be close to the linear expansion coefficient of the metal layer or metal constituting the metal layer described later, and the same or smaller. Also good.
  • the linear expansion coefficient of the polyimide film is 0 to 25 ppm / ° C., 5 to 22 ppm / ° C., 8 to 20 ppm / ° C., 10 to 18 ppm / ° C., etc. There may be.
  • the linear expansion coefficient may be a linear expansion coefficient in a specific temperature range (for example, 50 to 200 ° C.).
  • the method for measuring the linear expansion coefficient is not particularly limited, and for example, the linear expansion coefficient may be measured by the method described in Examples described later.
  • the glass transition temperature of the polyimide film is not particularly limited, but is, for example, 150 ° C. or higher (eg, 180 to 450 ° C.), preferably 200 ° C. or higher (eg, 230 to 400 ° C.), More preferably, it may be 250 ° C. or higher (for example, 260 to 380 ° C.).
  • the thickness of the polyimide film is not particularly limited, and can be appropriately selected according to the use.
  • the thickness of the polyimide film may be 1 to 200 ⁇ m (eg 2 to 150 ⁇ m), preferably 3 to 100 ⁇ m (eg 4 to 90 ⁇ m), more preferably 5 to 80 ⁇ m (eg 7 to 60 ⁇ m). , 50 ⁇ m or less, 40 ⁇ m or less, 30 ⁇ m or less, and the like. Since the polyimide film of the present invention can satisfy the desired performance without being laminated with the fluororesin film, it can easily cope with thinning.
  • the polyimide film may be a laminate of a plurality of polyimide films, and may usually be a single polyimide film.
  • the polyimide film (or polyimide constituting the polyimide film or polyamic acid) has a diamine component and a tetracarboxylic acid component as polymerization components.
  • the polymerization component may contain other polymerization components as long as the diamine component and the tetracarboxylic acid component are the main components.
  • a diamine component (diamine component (A)) and a tetracarboxylic acid component (tetracarboxylic acid component (B)) are polymerized in an organic solvent.
  • a polyamic acid (polyimide precursor) solution is obtained.
  • the polyamic acid is subjected to a cyclization reaction.
  • the polyamic acid (diamine component (A) and tetracarboxylic acid component (B)) is a component (or a component that can be efficiently cyclized by the chemical cyclization method) that can be applied with a chemical cyclization method (or a chemical cyclization method). Is preferred.
  • the diamine component (A) usually contains at least an aromatic diamine component.
  • the tetracarboxylic acid component (B) usually contains an aromatic tetracarboxylic acid component.
  • Polyimide may usually contain fluorine.
  • the method for containing fluorine is not particularly limited, but usually, at least a fluorine-containing polymerization component may be used as the polymerization component.
  • At least one component selected from the diamine component (A) and the tetracarboxylic acid component (B) may contain fluorine.
  • it does not specifically limit as an aspect containing a fluorine For example, the aspect etc. which substitute the hydrogen atom which comprises a diamine component and a tetracarboxylic-acid component by a fluorine atom, etc. may be sufficient.
  • a skeleton substituted with a fluorine atom for example, a fluoroalkane skeleton [for example, a perfluoroalkane skeleton (or a perfluoroalkyl group) such as a trifluoromethane skeleton (or trifluoromethyl group)] ].
  • a component having a hydrocarbon skeleton such as a fluoroarene skeleton (e.g., a fluorobenzene skeleton) may be used.
  • diamine component (A) can be broadly classified into, for example, a fluorine-free diamine component (A2) and a fluorine-containing diamine component (A1).
  • fluorine-free diamine component (A2) examples include diaminoarene (for example, paraphenylenediamine, metaphenylenediamine, 1,5-diaminonaphthalene, etc.), diaminobiaryl [or bis (aminoaryl), for example, benzidine, 3 , 3′-dimethoxybenzidine], di (aminoalkyl) arene (eg, paraxylylenediamine), di (aminoaryl) ether (eg, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, etc.) , Di (aminoaryl) alkanes (eg, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane), di (aminoaryl) sulfones (eg, 4,4′-diaminodip
  • the fluorine-free diamine component (A2) may be used alone or in combination of two or more.
  • the diamine component (A2) includes 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (4-aminophenoxy) benzene, and 1,4-bis (4-amino). It may contain at least one selected from phenoxy) benzene.
  • fluorine-containing diamine component (A1) a compound in which hydrogen (atom) constituting the fluorine-free diamine component (A2) is substituted with fluorine (atom), for example, fluorine-containing diaminobiaryl ⁇ or fluorine-containing bis (aminoaryl)
  • fluoroalkylbenzidines eg, fluoroC 1-10 alkylbenzidines such as 2,2′-bis (trifluoromethyl) benzidine, 3,3′-bis (trifluoromethyl) benzidine, preferably perfluoroC 1-4 alkylbenzidine etc.
  • fluorine-containing di (aminoaryl) alkanes ⁇ eg di (aminophenyl) fluoroalkanes eg di (amino) such as 2,2-bis (4-aminophenyl) hexafluoropropane, etc. phenyl) fluoro C 1-10 alkanes, preferably Etc.
  • fluoroalkylbenzidine particularly 2,2′-bis (trifluoromethyl) benzidine is preferable.
  • the fluorine-containing diamine component (A1) may be used alone or in combination of two or more.
  • the diamine component (A) may be used alone or in combination of two or more.
  • the diamine component (A) may contain at least a fluorine-containing diamine component (A1).
  • the proportion of the fluorine-containing diamine component (A1) is, for example, 20 mol% or more (for example, 25 to 100 mol%) of the diamine component (A), Preferably, it may be 30 mol% or more (for example, 40 mol% or more), more preferably 50 mol% or more (for example, 55 mol% or more), particularly 60 mol% or more (for example, 65 mol% or more), It can also be 70 mol% or more (for example, 75 mol% or more), 80 mol% or more (for example, 85 mol% or more), 90 mol% or more (for example, 95 mol% or more), and the like.
  • fluorine-containing diamine component (A1) and the fluorine-free diamine component (A2) may be suitably combined.
  • 0.9 / 0.1 to 1/99 eg, 99.5 / 0.5 to 5/95
  • 99/1 to 10/90 eg, 98/2 to 20/80
  • more preferably 97/3 to 30/70 for example, 96/4 to 35/65
  • 95/5 to 40/60 for example, 93/7 to 45/50
  • 92/8 to 50/50 for example, it may be about 90/10 to 55/45
  • 99/1 to 60/40 for example, 95/5 to 65/35.
  • Specific tetracarboxylic acid components (B) can be roughly classified into, for example, fluorine-free tetracarboxylic acid components (B2) and fluorine-containing tetracarboxylic acid components (B1).
  • non-fluorine-containing tetracarboxylic acid component (B2) examples include non-fluorine-containing tetracarboxylic acids and amide-forming derivatives thereof such as arenetetracarboxylic acid components [for example, pyromellitic acid, 2,3,6,7-naphthalenetetra Carboxylic acid, pyridine-2,3,5,6-tetracarboxylic acid, their acid anhydrides (pyromellitic acid anhydride, etc.)], bis (dicarboxyaryl) ether component (for example, 4,4′-oxydiphthalate) Acid, 4,4′-oxydiphthalic anhydride, etc.), biaryl tetracarboxylic acid component [for example, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3 ′, 3,4′-biphenyltetracarboxylic acid Acids, anhydrides thereof (3,3 ′, 4,4′-bipheny
  • the fluorine-free tetracarboxylic acid component (B2) may be used alone or in combination of two or more.
  • fluorine-containing tetracarboxylic acid component (B1) a compound in which hydrogen (atom) constituting the fluorine-free tetracarboxylic acid component is substituted with fluorine (atom), for example, a fluorine-containing bis (dicarboxyaryl) alkane ⁇ for example, Bis (dicarboxyphenyl) fluoroalkanes [eg bis (dicarboxyphenyl) fluoro C 1-10 alkanes such as 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, preferably bis (dicarboxyphenyl) per Fluoro C 1-4 alkane] and the like ⁇ .
  • a fluorine-containing bis (dicarboxyaryl) alkane for example, Bis (dicarboxyphenyl) fluoroalkanes [eg bis (dicarboxyphenyl) fluoro C 1-10 alkanes such as 4,4 ′-(hexaflu
  • the fluorine-containing tetracarboxylic acid component (B1) may be used alone or in combination of two or more.
  • the tetracarboxylic acid component (B) may be used alone or in combination of two or more.
  • the tetracarboxylic acid component (B) may contain at least a 3,3 ′, 4,4′-biphenyltetracarboxylic acid component.
  • the ratio of 3,3 ′, 4,4′-biphenyltetracarboxylic acid component is, for example, tetracarboxylic acid component 20 mol% or more (for example, 25 to 100 mol%) of the acid component (B), preferably 30 mol% or more (for example, 40 mol% or more), more preferably 50 mol% or more (for example, 55 mol% or more) In particular, it may be 60 mol% or more (for example, 65 mol% or more), 70 mol% or more (for example, 75 mol% or more), 80 mol% or more (for example, 85 mol% or more), 90 mol% or more. (For example, 95 mol% or more).
  • the tetracarboxylic acid component (B) may suitably contain a fluorine-containing tetracarboxylic acid component (B1).
  • the fluorine-containing tetracarboxylic acid component (B1) and the fluorine-free tetracarboxylic acid The component (B2) can also be combined.
  • the ratio of the fluorine-containing tetracarboxylic acid component (B1) is, for example, 1 mol% or more of the tetracarboxylic acid component (B) (for example, 1 to 100 mol%), preferably 2 mol% or more (eg 3 to 80 mol%), more preferably 5 mol% or more (eg 6 to 50 mol%), especially 10 mol% or more (eg 10 To 40 mol% or more), and usually 1 to 50 mol% (eg, 3 to 40 mol%, 5 to 35 mol%).
  • organic solvent used for forming the polyamic acid solution examples include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, N , N-dimethylacetamide, N, N-diethylacetamide and other acetamide solvents, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone and other pyrrolidone solvents, phenol, o-, m-, or p- Mention may be made of phenolic solvents such as cresol, xylenol, halogenated phenol and catechol, or aprotic polar solvents such as hexamethylphosphoramide and ⁇ -butyrolactone, which are used alone or as a mixture of two or more. It is desirable to use xylene.
  • aromatic hydrocarbons such as toluene are also possible
  • the polymerization method may be carried out by any known method. For example, (1) the total amount of the diamine component is first put in the solvent, and then the tetracarboxylic acid component is equivalent to the total amount of the diamine component (equal mole). In addition, a polymerization method. (2) A method in which the total amount of the tetracarboxylic acid component is first put in a solvent, and then the diamine component is added so as to be equivalent to the tetracarboxylic acid component for polymerization.
  • a polyamic acid solution (A) is prepared by reacting one diamine component and a tetracarboxylic acid component in a solvent so that either one becomes excessive, and the other diamine component and the tetracarboxylic acid in another solvent.
  • the polyamic acid solution (B) is prepared by reacting either component in excess. A method in which the polyamic acid solutions (A) and (B) thus obtained are mixed to complete the polymerization.
  • the polymerization method is not limited to these, and other known methods may be used.
  • the polyamic acid solution usually contains a solid content of about 5 to 40% by weight, and preferably may contain a solid content of about 10 to 30% by weight.
  • the viscosity of the polyamic acid solution may be usually about 10 to 2000 Pa ⁇ s as measured by a Brookfield viscometer, and preferably about 100 to 1000 Pa ⁇ s for stable liquid feeding. Good.
  • the polyamic acid in the organic solvent solution may be partially imidized.
  • the film formation (production) of the polyimide film is, for example, a step (1) of obtaining a gel film by cyclizing a polyamic acid solution (converting the polyamic acid or the polyamic acid solution into a gel film), and the obtained gel film. It can be obtained through a step (2) of drying (and solvent removal) and heat treatment. Note that drying and imidization proceed by drying and heat treatment.
  • the method for cyclizing the polyamic acid solution is not particularly limited. Specifically, (i) the gel film is obtained by casting the polyamic acid solution into a film and thermally dehydrating it. Or (ii) mixing a catalyst (cyclization catalyst) and a dehydrating agent (converting agent) in a polyamic acid solution and chemically decyclizing to produce a gel film, Examples thereof include a method for obtaining a gel film (chemical ring closure method), and the latter method (chemical ring closure method) is particularly preferable.
  • the polyimide film of the present invention is surprisingly required. It seems that it is easy to efficiently obtain physical properties and characteristics (dielectric characteristics, water absorption, CTE, etc.).
  • the chemical ring closure method is also suitable from the viewpoint of mass productivity.
  • the polyamic acid solution may contain a gelation retarder and the like. It does not specifically limit as a gel retarder, Acetyl acetone etc. can be used.
  • Cyclization catalysts include amines such as aliphatic tertiary amines (trimethylamine, triethylenediamine, etc.), aromatic tertiary amines (dimethylaniline, etc.), heterocyclic tertiary amines (eg, isoquinoline, pyridine, ⁇ -picoline and the like). These may be used individually by 1 type, and 2 or more types may be mixed and used for them. Of these, heterocyclic tertiary amines such as ⁇ -picoline are preferred.
  • the dehydrating agent examples include acid anhydrides such as aliphatic carboxylic acid anhydrides (eg, acetic anhydride, propionic anhydride, butyric anhydride), aromatic carboxylic acid anhydrides (eg, benzoic anhydride, etc.), and the like. . These may be used individually by 1 type, and 2 or more types may be mixed and used for them. Among these, acetic anhydride and / or benzoic anhydride are preferable, and acetic anhydride is particularly preferable.
  • acid anhydrides such as aliphatic carboxylic acid anhydrides (eg, acetic anhydride, propionic anhydride, butyric anhydride), aromatic carboxylic acid anhydrides (eg, benzoic anhydride, etc.), and the like. . These may be used individually by 1 type, and 2 or more types may be mixed and used for them. Among these, acetic anhydride and / or benzoic anhydride are preferable, and
  • a cyclization catalyst and a dehydrating agent is not specifically limited, For example, 1 mol or more (for example, 1.5 mol) with respect to 1 mol of amide groups (or carboxyl groups) of polyamic acid (or polyamic acid), respectively. About 10 mol).
  • the gel film is usually obtained by casting (coating) a polyamic acid solution (particularly, a polyamic acid solution in which a cyclization catalyst and a conversion agent are mixed) onto a support, and partially drying and curing (imidizing). Obtainable.
  • the polyamic acid solution is cast on a support from a base with a slit and formed into a film, and is heated by receiving heat from the support, heat from a heat source such as hot air or an electric heater.
  • the gel film may be obtained by ring-closing reaction and drying a volatile component such as a free organic solvent, and then peeled off from the support.
  • the gel film needs to have a self-supporting property in order to peel off, but usually the gel film obtained by the chemical cyclization method and the gel film obtained by the thermal cyclization method have greatly different modes. . That is, in the chemical ring closure method, gelation (conversion) can be performed by a catalyst, so that a self-supporting gel film (soft or wet gel film) containing a large amount of solvent can be obtained. A large amount of heat treatment is required to give supportability, and as a result, a gel film that is relatively hard (low residual solvent) is obtained.
  • a polyimide film having desired properties can be efficiently formed by using a gel film that has undergone a chemical ring closure method.
  • the support is not particularly limited, and examples thereof include a metal (for example, stainless steel) rotating drum, an endless belt, and the like.
  • the temperature of the support is not particularly limited, and may be, for example, 30 to 200 ° C, preferably 40 to 150 ° C, and more preferably 50 to 120 ° C.
  • the temperature of the support can be controlled by (i) a liquid or gas heat medium, (ii) radiant heat from an electric heater, or the like.
  • step (2) the gel film is dried (desolvent) and then heat-treated.
  • the step (2) may include a step of passing through a heating furnace (such as a tenter heating furnace) while drying both ends in the width direction of the gel film, drying, and then performing a heat treatment.
  • a heating furnace such as a tenter heating furnace
  • the gel film peeled off from the support is not particularly limited, but may usually be stretched in the transport direction while regulating the running speed with a rotating roll.
  • the stretching in the transport direction may be performed at a predetermined temperature (for example, a temperature of 140 ° C. or lower).
  • the draw ratio (MDX) is usually 1.05 to 1.9 times, preferably 1.1 to 1.6 times, more preferably 1.1 to 1.5 times (for example, 1.15). ⁇ 1.4 times).
  • the drying temperature is, for example, 210 ° C. or higher (eg, 213 to 500 ° C.), preferably 215 ° C. or higher (eg, 218 to 400 ° C.), more preferably 220 ° C. or higher (eg, 220 to 300 ° C.). You may go.
  • drying may be performed while suppressing drying unevenness (variation) in the film width direction.
  • the drying temperature unevenness in the film width direction is, for example, less than 25 ° C. (eg, 0 to 24 ° C.), preferably 22 ° C. or less (eg, 1 to 21 ° C.), more preferably 20 ° C. or less (eg, 2 to 2 ° C.). 19 ° C.), particularly 18 ° C. or lower (eg, 3 to 18 ° C.).
  • the drying temperature unevenness takes, for example, a plurality of points at a predetermined interval (for example, 200 mm) along the film width direction, and the difference (width) between the maximum value and the minimum value of the measured drying temperature is defined as the drying temperature unevenness. It can be measured.
  • Gel film (especially gel film stretched in the conveying direction) is heat-treated after drying.
  • the heat treatment temperature is not particularly limited, and may be, for example, 200 ° C. or higher (eg, 250 to 600 ° C.), preferably 300 ° C. or higher, more preferably 350 ° C. or higher.
  • the stretching in the width direction may be performed together with the heat treatment.
  • the draw ratio (TDX) is, for example, 1.05 to 1.9 times, preferably 1.1 to 1.6 times, and more preferably 1.1 to 1.5 times. It may be double (for example, 1.15 to 1.4 times).
  • the dielectric loss tangent, relative dielectric constant, CTE, water absorption, and the like may be easily reduced (or easily adjusted) in some cases.
  • the obtained polyimide film may be further subjected to annealing treatment or easy adhesion treatment (for example, electrical treatment such as corona treatment or plasma treatment or blast treatment).
  • the polyimide film of the present invention can be suitably used for laminating with a metal layer (metal foil) to form a metal laminate.
  • the polyimide film of the present invention is suitable as a film for circuit boards, in particular, a flexible printed circuit board (FPC) (particularly, an insulating film or a coverlay film).
  • FPC flexible printed circuit board
  • the present invention includes a metal laminate including (used) the polyimide film.
  • a metal laminate may particularly constitute a flexible printed circuit board (flexible board).
  • the polyimide film may be laminated on the metal layer, may constitute a base film in the metal laminate, or may constitute a cover lay (film). Both of these may be configured.
  • a metal laminate including a protective film and a cover lay film at least one of the base film and the cover lay may be formed of the polyimide film.
  • the polyimide film of the present invention may be suitably used as at least a base film (base film for forming a metal layer).
  • the type of metal constituting the metal layer is not particularly limited.
  • copper copper alone, copper alloy, etc.
  • stainless steel and its alloys nickel (nickel alone, nickel alloy, etc.), aluminum (aluminum) , Aluminum alloy, etc.).
  • a copper-clad laminate is obtained by laminating such a metal layer and a polyimide film.
  • the heat-resistant layer for example, plating processing of chromium, zinc, etc.
  • a silane coupling agent, etc. on these metal surfaces can also be utilized.
  • copper and / or nickel, zinc, iron, chromium, cobalt, molybdenum, tungsten, vanadium, beryllium, titanium, tin, manganese, aluminum, phosphorus, silicon, etc. and at least one component and copper are included.
  • copper alloys which are preferred for use in circuit processing.
  • Particularly preferable metal layers include copper formed by rolling or electrolytic plating.
  • the thickness of the metal layer is not particularly limited, but may be, for example, about 1 to 150 ⁇ m (for example, 3 to 50 ⁇ m).
  • the form of the laminate is not particularly limited, and depends on the purpose of use of the polyimide film (whether it is a substrate film or a coverlay).
  • a polyimide film and a metal layer may be directly laminated, or a polyimide film and a metal foil may be laminated (bonded) via an adhesive layer (adhesive layer).
  • the adhesive component constituting the adhesive layer is not particularly limited, and may be, for example, a thermosetting resin or a thermoplastic resin.
  • the metal laminate can be used for a flexible wiring board on which various miniaturized and densified parts are mounted if a desired pattern wiring is formed by etching the metal layer.
  • the application of the present invention is not limited to this, and it is needless to say that a laminated body including a metal layer can be used for various applications.
  • Dielectric characteristics were measured by connecting a perturbation method dielectric constant measuring device CP521 (for 5.8 GHz) manufactured by Agilent Technology Co., Ltd./Kanto Electronics Co., Ltd. to a network analyzer 8722A / C / D with a coaxial cable. Using a Mitutoyo lightmatic (Series 318) thickness gauge, 15 locations were arbitrarily selected from the entire surface of the film, the thicknesses were measured at these 15 locations, and the average was calculated to obtain the thickness.
  • CP521 for 5.8 GHz
  • a network analyzer 8722A / C / D with a coaxial cable.
  • Using a Mitutoyo lightmatic (Series 318) thickness gauge 15 locations were arbitrarily selected from the entire surface of the film, the thicknesses were measured at these 15 locations, and the average was calculated to obtain the thickness.
  • Glass-transition temperature Using a dynamic viscoelasticity measuring device DMS6000 manufactured by Hitachi High-Tech Science, measurement temperature range: 25 to 400 ° C., temperature rising rate: 2 ° C./min, frequency: 5 Hz, under nitrogen atmosphere. The temperature at the peak top of the obtained Tan ⁇ was defined as the glass transition temperature.
  • Example 1 In a 500 ml separable flask equipped with a DC stirrer, 36.0 g of 2,2′-bis (trifluoromethyl) benzidine and 231.0 g of N, N-dimethylacetamide were placed at 40 ° C. using a water bath in a nitrogen atmosphere. Stir. After stirring for 30 minutes, 33.0 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added in several portions and stirred for 1 hour to obtain a polyamic acid.
  • Example 2 In a 500 ml separable flask equipped with a DC stirrer, 33.5 g of 2,2′-bis (trifluoromethyl) benzidine and 231.0 g of N, N-dimethylacetamide were placed at 40 ° C. using a water bath in a nitrogen atmosphere. Stir. After stirring for 30 minutes, 21.5 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added in several portions and stirred for 1 hour. Thereafter, 13.9 g of 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride was added in several portions and stirred for 1 hour to obtain a polyamic acid. The obtained polyamic acid was formed into a film by the method described in Example 1 to obtain a polyimide film having a thickness of 25 ⁇ m.
  • Example 3 The addition amounts of 2,2′-bis (trifluoromethyl) benzidine and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride were 37.3 g and 24.0 g, respectively.
  • a polyimide film having a thickness of 25 ⁇ m was obtained by the same method as in Example 2 except that hexafluoroisopropylidene) diphthalic anhydride was changed to 7.6 g of pyromellitic anhydride.
  • Example 4 The amounts of 2,2′-bis (trifluoromethyl) benzidine and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride added were 35.7 g and 22.9 g, respectively, and 4,4 ′-( A polyimide film having a thickness of 25 ⁇ m was obtained in the same manner as in Example 2 except that hexafluoroisopropylidene) diphthalic anhydride was changed to 10.4 g of 4,4′-oxydiphthalic anhydride.
  • Example 5 The amount of addition of 2,2′-bis (trifluoromethyl) benzidine and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was 32.4 g and 20.8 g, respectively. Hexafluoroisopropylidene) diphthalic anhydride was changed to 15.8 g of 5,5 ′-[1-methyl-1,1-ethanediylbis (1,4-phenylene) bisoxy] bis (isobenzofuran-1,3-dione) A polyimide film with a thickness of 25 ⁇ m was obtained by the same method as in Example 2 except that.
  • Example 6 In a 500 ml separable flask equipped with a DC stirrer, 24.1 g of 2,2′-bis (trifluoromethyl) benzidine and 231.0 g of N, N-dimethylacetamide were placed at 40 ° C. using a water bath in a nitrogen atmosphere. Stir. After stirring for 30 minutes, 22.1 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added in several portions and stirred for 1 hour. Thereafter, 13.2 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane was added and stirred for 30 minutes.
  • Example 7 The amount of 2,2′-bis (trifluoromethyl) benzidine and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride added was 25.5 g and 23.5 g, respectively.
  • 4- (4-aminophenoxy) phenyl] propane was changed to 10.0 g of 1,3-bis (4-aminophenoxy) benzene, and then 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 10
  • a polyimide film having a thickness of 25 ⁇ m was obtained in the same manner as in Example 6 except that 0.1 g was added.
  • Example 8 The amount of 2,2′-bis (trifluoromethyl) benzidine and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride added was 25.5 g and 23.5 g, respectively.
  • 4- (4-aminophenoxy) phenyl] propane was changed to 10.0 g of 1,4-bis (4-aminophenoxy) benzene, and then 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 10
  • a polyimide film having a thickness of 25 ⁇ m was obtained in the same manner as in Example 6 except that 0.1 g was added.
  • Example 10 In a 500 ml separable flask equipped with a DC stirrer, 26.7 g of 2,2′-bis (trifluoromethyl) benzidine and 231.0 g of N, N-dimethylacetamide were placed at 40 ° C. using a water bath in a nitrogen atmosphere. Stir. After stirring for 30 minutes, 24.5 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added in several portions and stirred for 1 hour. Thereafter, 8.6 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane was added and stirred for 30 minutes.
  • Example 11 In a 500 ml separable flask equipped with a DC stirrer, 22.5 g of 2,2′-bis (trifluoromethyl) benzidine and 231.0 g of N, N-dimethylacetamide were placed at 40 ° C. using a water bath in a nitrogen atmosphere. Stir. After stirring for 30 minutes, 20.7 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added in several portions and stirred for 1 hour. Thereafter, 12.4 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane was added and stirred for 30 minutes.
  • Example 12 In a 500 ml separable flask equipped with a DC stirrer, 26.1 g of 2,2′-bis (trifluoromethyl) benzidine and 231.0 g of N, N-dimethylacetamide were placed at 40 ° C. using a water bath in a nitrogen atmosphere. Stir. After stirring for 30 minutes, 24.0 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added in several portions and stirred for 1 hour. Thereafter, 8.4 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane was added and stirred for 30 minutes.
  • Example 13 In a 500 ml separable flask equipped with a DC stirrer, 21.8 g of 2,2′-bis (trifluoromethyl) benzidine and 231.0 g of N, N-dimethylacetamide were placed at 40 ° C. using a water bath in a nitrogen atmosphere. Stir. After stirring for 30 minutes, 20.0 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added in several portions and stirred for 1 hour. Thereafter, 12.0 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane was added and stirred for 30 minutes.
  • Example 14 The polyamic acid solution obtained in Example 1 was cast into a glass plate using an applicator, heat-treated at 90 ° C. for 10 minutes, and a self-supporting gel film was obtained by a thermal ring closure method. The gel film was pinned on a metal frame with a 10 cm square needle, and heat-treated under conditions of 200 ° C. for 30 minutes, 300 ° C. for 20 minutes, and 320 ° C. for 5 minutes to obtain a polyimide film with a thickness of 25 ⁇ m.
  • Example 15 In a 500 ml separable flask equipped with a DC stirrer, 15.0 g of 2,2′-bis (trifluoromethyl) benzidine and 231.0 g of N, N-dimethylacetamide were placed at 40 ° C. using a water bath in a nitrogen atmosphere. Stir. After stirring for 30 minutes, 13.8 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added in several portions and stirred for 1 hour. Thereafter, 19.3 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane was added and stirred for 30 minutes.
  • Example 16 In a 500 ml separable flask equipped with a DC stirrer, 14.3 g of 2,2′-bis (trifluoromethyl) benzidine and 231.0 g of N, N-dimethylacetamide were placed at 40 ° C. using a water bath in a nitrogen atmosphere. Stir. After stirring for 30 minutes, 13.1 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added in several portions and stirred for 1 hour. Thereafter, 18.3 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane was added and stirred for 30 minutes.
  • a self-supporting gel film was obtained by a thermal ring closure method.
  • the gel film was pinned on a metal frame with a 10 cm square needle, and heat-treated under conditions of 200 ° C. for 30 minutes, 300 ° C. for 20 minutes, and 320 ° C. for 5 minutes to obtain a polyimide film with a thickness of 25 ⁇ m.
  • the above polyamic acid was not suitable for the chemical ring closure method for producing a gel film.
  • the obtained polyamic acid was formed into a film by the method described in Example 1 to obtain a polyimide film having a thickness of 25 ⁇ m.
  • the above polyamic acid was not suitable for the chemical ring closure method for producing a gel film.
  • TFMB 2,2′-bis (trifluoromethyl) benzidine
  • BAPP 2,2-bis [4- (4-aminophenoxy) phenyl] propane
  • 1,3-APB 1,3-bis (4-aminophenoxy)
  • Benzene 14-APB 1,4-bis (4-aminophenoxy) benzene
  • ODA 4,4′-oxydianiline
  • BPDA 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride
  • 6FDA 4,4 '-(Hexafluoroisopropylidene) diphthalic anhydride
  • PMDA pyromellitic anhydride
  • ODPA 4,4'-oxydiphthalic anhydride
  • BPADA 5,5'-[1-methyl-1,1-ethanediylbis (1,4-phenylene) bisoxy] bis (isobenzofuran-1,3-dione)
  • CTE linear expansion coefficient Tg: glass transition

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention fournit un film de polyimide destiné à être mis en œuvre en tant que carte de circuit imprimé souple. Le facteur de dissipation diélectrique de ce film de polyimide est inférieur ou égal à 0,007, son coefficient d'absorption d'eau est inférieur ou égal à 0,8, et son coefficient de dilatation linéique entre 50 et 200°C est inférieur ou égal à ３０ｐｐｍ／℃.
PCT/JP2018/012667 2017-03-28 2018-03-28 Film de polyimide Ceased WO2018181436A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017064025A JP2018165346A (ja) 2017-03-28 2017-03-28 ポリイミドフィルム
JP2017-064025 2017-03-28

Publications (1)

Publication Number Publication Date
WO2018181436A1 true WO2018181436A1 (fr) 2018-10-04

Family

ID=63677602

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/012667 Ceased WO2018181436A1 (fr) 2017-03-28 2018-03-28 Film de polyimide

Country Status (3)

Country Link
JP (1) JP2018165346A (fr)
TW (1) TW201840648A (fr)
WO (1) WO2018181436A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113260676A (zh) * 2019-12-13 2021-08-13 株式会社斗山 具有优异的耐候性的聚酰亚胺膜
US20210364919A1 (en) * 2019-01-23 2021-11-25 Microcosm Technology Co., Ltd. Photosensitive resin composition and application thereof
CN116144022A (zh) * 2023-02-27 2023-05-23 中国科学院山西煤炭化学研究所 一种聚酰亚胺聚合物、薄膜、制备方法及应用

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7429411B2 (ja) * 2018-11-06 2024-02-08 ユニチカ株式会社 高周波基板用積層体
TWI871330B (zh) * 2019-06-14 2025-02-01 美商杜邦電子股份有限公司 聚合物膜及電子裝置
KR102224504B1 (ko) * 2019-07-05 2021-03-09 피아이첨단소재 주식회사 폴리아믹산 조성물, 폴리아믹산 조성물의 제조 방법 및 이를 포함하는 폴리이미드
KR102224505B1 (ko) * 2019-07-05 2021-03-09 피아이첨단소재 주식회사 폴리아믹산 조성물, 폴리아믹산 조성물의 제조 방법, 이를 포함하는 폴리이미드 및 이를 포함하는 피복물
KR102224503B1 (ko) * 2019-07-05 2021-03-09 피아이첨단소재 주식회사 폴리아믹산 조성물, 폴리아믹산 조성물의 제조 방법, 이를 포함하는 폴리이미드 및 이를 포함하는 피복물
KR102260038B1 (ko) * 2019-09-27 2021-06-03 피아이첨단소재 주식회사 폴리아믹산 조성물, 폴리아믹산 조성물의 제조방법 및 이를 포함하는 폴리이미드
KR102260048B1 (ko) * 2019-09-27 2021-06-03 피아이첨단소재 주식회사 폴리아믹산 조성물, 폴리아믹산 조성물의 제조방법 및 이를 포함하는 폴리이미드
KR102260028B1 (ko) * 2019-09-27 2021-06-03 피아이첨단소재 주식회사 폴리아믹산 조성물, 폴리아믹산 조성물의 제조방법 및 이를 포함하는 폴리이미드
KR102260052B1 (ko) * 2019-09-27 2021-06-03 피아이첨단소재 주식회사 폴리아믹산 조성물, 폴리아믹산 조성물의 제조방법 및 이를 포함하는 폴리이미드
JP7438790B2 (ja) * 2020-03-04 2024-02-27 東レ・デュポン株式会社 接着剤付きポリイミドフィルムおよびフラットケーブル
KR102334495B1 (ko) * 2020-04-09 2021-12-06 피아이첨단소재 주식회사 폴리이미드 용액, 이의 제조방법, 이에 따른 폴리이미드, 및 이를 포함하는 반도체 장치
JPWO2022009782A1 (fr) 2020-07-10 2022-01-13
EP4190768A4 (fr) * 2020-08-05 2024-07-17 Central Glass Company, Limited Diamine fluorée ou son sel, procédé de production d'une diamine fluorée ou d'un sel de celle-ci, polyamide, procédé de production de polyamide, solution de polyamide, polyamide cyclisé, procédé de production de polyamide cyclisé, matériau isolant pour composant électronique haute fréquence, procédé de production d'un matériau isolant pour composant électronique haute fréquence, composant électronique haute fréquence, appareil haute fréquence et matériau isolant pour produire un composant électronique haute fréquence
JPWO2022085619A1 (fr) * 2020-10-22 2022-04-28

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014208644A1 (fr) * 2013-06-28 2014-12-31 新日鉄住金化学株式会社 Polyimide, film de résine et stratifié métallisé
JP2015127118A (ja) * 2013-12-27 2015-07-09 新日鉄住金化学株式会社 金属張積層体及び回路基板
JP2015193117A (ja) * 2014-03-31 2015-11-05 新日鉄住金化学株式会社 金属張積層体及び回路基板
JP2015199328A (ja) * 2014-03-31 2015-11-12 新日鉄住金化学株式会社 金属張積層体、回路基板及びポリイミド
WO2016159060A1 (fr) * 2015-03-31 2016-10-06 株式会社カネカ Film adhésif multicouche et stratifié revëtu de métal flexible
JP2017132898A (ja) * 2016-01-27 2017-08-03 株式会社有沢製作所 ポリイミド樹脂前駆体
JP2017136755A (ja) * 2016-02-03 2017-08-10 東レ・デュポン株式会社 低誘電多層ポリイミドフィルム
WO2018061727A1 (fr) * 2016-09-29 2018-04-05 新日鉄住金化学株式会社 Film polyimide, stratifié cuivré, et carte de circuit imprimé
WO2018079710A1 (fr) * 2016-10-31 2018-05-03 宇部興産株式会社 Film polyimide pour stratification métallique et stratifié polyimide métal utilisant celui-ci

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014208644A1 (fr) * 2013-06-28 2014-12-31 新日鉄住金化学株式会社 Polyimide, film de résine et stratifié métallisé
JP2015127118A (ja) * 2013-12-27 2015-07-09 新日鉄住金化学株式会社 金属張積層体及び回路基板
JP2015193117A (ja) * 2014-03-31 2015-11-05 新日鉄住金化学株式会社 金属張積層体及び回路基板
JP2015199328A (ja) * 2014-03-31 2015-11-12 新日鉄住金化学株式会社 金属張積層体、回路基板及びポリイミド
WO2016159060A1 (fr) * 2015-03-31 2016-10-06 株式会社カネカ Film adhésif multicouche et stratifié revëtu de métal flexible
JP2017132898A (ja) * 2016-01-27 2017-08-03 株式会社有沢製作所 ポリイミド樹脂前駆体
JP2017136755A (ja) * 2016-02-03 2017-08-10 東レ・デュポン株式会社 低誘電多層ポリイミドフィルム
WO2018061727A1 (fr) * 2016-09-29 2018-04-05 新日鉄住金化学株式会社 Film polyimide, stratifié cuivré, et carte de circuit imprimé
WO2018079710A1 (fr) * 2016-10-31 2018-05-03 宇部興産株式会社 Film polyimide pour stratification métallique et stratifié polyimide métal utilisant celui-ci

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210364919A1 (en) * 2019-01-23 2021-11-25 Microcosm Technology Co., Ltd. Photosensitive resin composition and application thereof
CN113260676A (zh) * 2019-12-13 2021-08-13 株式会社斗山 具有优异的耐候性的聚酰亚胺膜
CN113260676B (zh) * 2019-12-13 2025-02-07 株式会社斗山 具有优异的耐候性的聚酰亚胺膜
CN116144022A (zh) * 2023-02-27 2023-05-23 中国科学院山西煤炭化学研究所 一种聚酰亚胺聚合物、薄膜、制备方法及应用

Also Published As

Publication number Publication date
JP2018165346A (ja) 2018-10-25
TW201840648A (zh) 2018-11-16

Similar Documents

Publication Publication Date Title
WO2018181436A1 (fr) Film de polyimide
CN107011512B (zh) 聚酰亚胺树脂前体
TWI634986B (zh) 覆銅積層板、印刷配線板及其使用方法
JP7429519B2 (ja) 多層ポリイミドフィルム
JP6767759B2 (ja) ポリイミド、樹脂フィルム及び金属張積層板
JP7336031B2 (ja) 低誘電ポリイミドフィルムおよびその製造方法
JP7122162B2 (ja) 熱可塑性ポリイミドフィルム、多層ポリイミドフィルム、およびフレキシブル金属張積層板
JP6403460B2 (ja) 金属張積層体、回路基板及びポリイミド
JP2016188298A (ja) ポリイミド、樹脂フィルム、金属張積層体及び回路基板
JP2018145303A (ja) 多層ポリイミドフィルム
JP2017136755A (ja) 低誘電多層ポリイミドフィルム
KR20230117670A (ko) 금속 피복 적층판 및 회로 기판
JP2015193117A (ja) 金属張積層体及び回路基板
JP6014406B2 (ja) 高周波回路基板用カバーレイの取り付け方法及びそのカバーレイ
JP2020139039A (ja) ポリイミドフィルム
CN112175183B (zh) 聚酰亚胺膜
JP7525089B2 (ja) 多層ポリイミドフィルム
JP2020015237A (ja) 金属張積層板の製造方法及び回路基板の製造方法
JP7336030B2 (ja) 高接着低誘電ポリイミドフィルムおよびその製造方法
JP2023121512A (ja) 非熱可塑性ポリイミドフィルム、複層ポリイミドフィルム、及び金属張積層板
JP4615401B2 (ja) 積層体
TWI899086B (zh) 聚醯亞胺薄膜及其製造方法
JP7438790B2 (ja) 接着剤付きポリイミドフィルムおよびフラットケーブル
JP6767751B2 (ja) ポリアミド酸、ポリイミド、樹脂フィルム及び金属張積層板
JP2023146680A (ja) ポリアミド酸、ポリイミド、ポリイミドフィルムならびに多層フィルム

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18775493

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18775493

Country of ref document: EP

Kind code of ref document: A1