WO2018061727A1 - ポリイミドフィルム、銅張積層板及び回路基板 - Google Patents

ポリイミドフィルム、銅張積層板及び回路基板 Download PDF

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Publication number
WO2018061727A1
WO2018061727A1 PCT/JP2017/032642 JP2017032642W WO2018061727A1 WO 2018061727 A1 WO2018061727 A1 WO 2018061727A1 JP 2017032642 W JP2017032642 W JP 2017032642W WO 2018061727 A1 WO2018061727 A1 WO 2018061727A1
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Prior art keywords
parts
weight
residue
diamine
polyimide
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PCT/JP2017/032642
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English (en)
French (fr)
Japanese (ja)
Inventor
智典 安藤
哲平 西山
芳樹 須藤
亮 森
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新日鉄住金化学株式会社
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Application filed by 新日鉄住金化学株式会社 filed Critical 新日鉄住金化学株式会社
Priority to CN202210504040.4A priority Critical patent/CN114716707A/zh
Priority to CN201780059180.2A priority patent/CN109789689A/zh
Priority to JP2018542342A priority patent/JP6936239B2/ja
Priority to KR1020197008643A priority patent/KR102290631B1/ko
Publication of WO2018061727A1 publication Critical patent/WO2018061727A1/ja

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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
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—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
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • B32B2307/00—Properties of the layers or laminate
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    • B32B2307/732—Dimensional properties
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • 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
    • B32B2457/00—Electrical equipment
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—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
    • H05K1/0393—Flexible materials
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0133—Elastomeric or compliant polymer
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide

Definitions

  • the present invention relates to a polyimide film, a copper clad laminate, and a circuit board.
  • FPCs flexible printed wiring boards
  • HDDs high-density digital versatile disks
  • DVDs digital versatile disks
  • cables and connectors parts such as cables and connectors. I am doing.
  • Patent Document 1 In order to improve heat resistance and adhesiveness, a metal-clad laminate using polyimide as an insulating layer has been proposed (Patent Document 1).
  • Patent Document 1 it is known that the dielectric constant is generally lowered by using an aliphatic monomer as a polymer material, and an aliphatic (chain) tetracarboxylic dianhydride is used. Since the heat resistance of the polyimide obtained in this way is extremely low, it cannot be used for processing such as soldering, and there is a problem in practical use. However, when alicyclic tetracarboxylic dianhydride is used, it becomes a chain-like one It is said that polyimide having improved heat resistance can be obtained.
  • the polyimide film formed from such a polyimide has a dielectric constant of 10 or less at 10 GHz, the dielectric loss tangent exceeds 0.01, and the dielectric properties have not been sufficient.
  • many polyimides using the above-mentioned aliphatic monomers have a large linear thermal expansion coefficient, and there are problems that the dimensional change rate of the polyimide film is large and flame retardancy is reduced.
  • the object of the present invention is to have high dimensional stability and low hygroscopicity, and by reducing the dielectric loss tangent of the insulating layer, it is possible to reduce transmission loss and to be suitably used for a high-frequency circuit board. It is providing the polyimide film which can be performed.
  • the inventors of the present invention have made a non-thermoplastic polyimide layer mainly responsible for controlling the rate of dimensional change in the circuit board, and further, if necessary, thermoplastic polyimide responsible for adhesion to the copper foil.
  • the layer by selecting the monomer that will be the raw material of the polyimide, ensuring the dimensional stability required for the circuit board, and reducing the moisture absorption and lowering the dielectric loss tangent by controlling the ordering (crystallinity) of the polyimide As a result, the present invention has been completed.
  • the polyimide film of the 1st viewpoint of this invention is a polyimide film which has a thermoplastic polyimide layer containing a thermoplastic polyimide in at least one of the non-thermoplastic polyimide layers containing a non-thermoplastic polyimide.
  • the polyimide film according to the first aspect of the present invention is characterized by satisfying the following conditions (ai) to (a-iv).
  • the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer contains a tetracarboxylic acid residue and a diamine residue,
  • Tetracarboxylic acid residue BPDA residue
  • BPDA 4,4′-biphenyltetracarboxylic dianhydride
  • 1,4-phenylenebis (trimellitic acid monoester) dianhydride At least one tetracarboxylic acid residue (TAHQ residue) derived from the product (TAHQ) and tetracarboxylic acid residue (PMDA residue) derived from pyromellitic dianhydride (PMDA) and a few
  • the total of at least one tetracarboxylic acid residue (NTCDA residue) derived from 1,6,7-naphthalenetetracarboxylic dianhydride (NTCDA) is 80 parts by mole or more, Molar ratio
  • thermoplastic polyimide constituting the thermoplastic polyimide layer contains a tetracarboxylic acid residue and a diamine residue, and relative to 100 mole parts of the diamine residue,
  • the diamine residue derived from at least one diamine compound selected from the diamine compounds represented by the following general formulas (B1) to (B7) is 70 mol parts or more.
  • the coefficient of thermal expansion is within the range of 10 ppm / K to 30 ppm / K.
  • Df dielectric loss tangent at 10 GHz is 0.004 or less.
  • R 1 independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms
  • the linking group A is independently —O—, —S—, —CO
  • a divalent group selected from —, —SO—, —SO 2 —, —COO—, —CH 2 —, —C (CH 3 ) 2 —, —NH— or —CONH—
  • n 1 is independent Represents an integer of 0 to 4.
  • n 1 is independent
  • those that overlap with the formula (B2) are excluded, and in the formula (B5), those that overlap with the formula (B4) are excluded.
  • the polyimide film of the 1st viewpoint of this invention is a diamine compound represented with the following general formula (A1) with respect to 100 mol part of the diamine residue in the non-thermoplastic polyimide which comprises the said non-thermoplastic polyimide layer.
  • the diamine residue derived from may be 80 mol parts or more.
  • the linking group X represents a single bond or a divalent group selected from —COO—
  • Y independently represents hydrogen, a monovalent hydrocarbon group having 1 to 3 carbon atoms, or an alkoxy group.
  • N represents an integer of 0 to 2
  • p and q independently represent an integer of 0 to 4.
  • the polyimide film of the first aspect of the present invention is a diamine represented by the general formulas (B1) to (B7) with respect to 100 mole parts of the diamine residue in the thermoplastic polyimide constituting the thermoplastic polyimide.
  • a diamine residue derived from the diamine compound represented by the general formula (A1), wherein the diamine residue derived from at least one diamine compound selected from the compounds is in the range of 70 to 99 mol parts May be in the range of 1 to 30 mole parts.
  • the polyimide film of the 2nd viewpoint of this invention is a polyimide film which has a thermoplastic polyimide layer containing a thermoplastic polyimide in at least one of the non-thermoplastic polyimide layers containing a non-thermoplastic polyimide.
  • the polyimide film according to the second aspect of the present invention is characterized by satisfying the following conditions (bi) to (b-iv).
  • the coefficient of thermal expansion is in the range of 10 ppm / K to 30 ppm / K.
  • the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer contains a tetracarboxylic acid residue and a diamine residue, For 100 mole parts of the tetracarboxylic acid residue, At least one tetracarboxylic dianhydride selected from 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 1,4-phenylenebis (trimellitic acid monoester) dianhydride (TAHQ)
  • BPDA 4,4′-biphenyltetracarboxylic dianhydride
  • TAHQ 1,4-phenylenebis (trimellitic acid monoester) dianhydride
  • the tetracarboxylic acid residue derived from the anhydride is in the range of 30 to 60 parts by mole
  • the tetracarboxylic acid residue derived from pyromellitic dianhydride (PMDA) is in the range of 40 to 70 parts by
  • the diamine residue derived from the diamine compound represented by the following general formula (A1) is 80 parts by mole or more.
  • thermoplastic polyimide composing the thermoplastic polyimide layer contains a tetracarboxylic acid residue and a diamine residue, and with respect to 100 mole parts of the diamine residue,
  • the diamine residue derived from at least one diamine compound selected from the diamine compounds represented by the following general formulas (B1) to (B7) is in the range of 70 to 99 parts by mole,
  • the diamine residue derived from the diamine compound represented by the following general formula (A1) is in the range of 1 to 30 mol parts.
  • the linking group X represents a single bond or a divalent group selected from —COO—
  • Y independently represents hydrogen, a monovalent hydrocarbon group having 1 to 3 carbon atoms, or an alkoxy group.
  • N represents an integer of 0 to 2
  • p and q independently represent an integer of 0 to 4.
  • R 1 independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms
  • the linking group A is independently —O—, —S—, —CO
  • a divalent group selected from —, —SO—, —SO 2 —, —COO—, —CH 2 —, —C (CH 3 ) 2 —, —NH— or —CONH—
  • n 1 is independent Represents an integer of 0 to 4.
  • n 1 is independent
  • those that overlap with the formula (B2) are excluded, and in the formula (B5), those that overlap with the formula (B4) are excluded.
  • the non-thermoplastic polyimide and the thermoplastic polyimide may each have an imide group concentration of 33% by weight or less.
  • a polyimide film according to a third aspect of the present invention is a polyimide film having at least one non-thermoplastic polyimide layer, and satisfies the following conditions (ci) to (c-iii): .
  • the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer contains a tetracarboxylic acid residue and a diamine residue, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 1,4-phenylenebis (trimellitic acid monoester) dianhydride per 100 mole parts of the tetracarboxylic acid residue Of tetracarboxylic acid residues derived from at least one of the products (TAHQ) within a range of 30 to 60 mole parts, pyromellitic dianhydride (PMDA) and 2,3,6,7-naphthalenetetracarboxylic acid Containing tetracarboxylic
  • the linking group X represents a single bond or a divalent group selected from —COO—
  • Y independently represents hydrogen, a monovalent hydrocarbon having 1 to 3 carbon atoms, or an alkoxy group.
  • N represents an integer of 0 to 2
  • p and q independently represent an integer of 0 to 4.
  • the polyimide film of the third aspect of the present invention has 2 diamine residues derived from diamine compounds represented by the following general formulas (C1) to (C4) with respect to 100 mol parts of the diamine residues. It may be contained within a range of ⁇ 15 mol parts.
  • R 2 independently represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group or an alkylthio group, and the linking group A ′ is independently —O— or —SO 2.
  • 2 represents a divalent group selected from —CH 2 — or —C (CH 3 ) 2 —, and the linking group X1 is independently —CH 2 —, —O—CH 2 —O—, —O—C.
  • n 3 independently represents an integer of 1 to 4
  • the copper clad laminate according to the first, second or third aspect of the present invention comprises an insulating layer and a copper foil on at least one surface of the insulating layer, and the insulating layer is a polyimide according to any one of the above. It is characterized by including a film.
  • the circuit board according to the first, second or third aspect of the present invention is obtained by processing the copper foil of the copper-clad laminate into a wiring.
  • the polyimide film according to the first to third aspects of the present invention can achieve both of ensuring physical properties as a base resin layer and lowering the moisture absorption rate by forming a non-thermoplastic polyimide layer using a specific acid anhydride as a raw material. And low dielectric loss tangent.
  • the polyimide film of the first or second aspect of the present invention enables low moisture absorption and low dielectric loss tangent by forming a thermoplastic polyimide layer from a thermoplastic polyimide into which a specific diamine compound is introduced. did.
  • the multilayer film which combined both resin layers has a low hygroscopic property and a dielectric loss tangent, and is excellent also in the dimensional stability after thermocompression bonding of copper foil.
  • the polyimide film of the present invention and the copper-clad laminate using the same as an FPC material, it is possible to improve the reliability and yield in the circuit board, for example, transmitting a high frequency signal of 10 GHz or more.
  • Application to a circuit board or the like is also possible.
  • the polyimide film of the first embodiment of the present invention has a thermoplastic polyimide layer containing a thermoplastic polyimide on at least one of the non-thermoplastic polyimide layers containing a non-thermoplastic polyimide, and the above conditions (ai) to (a -iv).
  • the polyimide film of the second embodiment of the present invention has a thermoplastic polyimide layer containing a thermoplastic polyimide on at least one of the non-thermoplastic polyimide layers containing a non-thermoplastic polyimide, and the above conditions (bi) to (B-iv) is satisfied.
  • the thermoplastic polyimide layer is provided on one side or both sides of the non-thermoplastic polyimide layer.
  • the copper foil can be laminated on the surface of the thermoplastic polyimide layer.
  • one thermoplastic polyimide layer may satisfy the above condition (a-ii) or condition (b-iv). Both preferably satisfy the above condition (a-ii) or condition (b-iv).
  • the polyimide film of the third embodiment of the present invention has at least one non-thermoplastic polyimide layer made of non-thermoplastic polyimide and satisfies the above conditions (ci) to (c-iii). It is.
  • Non-thermoplastic polyimide generally means a polyimide that does not soften or show adhesiveness even when heated. In the present invention, it is measured using a dynamic viscoelasticity measuring device (DMA) at 30 ° C.
  • the storage elastic modulus is 1.0 ⁇ 10 9 Pa or higher, and the storage elastic modulus at 280 ° C. is 3.0 ⁇ 10 8 Pa or higher.
  • the “thermoplastic polyimide” is generally a polyimide whose glass transition temperature (Tg) can be clearly confirmed.
  • the storage elastic modulus at 30 ° C. measured by DMA is 1.0.
  • X10 9 Pa or higher which means a polyimide having a storage elastic modulus at 280 ° C. of less than 3.0 ⁇ 10 8 Pa.
  • the resin component of the non-thermoplastic polyimide layer is preferably made of non-thermoplastic polyimide.
  • the thermoplastic resin The resin component of the polyimide layer is preferably made of thermoplastic polyimide.
  • the non-thermoplastic polyimide layer constitutes a low thermal expansion polyimide layer
  • the thermoplastic polyimide layer constitutes a high thermal expansion polyimide layer.
  • the low thermal expansion polyimide layer is preferably a polyimide layer having a coefficient of thermal expansion (CTE) in the range of 1 ppm / K to 25 ppm / K, more preferably in the range of 3 ppm / K to 25 ppm / K.
  • CTE coefficient of thermal expansion
  • the high thermal expansion polyimide layer preferably has a CTE of 35 ppm / K or more, more preferably in the range of 35 ppm / K or more and 80 ppm / K or less, and still more preferably in the range of 35 ppm / K or more and 70 ppm / K or less.
  • a polyimide layer can be made into the polyimide layer which has desired CTE by changing suitably the combination of the raw material to be used, thickness, and drying / curing conditions.
  • a polyimide can be produced by reacting a tetracarboxylic dianhydride and a diamine compound in a solvent to form a polyamic acid and then ring-closing with heating.
  • a precursor of polyimide is obtained by dissolving a tetracarboxylic dianhydride and a diamine compound in an organic solvent in approximately equimolar amounts and stirring for 30 minutes to 24 hours at a temperature within a range of 0 to 100 ° C.
  • a polyamic acid is obtained.
  • the reaction components are dissolved so that the precursor to be produced is in the range of 5 to 30% by weight, preferably in the range of 10 to 20% by weight, in the organic solvent.
  • organic solvent used in the polymerization reaction examples include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N, N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), 2 -Butanone, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, dioxane, tetrahydrofuran, diglyme, triglyme, cresol and the like. Two or more of these solvents can be used in combination, and further, aromatic hydrocarbons such as xylene and toluene can be used in combination.
  • the amount of such organic solvent used is not particularly limited, but it should be adjusted so that the concentration of the polyamic acid solution obtained by the polymerization reaction is about 5 to 30% by weight. Is preferred.
  • the synthesized polyamic acid is usually advantageously used as a reaction solvent solution, but can be concentrated, diluted or substituted with another organic solvent as necessary. Moreover, since polyamic acid is generally excellent in solvent solubility, it is advantageously used.
  • the viscosity of the polyamic acid solution is preferably in the range of 500 cps to 100,000 cps. If it is out of this range, defects such as uneven thickness and streaks are likely to occur in the film during coating by a coater or the like.
  • the method for imidizing the polyamic acid is not particularly limited, and for example, heat treatment such as heating in the above-mentioned solvent under a temperature condition in the range of 80 to 400 ° C. for 1 to 24 hours is suitably employed.
  • Polyimide is formed by imidizing the above polyamic acid, and is produced by reacting a specific acid anhydride with a diamine compound. Therefore, by explaining the acid anhydride and diamine compound, the first, second Or the specific example of the non-thermoplastic polyimide of 3rd Embodiment and the thermoplastic polyimide of 1st or 2nd Embodiment is understood.
  • the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer contains a tetracarboxylic acid residue and a diamine residue.
  • the tetracarboxylic acid residue means a tetravalent group derived from tetracarboxylic dianhydride
  • the diamine residue means a divalent group derived from a diamine compound. Represents that.
  • the polyimide film of the first, second or third embodiment has an aromatic tetracarboxylic acid residue derived from an aromatic tetracarboxylic dianhydride and an aromatic diamine residue derived from an aromatic diamine. It is preferable to include.
  • the tetracarboxylic acid residue contained in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer may be 3,3 ′, 4,4′-biphenyltetracarboxylic Tetracarboxylic acid residues derived from at least one of acid dianhydride (BPDA) and 1,4-phenylenebis (trimellitic acid monoester) dianhydride (TAHQ) and pyromellitic dianhydride (PMDA) And a tetracarboxylic acid residue derived from at least one of 2,3,6,7-naphthalenetetracarboxylic dianhydride (NTCDA).
  • BPDA acid dianhydride
  • TAHQ 1,4-phenylenebis (trimellitic acid monoester) dianhydride
  • PMDA pyromellitic dianhydride
  • NTCDA 2,3,6,7-naphthalenetetracarboxylic dianhydride
  • a tetracarboxylic acid residue derived from BPDA (hereinafter also referred to as “BPDA residue”) and a tetracarboxylic acid residue derived from TAHQ (hereinafter also referred to as “TAHQ residue”) are polymer ordered. It is easy to form a structure, and the loss tangent and hygroscopicity can be reduced by suppressing the movement of molecules.
  • the BPDA residue can give the self-supporting property of the gel film as the polyamic acid of the polyimide precursor, but increases the CTE after imidization and lowers the glass transition temperature to lower the heat resistance. Become a trend.
  • the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer in the polyimide film of the first, second or third embodiment is based on 100 mol parts of the tetracarboxylic acid residue.
  • the total of the BPDA residue and the TAHQ residue is preferably controlled to be contained in the range of 30 to 60 parts by mole, more preferably in the range of 40 to 50 parts by mole. If the total of the BPDA residue and the TAHQ residue is less than 30 parts by mole, the formation of the ordered structure of the polymer becomes insufficient, the hygroscopic resistance is lowered, and the reduction of the dielectric loss tangent is insufficient. When it exceeds, there exists a possibility that heat resistance may fall besides the increase in the amount of change of CTE and in-plane retardation (RO).
  • RO in-plane retardation
  • a tetracarboxylic acid residue derived from pyromellitic dianhydride (hereinafter also referred to as “PMDA residue”) and a tetracarboxylic acid dianhydride derived from 2,3,6,7-naphthalenetetracarboxylic dianhydride.
  • Carboxylic acid residues (hereinafter also referred to as “NTCDA residues”) have rigidity, so that they increase the in-plane orientation, keep CTE low, and control RO and glass transition temperature. responsible residue.
  • the molecular weight of the PMDA residue is small, if the amount is too large, the imide group concentration of the polymer is increased, the polar group is increased and the hygroscopicity is increased, and the moisture content in the molecular chain is increased.
  • the dielectric loss tangent increases due to the influence.
  • the NTCDA residue tends to be brittle due to a highly rigid naphthalene skeleton, and tends to increase the elastic modulus.
  • the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer is a PMDA residue and an NTCDA residue with respect to 100 mole parts of the tetracarboxylic acid residue. Is preferably in the range of 40 to 70 mole parts, more preferably in the range of 50 to 60 mole parts, and still more preferably in the range of 50 to 55 mole parts. If the total of PMDA residues and NTCDA residues is less than 40 parts by mole, CTE may increase or heat resistance may decrease.
  • the imide group concentration of the polymer increases, There is a risk that low hygroscopicity is impaired due to an increase in the group, and that the dielectric loss tangent may increase or the film becomes brittle and the self-supporting property of the film is lowered.
  • the total of at least one of the BPDA residue and the TAHQ residue and at least one of the PMDA residue NTCDA residue is a tetracarboxylic acid. It is 80 mol parts or more, preferably 90 mol parts or more with respect to 100 mol parts of the residue.
  • a molar ratio ⁇ (BPDA) of at least one BPDA residue and TAHQ residue and at least one PMDA residue and NTCDA residue is defined.
  • the formation of an ordered structure of CTE and polymer is controlled.
  • the control of the in-plane orientation of the molecules in the polyimide is greater than that of other general acid anhydride components. This is possible and has the effect of suppressing the coefficient of thermal expansion (CTE) and improving the glass transition temperature (Tg).
  • CTE coefficient of thermal expansion
  • Tg glass transition temperature
  • BPDA and TAHQ have a higher molecular weight than PMDA, the imide group concentration is reduced by increasing the charging ratio, and this is effective in reducing dielectric loss tangent and moisture absorption.
  • the preparation ratio of BPDA and TAHQ is increased, the in-plane orientation of molecules in the polyimide is lowered, leading to an increase in CTE.
  • the total amount of PMDA and NTCDA is in the range of 40 to 70 mol parts, preferably in the range of 50 to 60 mol parts, with respect to 100 mol parts of the total acid anhydride component of the raw material. More preferably, it is in the range of 50 to 55 mole parts.
  • the total charge amount of PMDA and NTCDA is less than 40 mol parts with respect to 100 mol parts of the total acid anhydride component of the raw material, the in-plane orientation of the molecule is lowered, making it difficult to reduce CTE, and Tg The heat resistance and dimensional stability of the film at the time of heating due to the decrease in the thickness are reduced.
  • the total amount of PMDA and NTCDA exceeds 70 mol parts, the moisture absorption rate tends to deteriorate due to an increase in the imide group concentration, or the elastic modulus tends to increase.
  • BPDA and TAHQ are effective in suppressing molecular motion and lowering the dielectric loss tangent and lowering the moisture absorption rate by lowering the imide group concentration, but increase the CTE as a polyimide film after imidization.
  • the total charge amount of BPDA and TAHQ is in the range of 30 to 60 mol parts, preferably in the range of 40 to 50 mol parts, with respect to 100 mol parts of the total acid anhydride component of the raw material. More preferably, it is within the range of 40 to 45 mole parts.
  • Examples of tetracarboxylic acid residues other than the BPDA residue, TAHQ residue, PMDA residue, and NTCDA residue contained in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer include, for example, 3, 3 ′, 4 , 4'-Diphenylsulfonetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 2,3 ', 3,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3 ' -2,3,3 ', 4'- or 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 2,3 ', 3,4'-diphenyl ether tetracarboxylic dianhydride, bis (2,3-Dicarboxyphenyl) ether dianhydride, 3,3 ′′, 4,4 ′′-, 2,3,3 ′′, 4 ′′-or 2,2 ′′
  • the diamine residue contained in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer is derived from a diamine compound represented by the general formula (A1). A diamine residue is preferred.
  • the linking group X represents a single bond or a divalent group selected from —COO—
  • Y independently represents hydrogen, a monovalent hydrocarbon group having 1 to 3 carbon atoms, or an alkoxy group.
  • N represents an integer of 0 to 2
  • p and q independently represent an integer of 0 to 4.
  • “independently” means that in the above formula (A1), the plurality of linking groups A, the plurality of substituents Y, and the integers p and q may be the same or different.
  • the hydrogen atoms in the two terminal amino groups may be substituted. For example, —NR 3 R 4 (wherein R 3 and R 4 are independently alkyl groups, etc. Meaning any substituent).
  • the diamine compound represented by the general formula (A1) (hereinafter sometimes referred to as “diamine (A1)”) is an aromatic diamine having two benzene rings. Since the diamine (A1) has a rigid structure, it has an action of imparting an ordered structure to the entire polymer. Therefore, a low gas permeability and low hygroscopic polyimide can be obtained, and moisture inside the molecular chain can be reduced, so that the dielectric loss tangent can be lowered.
  • the linking group X is preferably a single bond.
  • diamine (A1) examples include 1,4-diaminobenzene (p-PDA; paraphenylenediamine), 2,2′-dimethyl-4,4′-diaminobiphenyl (m-TB), and 2,2′-.
  • examples thereof include n-propyl-4,4′-diaminobiphenyl (m-NPB) and 4-aminophenyl-4′-aminobenzoate (APAB).
  • the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer of the first or second embodiment preferably has a diamine residue derived from the diamine (A1) with respect to 100 mole parts of the diamine residue. 80 mol parts or more, more preferably 85 mol parts or more.
  • the diamine (A1) in an amount within the above range, the rigid structure derived from the monomer facilitates the formation of an ordered structure throughout the polymer, has low gas permeability, low hygroscopicity, and low dielectric loss tangent. Non-thermoplastic polyimide is easily obtained.
  • the diamine residue derived from the diamine (A1) is from 80 to 85 parts by mole with respect to 100 parts by mole of the diamine residue in the non-thermoplastic polyimide.
  • 1,4-diaminobenzene is preferably used as the diamine (A1) from the viewpoint of being more rigid and having an excellent in-plane orientation.
  • the other diamine residue contained in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer is, for example, 2,2-bis- [4- (3-aminophenoxy ) Phenyl] propane, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) biphenyl, bis [1- (3-aminophenoxy)] biphenyl, bis [4- (3 -Aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy)] benzophenone, 9,9-bis [4- (3-aminophenoxy) phenyl ] Fluorene, 2,2-bis- [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis- [4- (3-aminophenoxy) phen
  • the diamine (A1) is added to 100 mol parts of the total diamine component of the raw material as defined in the above condition (ci). On the other hand, it is 70 mol parts or more, for example, in the range of 70 to 90 mol parts, preferably in the range of 80 to 90 mol parts. On the other hand, when the amount of diamine (A1) charged exceeds 90 mol parts, the elongation of the film may decrease.
  • the non-thermoplastic polyimide used in the third embodiment is at least one aromatic selected from the group consisting of aromatic diamines represented by the general formulas (C1) to (C4) as a diamine component of the raw material. Preference is given to using diamines. Since the diamines (C1) to (C4) have bulky substituents and flexible portions, flexibility can be imparted to the polyimide. Further, since the diamines (C1) to (C4) can improve gas permeability, they have an effect of suppressing foaming during the production of the multilayer film and the metal-clad laminate.
  • one or more aromatic diamines selected from diamines (C1) to (C4) may be used within a range of 2 to 15 parts by mole with respect to 100 parts by mole of the total diamine component. preferable.
  • the amount of diamine (C1) to (C4) is less than 2 mole parts, foaming may occur when a multilayer film and a metal-clad laminate are produced.
  • the amount of diamine (C1) to (C4) charged exceeds 15 parts by mole, the molecular orientation is lowered and it is difficult to reduce the CTE.
  • R 2 independently represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group or an alkylthio group
  • the linking group A ′ is independently —O—, —SO A divalent group selected from 2 —, —CH 2 — or —C (CH 3 ) 2 —, preferably a divalent group selected from —O—, —CH 2 — or —C (CH 3 ) 2 —.
  • the linking group X1 is independently —CH 2 —, —O—CH 2 —O—, —O—C 2 H 4 —O—, —O—C 3 H 6 —O—, —O—C 4.
  • n 3 independently represents an integer of 1 to 4
  • “independently” refers to a plurality of linking groups A ′, a plurality of linking groups X1, a plurality of substituents R in one or more of the above formulas (C1) to (C4). It means that two or a plurality of n 3 and n 4 may be the same or different.
  • hydrogen atoms in the two terminal amino groups may be substituted.
  • —NR 3 R 4 wherein R 3 and R 4 are independently Meaning an arbitrary substituent such as an alkyl group).
  • Examples of the aromatic diamine represented by the general formula (C1) include 2,6-diamino-3,5-diethyltoluene and 2,4-diamino-3,5-diethyltoluene.
  • Examples of the aromatic diamine represented by the general formula (C2) include 2,4-diamino-3,3′-diethyl-5,5′-dimethyldiphenylmethane and bis (4-amino-3-ethyl-5- And methylphenyl) methane.
  • Examples of the aromatic diamine represented by the general formula (C3) include 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene and 1,4-bis [2- (4-amino). Phenyl) -2-propyl] benzene, 1,4-bis (4-aminophenoxy) -2,5-di-tert-butylbenzene, and the like.
  • Examples of the aromatic diamine represented by the general formula (C4) include 2,2-bis [4- (4-aminophenoxy) phenyl] propane.
  • the non-thermoplastic polyimide constituting the polyimide film of the third embodiment has 70 mol parts or more of residues derived from diamine (A1) with respect to 100 mol parts of diamine residues,
  • the residue is preferably controlled so as to contain a residue derived from diamines (C1) to (C4) within a range of 2 to 15 mol parts within a range of 70 to 90 mol parts.
  • other diamines that can be used as a raw material for polyimide include, for example, 2,2-bis- [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4 -(4-Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2-trifluoro-4-aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (4-aminophenoxy) 2 , 3,6-trimethyl-benzene, 1,4-bis (4-aminophenoxymethyl) propane, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) methane, 1,4-bis (4-aminophenoxy) ethane, 1,4-bis (4-aminophenoxy) propane 1,
  • BPDA, TAHQ, PMDA, and NTCDA are used as the acid anhydride component that is a raw material for polyimide
  • diamine (A1) and diamines (C1) to (C4) are used as the diamine components in the above molar ratios, respectively.
  • the polyimide film of the third embodiment has a low dielectric constant, a low dielectric loss tangent, and a low hygroscopicity, so that it is preferable as a base resin in an insulating resin layer of a copper clad laminate that is a raw material for FPC, for example. It is.
  • aromatic tetracarboxylic acid anhydride and aromatic diamine are used as the raw material for polyimide, the problem of dimensional change due to heating is less likely to occur, and it has flame retardancy. There is no need to blend. Therefore, by using the polyimide film of the third embodiment and the copper-clad laminate using the polyimide film, it is possible to improve the reliability and yield of a circuit board such as an FPC.
  • non-thermoplastic polyimide of the first, second or third embodiment when the types of the tetracarboxylic acid residue and diamine residue, or two or more kinds of tetracarboxylic acid residues or diamine residues are applied By selecting the respective molar ratios, the thermal expansion coefficient, storage elastic modulus, tensile elastic modulus and the like can be controlled.
  • a non-thermoplastic polyimide when it has a plurality of polyimide structural units, it may exist as a block or randomly, but it is random from the viewpoint of suppressing variation in in-plane retardation (RO). It is preferable that it exists in.
  • the tetracarboxylic acid residue and the diamine residue contained in the non-thermoplastic polyimide are both aromatic groups, so that the dimensions of the polyimide film in a high temperature environment are as follows. This is preferable because accuracy can be improved and the amount of change in in-plane retardation (RO) can be reduced.
  • concentration of a non-thermoplastic polyimide is 33 weight% or less.
  • the “imide group concentration” means a value obtained by dividing the molecular weight of the imide group (— (CO) 2 —N—) in the polyimide by the molecular weight of the entire polyimide structure.
  • the imide group concentration exceeds 33% by weight, the molecular weight of the resin itself is reduced, and the low hygroscopicity is also deteriorated due to an increase in polar groups.
  • the weight average molecular weight of the non-thermoplastic polyimide is preferably in the range of, for example, 10,000 to 400,000, more preferably in the range of 50,000 to 350,000. preferable.
  • the weight average molecular weight is less than 10,000, the strength of the film tends to decrease and the film tends to become brittle.
  • the weight average molecular weight exceeds 400,000, the viscosity increases excessively, and defects such as film thickness unevenness and streaks tend to occur during the coating operation.
  • thermoplastic polyimide constituting the thermoplastic polyimide layer contains a tetracarboxylic acid residue and a diamine residue, and is from an aromatic tetracarboxylic dianhydride. It preferably contains an aromatic tetracarboxylic acid residue derived from and an aromatic diamine residue derived from an aromatic diamine.
  • thermoplastic polyimide constituting the thermoplastic polyimide layer
  • tetracarboxylic acid residue used in the thermoplastic polyimide constituting the thermoplastic polyimide layer should be the same as the tetracarboxylic acid residue exemplified in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer. Can do.
  • a diamine residue derived from a diamine compound represented by the general formulas (B1) to (B7) is preferable.
  • R 1 independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms
  • the linking group A is independently —O—, —S—, —CO—.
  • n 1 is independently An integer from 0 to 4 is shown.
  • those that overlap with the formula (B2) are excluded, and in the formula (B5), those that overlap with the formula (B4) are excluded.
  • the diamine represented by the formula (B1) (hereinafter sometimes referred to as “diamine (B1)”) is an aromatic diamine having two benzene rings.
  • This diamine (B1) has high flexibility because the degree of freedom of the polyimide molecular chain is increased because the amino group directly connected to at least one benzene ring and the divalent linking group A are in the meta position. It is thought that it contributes to the improvement of the flexibility of the polyimide molecular chain. Therefore, the thermoplasticity of a polyimide increases by using diamine (B1).
  • the linking group A is preferably —O—, —CH 2 —, —C (CH 3 ) 2 —, —CO—, —SO 2 —, —S—.
  • diamine (B1) examples include 3,3′-diaminodiphenylmethane, 3,3′-diaminodiphenylpropane, 3,3′-diaminodiphenyl sulfide, 3,3′-diaminodiphenylsulfone, and 3,3′-diamino.
  • the diamine represented by the formula (B2) (hereinafter sometimes referred to as “diamine (B2)”) is an aromatic diamine having three benzene rings.
  • This diamine (B2) has high flexibility because the degree of freedom of the polyimide molecular chain is increased because the amino group directly connected to at least one benzene ring and the divalent linking group A are in the meta position. It is thought that it contributes to the improvement of the flexibility of the polyimide molecular chain. Therefore, the use of diamine (B2) increases the thermoplasticity of the polyimide.
  • the linking group A is preferably —O—.
  • Examples of the diamine (B2) include 1,4-bis (3-aminophenoxy) benzene, 3- [4- (4-aminophenoxy) phenoxy] benzenamine, 3- [3- (4-aminophenoxy) phenoxy] Examples thereof include benzeneamine.
  • the diamine represented by the formula (B3) (hereinafter sometimes referred to as “diamine (B3)”) is an aromatic diamine having three benzene rings.
  • This diamine (B3) has high flexibility because the degree of freedom of the polyimide molecular chain is increased because two divalent linking groups A directly connected to one benzene ring are in the meta position. Therefore, it is thought that it contributes to the improvement of the flexibility of the polyimide molecular chain. Therefore, the use of diamine (B3) increases the thermoplasticity of the polyimide.
  • the linking group A is preferably —O—.
  • diamine (B3) examples include 1,3-bis (4-aminophenoxy) benzene (TPE-R), 1,3-bis (3-aminophenoxy) benzene (APB), 4,4 ′-[2- Methyl- (1,3-phenylene) bisoxy] bisaniline, 4,4 '-[4-methyl- (1,3-phenylene) bisoxy] bisaniline, 4,4'-[5-methyl- (1,3-phenylene) ) Bisoxy] bisaniline and the like.
  • the diamine represented by the formula (B4) (hereinafter sometimes referred to as “diamine (B4)”) is an aromatic diamine having four benzene rings.
  • This diamine (B4) has a high flexibility because the amino group directly connected to at least one benzene ring and the divalent linking group A are in the meta position, thereby improving the flexibility of the polyimide molecular chain. It is thought to contribute. Therefore, the use of diamine (B4) increases the thermoplasticity of the polyimide.
  • the linking group A is preferably —O—, —CH 2 —, —C (CH 3 ) 2 —, —SO 2 —, —CO—, —CONH—.
  • Examples of the diamine (B4) include bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy)] benzophenone, bis [4,4 ′-(3-aminophenoxy)] benzanilide and the like can be mentioned.
  • the diamine represented by the formula (B5) (hereinafter sometimes referred to as “diamine (B5)”) is an aromatic diamine having four benzene rings.
  • This diamine (B5) has high flexibility because the degree of freedom of the polyimide molecular chain is increased by having two divalent linking groups A directly connected to at least one benzene ring in the meta position. It is thought that it contributes to the improvement of the flexibility of the polyimide molecular chain. Therefore, the thermoplasticity of polyimide increases by using diamine (B5).
  • the linking group A is preferably —O—.
  • Examples of the diamine (B5) include 4- [3- [4- (4-aminophenoxy) phenoxy] phenoxy] aniline, 4,4 ′-[oxybis (3,1-phenyleneoxy)] bisaniline, and the like. .
  • the diamine represented by the formula (B6) (hereinafter sometimes referred to as “diamine (B6)”) is an aromatic diamine having four benzene rings.
  • This diamine (B6) has high flexibility by having at least two ether bonds, and is considered to contribute to the improvement of the flexibility of the polyimide molecular chain. Therefore, the use of diamine (B6) increases the thermoplasticity of the polyimide.
  • the linking group A is preferably —C (CH 3 ) 2 —, —O—, —SO 2 —, or —CO—.
  • diamine (B6) examples include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), bis [4- (4-aminophenoxy) phenyl] ether (BAPE), and bis [4 -(4-Aminophenoxy) phenyl] sulfone (BAPS), bis [4- (4-aminophenoxy) phenyl] ketone (BAPK) and the like can be mentioned.
  • BAPP 2,2-bis [4- (4-aminophenoxy) phenyl] propane
  • BAPE bis [4- (4-aminophenoxy) phenyl] ether
  • BAPS bis [4 -(4-Aminophenoxy) phenyl] sulfone
  • BAPK bis [4- (4-aminophenoxy) phenyl] ketone
  • the diamine represented by the formula (B7) (hereinafter sometimes referred to as “diamine (B7)”) is an aromatic diamine having four benzene rings. Since this diamine (B7) has divalent linking groups A having high flexibility on both sides of the diphenyl skeleton, it is considered that this diamine (B7) contributes to improvement in flexibility of the polyimide molecular chain. Therefore, the thermoplasticity of polyimide increases by using diamine (B7).
  • the linking group A is preferably —O—.
  • Examples of the diamine (B7) include bis [4- (3-aminophenoxy)] biphenyl, bis [4- (4-aminophenoxy)] biphenyl, and the like.
  • the thermoplastic polyimide constituting the thermoplastic polyimide layer is at least one diamine selected from diamine (B1) to diamine (B7) with respect to 100 mole parts of the diamine residue.
  • a diamine residue derived from the compound is contained in an amount of 70 mol parts or more, preferably 70 mol parts or more and 99 mol parts or less, more preferably 80 mol parts or more and 95 mol parts or less. Since diamine (B1) to diamine (B7) have a flexible molecular structure, the flexibility of the polyimide molecular chain is improved by using at least one diamine compound selected from these in an amount within the above range. And thermoplasticity can be imparted. If the total amount of diamine (B1) to diamine (B7) is less than 70 parts by mole with respect to 100 parts by mole of the total diamine component, sufficient thermoplasticity cannot be obtained due to insufficient flexibility of the polyimide resin.
  • a diamine residue contained in the thermoplastic polyimide constituting the thermoplastic polyimide layer a diamine residue derived from a diamine compound represented by the general formula (A1) is also preferable.
  • the diamine compound [diamine (A1)] represented by the formula (A1) is as described in the description of the non-thermoplastic polyimide. Since the diamine (A1) has a rigid structure and has an action of imparting an ordered structure to the entire polymer, the dielectric loss tangent and hygroscopicity can be reduced by suppressing the movement of molecules. Furthermore, by using it as a raw material for thermoplastic polyimide, a polyimide having low gas permeability and excellent long-term heat-resistant adhesion can be obtained.
  • the thermoplastic polyimide constituting the thermoplastic polyimide layer is preferably a diamine residue derived from the diamine (A1), preferably in the range of 1 to 30 mol parts, More preferably, it may be contained within the range of 5 mol parts or more and 20 mol parts or less.
  • the diamine (A1) in an amount within the above range, an ordered structure is formed in the entire polymer due to the rigid structure derived from the monomer, so that the gas permeability and hygroscopicity are low while being thermoplastic, A polyimide having excellent heat-resistant adhesion can be obtained.
  • thermoplastic polyimide constituting the thermoplastic polyimide layer can contain a diamine residue derived from a diamine compound other than the diamines (A1) and (B1) to (B7) as long as the effects of the invention are not impaired.
  • thermoplastic polyimide the coefficient of thermal expansion is determined by selecting the types of the tetracarboxylic acid residue and diamine residue, and the molar ratios when two or more tetracarboxylic acid residues or diamine residues are applied. , Tensile modulus, glass transition temperature and the like can be controlled. Further, in the thermoplastic polyimide, when having a plurality of polyimide structural units, they may exist as a block or randomly, but are preferably present at random.
  • the tetracarboxylic acid residue and the diamine residue contained in the thermoplastic polyimide are both aromatic groups, so that the dimensional accuracy of the polyimide film in a high-temperature environment is increased.
  • the amount of change in in-plane retardation (RO) can be suppressed.
  • the imide group concentration of the thermoplastic polyimide is preferably 33% by weight or less.
  • the “imide group concentration” means a value obtained by dividing the molecular weight of the imide group (— (CO) 2 —N—) in the polyimide by the molecular weight of the entire polyimide structure.
  • the imide group concentration exceeds 33% by weight, the molecular weight of the resin itself is reduced, and the low hygroscopicity is also deteriorated due to an increase in polar groups.
  • the increase in CTE accompanying the decrease in imide group concentration is suppressed, Ensures low hygroscopicity.
  • the weight average molecular weight of the thermoplastic polyimide is preferably in the range of, for example, 10,000 to 400,000, and more preferably in the range of 50,000 to 350,000.
  • weight average molecular weight is less than 10,000, the strength of the film tends to decrease and the film tends to become brittle.
  • weight average molecular weight exceeds 400,000, the viscosity increases excessively, and defects such as film thickness unevenness and streaks tend to occur during the coating operation.
  • thermoplastic polyimide constituting the thermoplastic polyimide layer can improve the adhesion with the copper foil.
  • thermoplastic polyimide has a glass transition temperature in the range of 200 ° C. to 350 ° C., preferably in the range of 200 ° C. to 320 ° C.
  • thermoplastic polyimide constituting the thermoplastic polyimide layer is, for example, an adhesive layer in an insulating resin of a circuit board. Therefore, a completely imidized structure is most preferable in order to suppress copper diffusion. However, a part of the polyimide may be amic acid.
  • the imidation ratio was measured at about 1015 cm ⁇ 1 by measuring the infrared absorption spectrum of the polyimide thin film by a single reflection ATR method using a Fourier transform infrared spectrophotometer (commercial product: FT / IR620 manufactured by JASCO). And the absorbance of C ⁇ O stretching derived from an imide group of 1780 cm ⁇ 1 , based on the benzene ring absorber.
  • the polyimide film of the first, second or third embodiment is not particularly limited as long as it satisfies the above conditions, and may be a film (sheet) made of an insulating resin, copper foil, It may be an insulating resin film laminated on a substrate such as a resin sheet such as a glass plate, a polyimide film, a polyamide film, or a polyester film.
  • the thickness of the polyimide film of 1st, 2nd or 3rd embodiment can be set to the thickness within a predetermined range according to the purpose to be used.
  • the thickness of the polyimide film is preferably in the range of 8 to 50 ⁇ m, for example, and more preferably in the range of 11 to 26 ⁇ m. If the thickness of the polyimide film is less than the lower limit, problems such as inability to ensure electrical insulation and difficulty in handling in the production process due to a decrease in handling properties may occur.
  • the thickness of the polyimide film exceeds the above upper limit value, for example, it is necessary to control the manufacturing conditions for controlling the in-plane retardation (RO) with high accuracy, resulting in problems such as a decrease in productivity.
  • RO in-plane retardation
  • the thickness ratio of the non-thermoplastic polyimide layer to the thermoplastic polyimide layer is 1.5 to 6.0. It is good to be within the range. If the value of this ratio is less than 1.5, the non-thermoplastic polyimide layer with respect to the entire polyimide film becomes thin, so that the variation in in-plane retardation (RO) tends to be large, and if it exceeds 6.0, the thermoplastic polyimide layer Therefore, the adhesion reliability between the polyimide film and the copper foil is likely to decrease.
  • RO in-plane retardation
  • Control of this in-plane retardation has a correlation with the resin structure of each polyimide layer which comprises a polyimide film, and its thickness.
  • the thermoplastic polyimide layer which is a resin structure with adhesiveness, that is, high thermal expansion or softening, greatly affects the value of RO of the polyimide film as the thickness increases, so the ratio of the thickness of the non-thermoplastic polyimide layer Increase the thickness and decrease the thickness ratio of the thermoplastic polyimide layer to reduce the RO value of the polyimide film and its variation.
  • the polyimide film has a film width in the range of 490 mm or more and 1100 mm or less and a long length of 20 m or more from the viewpoint of increasing the effect of improving the dimensional accuracy of the polyimide film.
  • the effect of invention becomes especially remarkable, so that the width direction (henceforth TD direction) is wide.
  • the longitudinal direction of a long polyimide film is called MD direction.
  • the polyimide film of the second embodiment has an in-plane retardation (RO) value in the range of 5 nm to 50 nm, preferably in the range of 5 nm to 20 nm, more preferably in the range of 5 nm to 15 nm. .
  • the variation in the TD direction ( ⁇ RO) is 10 nm or less, preferably 5 nm or less, more preferably 3 nm or less, and is controlled within such a range, so that the film has a thickness of 25 ⁇ m or more.
  • the dimensional accuracy is high.
  • the polyimide film of the second embodiment has an in-plane retardation (RO) change amount of 20 nm or less, preferably 10 nm or less before and after pressurization at a pressure of 340 MPa / m 2 and a holding time of 15 minutes in an environment at a temperature of 320 ° C. More preferably, it is 5 nm or less.
  • RO in-plane retardation
  • the polyimide film of 2nd Embodiment is the temperature exceeding the glass transition temperature of the polyimide which comprises a thermoplastic polyimide layer, the variation
  • the coefficient of thermal expansion (CTE) of the entire film is in the range of 10 ppm / K to 30 ppm / K, preferably in the range of 10 ppm / K to 25 ppm / K. The inside is good, and the range of 10 to 20 ppm / K is more preferable.
  • the coefficient of thermal expansion (CTE) of the polyimide film of the third embodiment is the same as that of the first or second embodiment.
  • the dielectric loss tangent (Tan ⁇ ) at 10 GHz as measured by a split post-derivative resonator (SPDR) as the whole insulating layer is 0.004 or less, more preferably 0.001 or more and 0. Within the range of 0.004 or less, more preferably within the range of 0.002 or more and 0.003 or less.
  • the dielectric loss tangent of the insulating layer In order to improve the dielectric characteristics of the circuit board, it is particularly important to control the dielectric loss tangent of the insulating layer. By setting the dielectric loss tangent within the above range, the effect of reducing transmission loss increases. Therefore, when applying a polyimide film as an insulating layer of a high frequency circuit board, for example, transmission loss can be reduced efficiently.
  • the dielectric tangent of the insulating layer at 10 GHz exceeds 0.004
  • inconveniences such as loss of an electric signal are likely to occur on a high-frequency signal transmission path.
  • the lower limit value of the dielectric loss tangent at 10 GHz of the insulating layer is not particularly limited, but physical property control in the case of applying polyimide as the insulating layer of the circuit board is considered.
  • the dielectric constant at 10 GHz as a whole is 4 to ensure impedance matching. It is preferably 0 or less.
  • the dielectric constant at 10 GHz of the insulating layer exceeds 4.0, when used on a circuit board such as an FPC, the dielectric loss of the insulating layer is deteriorated, and the inconvenience such as loss of an electric signal on a high-frequency signal transmission path. Is likely to occur.
  • the polyimide film of the first embodiment or the second embodiment has a moisture absorption rate of 0. 23 ° C. and 50% RH in order to reduce the influence of humidity when used for a circuit board such as an FPC. It is preferably 7% by weight or less.
  • the moisture absorption rate of the polyimide film exceeds 0.7% by weight, when used for a circuit board such as an FPC, it is easily affected by humidity, and inconveniences such as fluctuations in the transmission speed of high-frequency signals are likely to occur.
  • the polyimide film of the third embodiment takes into consideration the influence on the dimensional stability and dielectric properties of the polyimide film, and has a moisture absorption rate of 0.2 when humidity is adjusted at 23 ° C. and 50% RH for 24 hours. It is preferable that it is 65 weight% or less. If the moisture absorption rate exceeds 0.65% by weight, the dimensional stability and dielectric characteristics of the polyimide film may be deteriorated. The fact that the moisture absorption is 0.65% by weight or less means that the polar group concentration in the polyimide is low and that the ordered structure of the polymer chain is likely to be formed. It is preferable for improvement. However, since the HAZE value tends to increase with the formation of the ordered structure of the polymer chain when the moisture absorption rate decreases, it is preferable to consider the HAZE value described later.
  • the tensile elastic modulus of the polyimide film of the second embodiment is preferably in the range of 3.0 to 10.0 GPa, and preferably in the range of 4.5 to 8.0 GPa. If the tensile modulus of the polyimide film is less than 3.0 GPa, the strength of the polyimide itself will decrease, and handling problems such as film tearing may occur when processing a copper clad laminate on a circuit board. . On the other hand, when the tensile modulus of the polyimide film exceeds 10.0 GPa, the bending resistance of the copper clad laminate is increased, resulting in an increase in bending stress applied to the copper wiring when the copper clad laminate is folded. Bending resistance is reduced. By setting the tensile elastic modulus of the polyimide film within the above range, the strength and flexibility of the polyimide film are ensured.
  • the polyimide film of the third embodiment has a glass transition temperature of 300 ° C. or higher as defined in the above condition (c-ii).
  • the glass transition temperature is less than 300 ° C., problems such as film swell and peeling from the wiring tend to occur when a CCL using the polyimide film of the third form or an FPC is manufactured.
  • the glass transition temperature is set to 300 ° C. or higher, the solder heat resistance and dimensional stability of the polyimide film are enhanced.
  • the polyimide film of the third embodiment is prepared by applying a polyamic acid solution, which is a polyimide precursor, onto a copper foil having a ten-point average roughness (Rz) of 0.6 ⁇ m and imidizing it.
  • a polyamic acid solution which is a polyimide precursor
  • the HAZE value based on JIS K 7136 is preferably in the range of 62 to 75%. .
  • the HAZE value exceeds 75%, the visibility through the polyimide film of the third embodiment is lowered.
  • the alignment to the alignment mark becomes difficult, and the practicality may be reduced.
  • the HAZE value is less than 62%, the visibility becomes high, but the formation of an ordered structure of the polyimide polymer chain has not progressed, so that the moisture absorption characteristics and the dielectric characteristics may be impaired.
  • the preferable value of the HAZE value is set in the range of 62 to 75%. Yes.
  • the polyimide film of the third embodiment preferably has a film elongation of 30% or more.
  • the polyimide film of the third embodiment when used as an insulating layer of an FPC, it is necessary to bend and store it in a small space in a housing of a mobile device or the like. In such a usage pattern, if the film elongation is low, the wiring may be disconnected. Therefore, the polyimide film of the third embodiment has a preferable film elongation of 30% or more.
  • the polyimide film of 1st, 2nd or 3rd embodiment may contain an inorganic filler in a non-thermoplastic polyimide layer or a thermoplastic polyimide layer as needed.
  • an inorganic filler in a non-thermoplastic polyimide layer or a thermoplastic polyimide layer as needed.
  • Specific examples include silicon dioxide, aluminum oxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride, and calcium fluoride. These may be used alone or in combination of two or more.
  • a polyimide film is produced by applying and drying a polyamic acid solution on a supporting substrate and then imidizing it. [2] After applying and drying a polyamic acid solution on a supporting substrate, the polyamic acid gel film is peeled off from the supporting substrate and imidized to produce a polyimide film.
  • the polyimide film of 1st Embodiment or 2nd Embodiment is a polyimide film which consists of a polyimide layer of multiple layers
  • a method of applying and drying a polyamic acid solution a plurality of times and then imidizing (hereinafter referred to as a casting method), [4] Multilayer extrusion was simultaneously applied and dried in a state where the polyamic acid was laminated in multiple layers. Then, the method (henceforth a multilayer extrusion method) which performs imidation is mentioned.
  • the polyimide film of the third embodiment is applied as one layer in a multilayer polyimide film composed of a plurality of polyimide layers.
  • the method for applying the polyimide solution (or polyamic acid solution) on the substrate is not particularly limited, and for example, it can be applied by a coater such as a comma, die, knife, lip or the like.
  • a coater such as a comma, die, knife, lip or the like.
  • a method of repeatedly applying and drying a polyimide solution (or polyamic acid solution) on a substrate is preferable.
  • the method of [1] is, for example, the following steps 1a to 1c; (1a) applying a polyamic acid solution to a supporting substrate and drying; (1b) forming a polyimide layer by heat-treating polyamic acid on a supporting substrate and imidizing; (1c) a step of obtaining a polyimide film by separating the support substrate and the polyimide layer; Can be included.
  • the method of [2] is, for example, the following steps 2a to 2c; (2a) applying a polyamic acid solution to a supporting substrate and drying; (2b) a step of separating the support substrate and the polyamic acid gel film; (2c) a step of obtaining a polyimide film by heat-treating the polyamic acid gel film and imidizing; Can be included.
  • the method [3] is the same as the method [1] or [2] except that the step 1a or the step 2a is repeated a plurality of times to form a polyamic acid laminated structure on the support substrate. It can be carried out in the same manner as the method [1] or [2].
  • the method [4] is the same as the method [1] except that in step 1a of the method [2] or step 2a of the method [2], the laminated structure of polyamic acid is simultaneously applied and dried by multilayer extrusion. It can be carried out in the same manner as the method [1] or [2].
  • the polyimide film produced in the first, second or third embodiment preferably completes imidization of polyamic acid on a supporting substrate. Since the polyamic acid resin layer is imidized in a state of being fixed to the support substrate, it is possible to suppress the expansion and contraction change of the polyimide layer in the imidization process, and to maintain the thickness and dimensional accuracy of the polyimide film. Further, when the polyimide film of the third embodiment is applied as one layer in a multilayer polyimide film composed of a plurality of polyimide layers, a heat treatment for imidization is performed at a temperature within a range of 120 ° C. to 360 ° C., for example. In addition, the heat treatment time is controlled to 5 minutes or more, preferably within the range of 10 minutes to 20 minutes, so that foaming can be effectively suppressed and problems such as swelling of the polyimide layer can be prevented.
  • Polyimide film that has completed imidization of polyamic acid on the supporting substrate is generated when the polyimide film is separated from the supporting substrate by tension on the polyimide film, for example, when peeling using a knife edge or the like.
  • the polyimide film is stretched by stress or the like on the polyimide film, and variations in in-plane retardation (RO) of the polyimide film are likely to occur.
  • the polyimide film according to the second embodiment has a non-thermoplastic polyimide layer and a polyimide constituting the thermoplastic polyimide layer, both of which easily form an ordered structure.
  • the RO can be controlled by dispersing in the above.
  • in-plane retardation can be controlled.
  • conditions such as the stretching operation and the heating rate during imidization, the imidation completion temperature, and the load.
  • the copper clad laminate of the first, second or third embodiment includes an insulating layer and a copper foil on at least one surface of the insulating layer, and a part or all of the insulating layer is the first, What is necessary is just to be formed using the polyimide film of 2nd or 3rd Embodiment.
  • the layer which touches copper foil in an insulating layer is a thermoplastic polyimide layer. Therefore, about the polyimide film of 3rd Embodiment, it is preferable to use as a copper clad laminated board in the state laminated
  • the copper foil is provided on one side or both sides of the insulating layer. That is, the copper-clad laminate of the first, second, or third embodiment may be a single-sided copper-clad laminate (single-sided CCL) or a double-sided copper-clad laminate (double-sided CCL). In the case of single-sided CCL, the copper foil laminated on one side of the insulating layer is referred to as “first copper foil layer” in the present invention.
  • the copper foil laminated on one side of the insulating layer is referred to as the “first copper foil layer” in the present invention, and the surface of the insulating layer opposite to the side on which the first copper foil is laminated
  • the copper foil laminated on each other is referred to as a “second copper foil layer” in the present invention.
  • the copper-clad laminate of the first, second or third embodiment is used as an FPC by forming a copper wiring by etching a copper foil to form a wiring circuit.
  • the copper-clad laminate is prepared, for example, by preparing a resin film including the polyimide film of the first, second, or third embodiment, and sputtering a metal to form a seed layer. You may prepare by forming a copper foil layer by plating.
  • the copper-clad laminate is prepared by preparing a resin film including the polyimide film of the first, second or third embodiment, and laminating a copper foil on the resin film by a method such as thermocompression bonding. It may be prepared.
  • the copper-clad laminate casts a coating solution containing a polyamic acid which is a polyimide precursor on a copper foil, and after drying to form a coating film, heat treatment is imidized to form a polyimide layer. May be prepared.
  • first copper foil the copper foil used for the first copper foil layer
  • first copper foil is particularly For example, rolled copper foil or electrolytic copper foil may be used.
  • a commercially available copper foil can be used as the first copper foil.
  • the thickness of the first copper foil is preferably 18 ⁇ m or less, more preferably in the range of 6 to 13 ⁇ m, still more preferably in the range of 6 to 12 ⁇ m. Good.
  • the bendability of the copper clad laminate (or FPC) can be improved by setting the thickness of the first copper foil to 13 ⁇ m or less, preferably 13 ⁇ m or less, and more preferably 12 ⁇ m or less.
  • the lower limit value of the thickness of the first copper foil is preferably 6 ⁇ m.
  • the tensile elastic modulus of the first copper foil is preferably in the range of 10 to 35 GPa, for example, and more preferably in the range of 15 to 25 GPa.
  • the flexibility tends to be high when annealed by heat treatment. Therefore, if the tensile elastic modulus of the copper foil is less than the lower limit, the rigidity of the first copper foil itself is reduced by heating in the step of forming the insulating layer on the long first copper foil. .
  • the tensile modulus of the first copper foil may be in the above range.
  • the second copper foil layer is laminated on the surface of the insulating layer opposite to the first copper foil layer. It does not specifically limit as copper foil (2nd copper foil) used for a 2nd copper foil layer, For example, rolled copper foil or electrolytic copper foil may be sufficient. A commercially available copper foil can also be used as the second copper foil. In addition, you may use the same thing as 1st copper foil as 2nd copper foil.
  • the copper-clad laminate of the first, second or third embodiment is mainly useful as a circuit board material such as FPC. That is, the FPC according to one embodiment of the present invention is formed by processing the copper foil of the copper-clad laminate of the first, second, or third embodiment into a pattern by a conventional method to form a wiring layer. Can be manufactured.
  • Glass transition temperature is a rate of temperature increase from 30 ° C. to 400 ° C. using a polyimide film having a size of 5 mm ⁇ 20 mm, using a dynamic viscoelasticity measuring device (DMA: manufactured by UBM, trade name: E4000F). Measurement was performed at 4 ° C./min and a frequency of 11 Hz, and the temperature at which the change in elastic modulus (tan ⁇ ) was maximum was taken as the glass transition temperature.
  • DMA dynamic viscoelasticity measuring device
  • CTE coefficient of thermal expansion
  • the dielectric constant and dielectric loss tangent of the resin sheet at a frequency of 10 GHz were measured using a vector network analyzer (manufactured by Agilent, trade name E8363C) and a split post dielectric resonator (SPDR resonator). The material used for the measurement was left for 24 hours under the conditions of temperature: 24-26 ° C., humidity: 45-55%.
  • the surface roughness of the copper foil is AFM (manufactured by Bruker AXS, trade name: Dimension Icon type SPM), probe (manufactured by Bruker AXS, trade name: TESPA (NCHV), tip radius of curvature 10 nm, Using a spring constant of 42 N / m 2), a tapping mode was used to measure the 80 ⁇ m ⁇ 80 ⁇ m range of the copper foil surface, and the ten-point average roughness (Rz) was determined.
  • AFM manufactured by Bruker AXS, trade name: Dimension Icon type SPM
  • probe manufactured by Bruker AXS, trade name: TESPA (NCHV)
  • tip radius of curvature 10 nm Using a spring constant of 42 N / m 2), a tapping mode was used to measure the 80 ⁇ m ⁇ 80 ⁇ m range of the copper foil surface, and the ten-point average roughness (Rz) was determined.
  • the other copper foil was peeled off at a rate of 50 mm / min in the 90 ° direction by fixing to an aluminum plate with a tape, and the median strength when peeling from the resin layer by 10 mm was determined.
  • those having a peel strength of 1.0 kN / m or more are ⁇ (excellent)
  • those having a peel strength of 0.7 kN / m or more and less than 1.0 kN / m are ⁇ (good)
  • 0.4 kN / m or more and 0.7 kN / m Those less than m were evaluated as ⁇ (possible), and those less than 0.4 kN / m were evaluated as ⁇ (impossible).
  • the retardation in the in-plane direction of the polyimide film was determined using a birefringence meter (trade name; wide range birefringence evaluation system WPA-100, manufactured by Photonic Lattice). The measurement wavelength is 543 nm.
  • HAZE value The evaluation of the HAZE value was performed by a measurement method described in JIS K 7136 with respect to a polyimide film having a size of 5 cm ⁇ 5 cm using a haze measuring device (turbidimeter: manufactured by Nippon Denshoku Industries Co., Ltd., trade name: NDH5000). .
  • BPDA 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride
  • PMDA pyromellitic dianhydride
  • NTCDA 2,3,6,7-naphthalenetetracarboxylic dianhydride
  • TAHQ 1,4- Phenylenebis (trimellitic acid monoester) dianhydride
  • TMEG ethylene glycol bisanhydro trimellitate
  • m-TB 2,2'-dimethyl-4,4'-diaminobiphenyl
  • TPE-R 1,3-bis ( 4-Aminophenoxy) benzene
  • TPE-Q 1,4-bis (4-aminophenoxy) benzene
  • APB 1,3-bis (3-aminophenoxy) benzene
  • 3,3′-DAPM 3,3′-diamino- Diphenylmethane
  • DTBAB 1,4-bis (4-aminophenoxy) -2,5-di
  • the polyamic acid solution A-1 was uniformly applied on one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution to prepare polyimide film A-1 (thermoplastic, Tg; 256 ° C., moisture absorption rate: 0.36 wt%). did.
  • the imide group concentration of the polyimide constituting the polyimide film A-1 was 26.4% by weight.
  • the polyamic acid solution A-2 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of a 12 ⁇ m thick electrolytic copper foil so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was removed by etching using a ferric chloride aqueous solution to prepare a polyimide film A-2 (thermoplastic, Tg; 242 ° C., moisture absorption rate: 0.35% by weight). did. Further, the imide group concentration of the polyimide constituting the polyimide film A-2 was 26.5% by weight.
  • the polyamic acid solution A-3 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of a 12 ⁇ m thick electrolytic copper foil so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution to prepare polyimide film A-3 (thermoplastic, Tg; 240 ° C., moisture absorption rate: 0.31 wt%). did. Further, the imide group concentration of the polyimide constituting the polyimide film A-3 was 26.9% by weight.
  • the polyamic acid solution A-4 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution to prepare polyimide film A-4 (thermoplastic, Tg; 240 ° C., moisture absorption rate: 0.29 wt%). did. Further, the imide group concentration of the polyimide constituting the polyimide film A-4 was 27.1% by weight.
  • the polyamic acid solution A-5 was uniformly applied on one surface (surface roughness Rz; 2.1 ⁇ m) of a 12 ⁇ m thick electrolytic copper foil so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution to prepare polyimide film A-5 (thermoplastic, Tg; 244 ° C., moisture absorption rate: 0.27 wt%). did. Further, the imide group concentration of the polyimide constituting the polyimide film A-5 was 27.4% by weight.
  • the polyamic acid solution A-6 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution to prepare polyimide film A-6 (thermoplastic, Tg; 248 ° C., moisture absorption rate: 0.27 wt%). did.
  • the imide group concentration of the polyimide constituting the polyimide film A-6 was 27.8% by weight.
  • the polyamic acid solution A-7 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was removed by etching using an aqueous ferric chloride solution to prepare polyimide film A-7 (thermoplastic, Tg: 239 ° C., moisture absorption rate: 0.31 wt%). did. Further, the imide group concentration of the polyimide constituting the polyimide film A-7 was 27.0% by weight.
  • the polyamic acid solution A-8 was uniformly applied on one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution to prepare polyimide film A-8 (thermoplastic, Tg: 235 ° C., moisture absorption rate: 0.31 wt%). did. Further, the imide group concentration of the polyimide constituting the polyimide film A-8 was 27.1% by weight.
  • the polyamic acid solution A-9 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution to prepare polyimide film A-9 (thermoplastic, Tg; 278 ° C., moisture absorption rate: 0.34% by weight). did.
  • the imide group concentration of the polyimide constituting the polyimide film A-9 was 22.6% by weight.
  • the polyamic acid solution A-10 was uniformly applied on one surface (surface roughness Rz; 2.1 ⁇ m) of a 12 ⁇ m thick electrolytic copper foil so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution to prepare polyimide film A-10 (thermoplastic, Tg; 276 ° C., moisture absorption rate: 0.41 wt%). did.
  • the imide group concentration of the polyimide constituting the polyimide film A-10 was 28.0% by weight.
  • the polyamic acid solution A-11 was uniformly applied on one surface (surface roughness Rz; 2.1 ⁇ m) of a 12 ⁇ m thick electrolytic copper foil so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution to prepare polyimide film A-11 (thermoplastic, Tg; 244 ° C., moisture absorption rate: 0.39 wt%). did.
  • the imide group concentration of the polyimide constituting the polyimide film A-11 was 26.5% by weight.
  • the polyamic acid solution A-12 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution, and polyimide film A-12 (non-thermoplastic, Tg: 322 ° C., moisture absorption rate: 0.57 wt%) was removed. Prepared.
  • the imide group concentration of the polyimide constituting the polyimide film A-12 was 31.8% by weight.
  • the polyamic acid solution A-13 was uniformly applied on one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution, and polyimide film A-13 (non-thermoplastic, Tg: 332 ° C., moisture absorption rate: 0.63% by weight) was removed. Prepared. Further, the imide group concentration of the polyimide constituting the polyimide film A-13 was 32.4% by weight.
  • the polyamic acid solution A-14 was uniformly applied on one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution, and polyimide film A-14 (non-thermoplastic, Tg: 322 ° C., moisture absorption rate: 0.61 wt%) was removed. Prepared.
  • the imide group concentration of the polyimide constituting the polyimide film A-14 was 31.6% by weight.
  • the polyamic acid solution A-15 was uniformly applied on one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution, and polyimide film A-15 (non-thermoplastic, Tg: 324 ° C., moisture absorption rate: 0.58 wt%) was removed. Prepared.
  • the imide group concentration of the polyimide constituting the polyimide film A-15 was 31.4% by weight.
  • the polyamic acid solution A-16 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of a 12 ⁇ m thick electrolytic copper foil so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution, and polyimide film A-16 (non-thermoplastic, Tg; 330 ° C., moisture absorption rate: 0.59 wt%) was removed. Prepared. Further, the imide group concentration of the polyimide constituting the polyimide film A-16 was 31.8% by weight.
  • the polyamic acid solution A-17 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization. About the obtained metal-clad laminate, the copper foil was removed by etching using a ferric chloride aqueous solution, and polyimide film A-17 (non-thermoplastic, Tg: 342 ° C., moisture absorption rate: 0.56 wt%) was removed. Prepared. The imide group concentration of the polyimide constituting the polyimide film A-17 was 32.3% by weight.
  • the polyamic acid solution A-18 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of a 12 ⁇ m thick electrolytic copper foil so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution, and polyimide film A-18 (non-thermoplastic, Tg: 314 ° C., moisture absorption rate: 0.59 wt%) was removed. Prepared.
  • the imide group concentration of the polyimide constituting the polyimide film A-18 was 31.7% by weight.
  • the polyamic acid solution A-19 was uniformly applied on one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution, and polyimide film A-19 (non-thermoplastic, Tg: 311 ° C., moisture absorption rate: 0.58 wt%) was removed. Prepared. Further, the imide group concentration of the polyimide constituting the polyimide film A-19 was 31.4% by weight.
  • the polyamic acid solution A-20 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution, and polyimide film A-20 (non-thermoplastic, Tg; 312 ° C., moisture absorption rate: 0.61% by weight) was removed. Prepared.
  • the imide group concentration of the polyimide constituting the polyimide film A-20 was 32.1% by weight.
  • the polyamic acid solution A-21 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of a 12 ⁇ m thick electrolytic copper foil so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution, and polyimide film A-21 (non-thermoplastic, Tg; 320 ° C., moisture absorption rate: 0.65 wt%) was removed. Prepared. Further, the imide group concentration of the polyimide constituting the polyimide film A-21 was 31.9% by weight.
  • the polyamic acid solution A-22 was uniformly applied to one side (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution, and polyimide film A-22 (non-thermoplastic, Tg: 322 ° C., moisture absorption rate: 0.57 wt%) was removed. Prepared.
  • the imide group concentration of the polyimide constituting the polyimide film A-22 was 32.0% by weight.
  • the polyamic acid solution A-23 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution, and polyimide film A-23 (non-thermoplastic, Tg: 291 ° C., moisture absorption rate: 0.59 wt%) was removed. Prepared.
  • the imide group concentration of the polyimide constituting the polyimide film A-23 was 30.7% by weight.
  • the polyamic acid solution A-24 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization. About the obtained metal-clad laminate, the copper foil was removed by etching using a ferric chloride aqueous solution, and polyimide film A-24 (non-thermoplastic, Tg; 400 ° C. or higher, moisture absorption rate: 0.78 wt%) was prepared. Further, the imide group concentration of the polyimide constituting the polyimide film A-24 was 34.2% by weight.
  • the polyamic acid solution A-25 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization. About the obtained metal-clad laminate, the copper foil was removed by etching using a ferric chloride aqueous solution, and polyimide film A-25 (non-thermoplastic, Tg; 400 ° C. or higher, moisture absorption rate: 0.57% by weight) was prepared. Further, the imide group concentration of the polyimide constituting the polyimide film A-25 was 30.2% by weight.
  • the polyamic acid solution A-26 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution, and polyimide film A-26 (non-thermoplastic, Tg; 304 ° C., moisture absorption rate: 0.49 wt%) was removed. Prepared. Further, the imide group concentration of the polyimide constituting the polyimide film A-26 was 26.9% by weight.
  • Example A-1 After uniformly applying the polyamic acid solution A-1 to a thickness of about 2 to 3 ⁇ m on one side (surface roughness Rz; 0.6 ⁇ m) of a 12 ⁇ m thick electrolytic copper foil, The solvent was removed by heating to dryness. Next, the polyamic acid solution A-15 was uniformly applied thereon so that the thickness after curing was about 21 ⁇ m, and dried by heating at 120 ° C. to remove the solvent. Further, the polyamic acid solution A-1 was uniformly applied thereon so that the thickness after curing was about 2 to 3 ⁇ m, and then dried by heating at 120 ° C. to remove the solvent.
  • stepwise heat processing was performed in 30 minutes from 120 degreeC to 360 degreeC, and imidation was completed.
  • the copper foil was etched away using an aqueous ferric chloride solution, and multilayer polyimide film A-1 (CTE; 22 ppm / K, moisture absorption; 0.54% by weight, dielectric constant; 3.58, dielectric loss tangent; 0.0031) was adjusted.
  • Example A-2 to Example A-21, Reference Example A-1 to Reference Example A-2 Example A-2 to Example A-21 and Reference Example A-1 to Reference Example A-2 were the same as Example A-1, except that the polyamic acid solutions shown in Tables 1 to 4 were used.
  • Multilayer polyimide films A-2 to A-23 were obtained.
  • CTE, moisture absorption, dielectric constant and dielectric loss tangent of the obtained multilayer polyimide films A-2 to A-23 were determined. The measurement results are shown in Tables 1 to 4.
  • Example A-22 to Example A-23 The multilayer polyimide films A-24 to A-25 of Examples A-22 to A-23 were obtained in the same manner as in Example A-1, except that the polyamic acid solution shown in Table 5 was used. CTE, moisture absorption rate, dielectric constant, and dielectric loss tangent of the obtained multilayer polyimide films A-24 to A-25 were determined. Table 5 shows the measurement results.
  • the polyamic acid solution B-1 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution to prepare a polyimide film B-1 (thermoplastic, Tg; 256 ° C., moisture absorption rate: 0.36 wt%). did. Further, the imide group concentration of the polyimide constituting the polyimide film B-1 was 26.4% by weight.
  • the polyamic acid solution B-2 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution to prepare polyimide film B-2 (thermoplastic, Tg; 242 ° C., moisture absorption rate: 0.35 wt%). did. Further, the imide group concentration of the polyimide constituting the polyimide film B-2 was 26.5% by weight.
  • the polyamic acid solution B-3 was uniformly applied on one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution to prepare polyimide film B-3 (thermoplastic, Tg; 240 ° C., moisture absorption rate: 0.31 wt%). did.
  • the imide group concentration of the polyimide constituting the polyimide film B-3 was 26.9% by weight.
  • the reaction vessel contains 68.586 parts by weight of m-TB (0.323 mole part) and 535.190 parts by weight of TPE-R (1.831 mole part) and the solid content concentration after polymerization. DMAc in an amount of 12% by weight was added and dissolved by stirring at room temperature. Next, after adding 143.758 parts by weight of PMDA (0.659 parts by mole) and 452.466 parts by weight of BPDA (1.538 parts by weight), the polymerization reaction was continued by stirring at room temperature for 3 hours, A polyamic acid solution B-4 was obtained. The solution viscosity of the polyamic acid solution B-4 was 1,580 cps.
  • the polyamic acid solution B-4 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of a 12 ⁇ m thick electrolytic copper foil so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution to prepare polyimide film B-4 (thermoplastic, Tg; 240 ° C., moisture absorption rate: 0.29 wt%). did. Further, the imide group concentration of the polyimide constituting the polyimide film B-4 was 27.1% by weight.
  • the polyamic acid solution B-5 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution to prepare polyimide film B-5 (thermoplastic, Tg; 244 ° C., moisture absorption rate: 0.27 wt%). did. Further, the imide group concentration of the polyimide constituting the polyimide film B-5 was 27.4% by weight.
  • the polyamic acid solution B-6 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution to prepare polyimide film B-6 (thermoplastic, Tg; 248 ° C., moisture absorption rate: 0.27 wt%). did.
  • the imide group concentration of the polyimide constituting the polyimide film B-6 was 27.8% by weight.
  • the polyamic acid solution B-7 was uniformly applied on one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution to prepare polyimide film B-7 (thermoplastic, Tg: 239 ° C., moisture absorption rate: 0.31 wt%). did. Further, the imide group concentration of the polyimide constituting the polyimide film B-7 was 27.0% by weight.
  • the polyamic acid solution B-8 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of a 12 ⁇ m thick electrolytic copper foil so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution to prepare polyimide film B-8 (thermoplastic, Tg: 235 ° C., moisture absorption rate: 0.31 wt%). did. Further, the imide group concentration of the polyimide constituting the polyimide film B-8 was 27.1% by weight.
  • the polyamic acid solution B-9 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution to prepare polyimide film B-9 (thermoplastic, Tg: 278 ° C., moisture absorption: 0.34 wt%). did. Further, the imide group concentration of the polyimide constituting the polyimide film B-9 was 22.6% by weight.
  • the polyamic acid solution B-10 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was removed by etching using an aqueous ferric chloride solution to prepare polyimide film B-10 (thermoplastic, Tg; 276 ° C., moisture absorption rate: 0.41 wt%). did. Further, the imide group concentration of the polyimide constituting the polyimide film B-10 was 28.0% by weight.
  • the polyamic acid solution B-11 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution to prepare polyimide film B-11 (thermoplastic, Tg; 244 ° C., moisture absorption rate: 0.39 wt%). did. Further, the imide group concentration of the polyimide constituting the polyimide film B-11 was 26.5% by weight.
  • the polyamic acid solution B-12 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was removed by etching using an aqueous ferric chloride solution to prepare polyimide film B-12 (thermoplastic, Tg: 260 ° C., moisture absorption rate: 0.28 wt%). did.
  • the imide group concentration of the polyimide constituting the polyimide film B-12 was 28.7% by weight.
  • the polyamic acid solution B-13 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution, and polyimide film B-13 (non-thermoplastic, Tg: 305 ° C., moisture absorption rate: 0.52% by weight) was obtained. Prepared.
  • the imide group concentration of the polyimide constituting the polyimide film B-13 was 31.2% by weight.
  • the polyamic acid solution B-14 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution, and polyimide film B-14 (non-thermoplastic, Tg: 322 ° C., moisture absorption rate: 0.57 wt%) was removed. Prepared. Further, the imide group concentration of the polyimide constituting the polyimide film B-14 was 31.8% by weight.
  • the polyamic acid solution B-15 was uniformly applied on one surface (surface roughness Rz; 2.1 ⁇ m) of a 12 ⁇ m thick electrolytic copper foil so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization. About the obtained metal-clad laminate, the copper foil was removed by etching using a ferric chloride aqueous solution, and polyimide film B-15 (non-thermoplastic, Tg: 332 ° C., moisture absorption rate: 0.63% by weight) was removed. Prepared. Further, the imide group concentration of the polyimide constituting the polyimide film B-15 was 32.4% by weight.
  • the polyamic acid solution B-16 was uniformly applied on one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization. About the obtained metal-clad laminate, the copper foil was etched away using an aqueous ferric chloride solution, and polyimide film B-16 (non-thermoplastic, Tg: 322 ° C., moisture absorption rate: 0.61 wt%) was removed. Prepared. Further, the imide group concentration of the polyimide constituting the polyimide film B-16 was 31.6% by weight.
  • the polyamic acid solution B-17 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution, and polyimide film B-17 (non-thermoplastic, Tg; 324 ° C., moisture absorption rate: 0.58 wt%) was removed. Prepared. Further, the imide group concentration of the polyimide constituting the polyimide film B-17 was 31.4% by weight.
  • the polyamic acid solution B-18 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was removed by etching using a ferric chloride aqueous solution, and polyimide film B-18 (non-thermoplastic, Tg; 330 ° C., moisture absorption rate: 0.59 wt%) was removed. Prepared. Further, the imide group concentration of the polyimide constituting the polyimide film B-18 was 31.8% by weight.
  • the reaction vessel contained 616.159 parts by weight of m-TB (2.902 mole part) and 94.275 parts by weight of TPE-R (0.322 mole part) and the solid content concentration after polymerization. DMAc in an amount of 15% by weight was added and dissolved by stirring at room temperature. Next, after adding 415.723 parts by weight of PMDA (1.906 parts by mole) and 373.843 parts by weight of BPDA (1.271 parts by weight), the polymerization reaction was continued by stirring at room temperature for 3 hours, A polyamic acid solution B-19 was obtained. The solution viscosity of the polyamic acid solution B-19 was 31,500 cps.
  • the polyamic acid solution B-19 was uniformly applied on one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution, and polyimide film B-19 (non-thermoplastic, Tg; 342 ° C., moisture absorption rate: 0.56 wt%) was removed. Prepared. Further, the imide group concentration of the polyimide constituting the polyimide film B-19 was 32.3% by weight.
  • the polyamic acid solution B-20 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was removed by etching using a ferric chloride aqueous solution, and polyimide film B-20 (non-thermoplastic, Tg: 364 ° C., moisture absorption rate: 0.68 wt%) was removed. Prepared. Further, the imide group concentration of the polyimide constituting the polyimide film B-20 was 32.9% by weight.
  • the polyamic acid solution B-21 was uniformly applied on one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization. About the obtained metal-clad laminate, the copper foil was removed by etching using an aqueous ferric chloride solution, and polyimide film B-21 (non-thermoplastic, Tg; 296 ° C., moisture absorption rate: 0.54% by weight) was prepared. The imide group concentration of the polyimide constituting the polyimide film B-21 was 26.8% by weight.
  • the reaction vessel contained 587.744 parts by weight of m-TB (2.769 mole parts) and 89.927 parts by weight of TPE-R (0.308 mole parts) and the solid content concentration after polymerization. DMAc in an amount of 15% by weight was added and dissolved by stirring at room temperature. Next, after adding 198.275 parts by weight of PMDA (0.909 mole parts) and 624.054 parts by weight of BPDA (2.121 mole parts), the polymerization reaction was continued for 3 hours at room temperature, A polyamic acid solution B-22 was obtained. The solution viscosity of the polyamic acid solution B-22 was 26,800 cps.
  • the polyamic acid solution B-22 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution, and polyimide film B-22 (non-thermoplastic, Tg; 291 ° C., moisture absorption rate: 0.59 wt%) was removed. Prepared.
  • the imide group concentration of the polyimide constituting the polyimide film B-22 was 30.7% by weight.
  • the polyamic acid solution B-23 was uniformly applied to one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was removed by etching using a ferric chloride aqueous solution, and polyimide film B-23 (non-thermoplastic, Tg: 285 ° C., moisture absorption rate: 0.53% by weight) was removed. Prepared. Further, the imide group concentration of the polyimide constituting the polyimide film B-23 was 30.7% by weight.
  • the polyamic acid solution B-24 was uniformly applied on one surface (surface roughness Rz; 2.1 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then 120 ° C. And dried by heating to remove the solvent. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization. About the obtained metal-clad laminate, the copper foil was removed by etching using a ferric chloride aqueous solution, and polyimide film B-24 (non-thermoplastic, Tg; 400 ° C. or higher, moisture absorption rate: 0.78 wt%) was prepared. Further, the imide group concentration of the polyimide constituting the polyimide film B-24 was 34.2% by weight.
  • Example B-1 Using a multi-manifold type three-coextrusion multi-layer die on an endless belt-like stainless steel support substrate, the polyamic acid solution B-2 / polyamic acid solution B-18 / polyamic acid solution B-2 in the order 3 The solvent was removed by continuously extruding and applying in a layer structure and drying by heating at 130 ° C. for 3 minutes. Thereafter, stepwise heat treatment is performed from 130 ° C. to 360 ° C. to complete imidization, and the thickness of the thermoplastic polyimide layer / non-thermoplastic polyimide layer / thermoplastic polyimide layer is 2.0 ⁇ m / 21 ⁇ m / 2.0 ⁇ m, respectively.
  • a polyimide film B-1 ′ was prepared.
  • the polyimide film B-1 ′ on the supporting substrate was peeled off by a knife edge method to prepare a long polyimide film B-1 having a length in the width direction of 1100 mm.
  • the evaluation results of the long polyimide film B-1 are as follows. CTE; 19ppm / K In-plane retardation (RO); 9 nm Variation in in-plane retardation (RO) in width direction (TD direction) ( ⁇ RO); 2 nm Change amount of in-plane retardation (RO) before and after pressurization under a temperature of 320 ° C. under a pressure of 340 MPa / m 2 and a holding period of 15 minutes; 13 nm Moisture absorption rate: 0.56% by weight Dielectric constant (10 GHz); 3.56, dielectric loss tangent (10 GHz); 0.0032
  • Example B-2 to Example B-18, Reference Example B-1 to Reference Example B-5 Example B-2 to Example B-18 and Reference Example B-1 to Reference Example B-5 were the same as Example B-1, except that the polyamic acid solutions shown in Tables 6 to 9 were used.
  • Long polyimide films B-2 to B-23 were obtained.
  • the amount of change in in-plane retardation (RO) before and after pressurization with a pressure of 340 MPa / m 2 and a holding period of 15 minutes, and the moisture absorption rate were determined.
  • the measurement results are shown in Tables 6 to 9.
  • Example B-19 On the surface of a long copper foil (rolled copper foil, manufactured by JX Metals Co., Ltd., trade name: GHY5-93F-HA-V2 foil, thickness: 12 ⁇ m, tensile modulus after heat treatment: 18 GPa), polyamic acid solution B -2 was uniformly applied so that the thickness after curing was 2.0 ⁇ m, and then dried by heating at 120 ° C. for 1 minute to remove the solvent. On top of this, the polyamic acid solution B-18 was uniformly applied so as to have a cured thickness of 21 ⁇ m, and then dried by heating at 120 ° C. for 3 minutes to remove the solvent.
  • the polyamic acid B-2 was uniformly applied thereon so that the thickness after curing was 2.0 ⁇ m, and then dried by heating at 120 ° C. for 1 minute to remove the solvent. Thereafter, stepwise heat treatment was performed from 130 ° C. to 360 ° C., and after imidization was completed, a single-sided copper-clad laminate B-1 was prepared. Copper foil is laminated on the polyimide layer side of this single-sided copper-clad laminate B-1, and thermocompression bonded for 15 minutes at a temperature of 320 ° C. and a pressure of 340 MPa / m 2 to prepare a double-sided copper-clad laminate B-1. did. Cast surface side peel strength: ⁇ , crimp side peel strength: ⁇
  • Example B-20 to Example B-36, Reference Example B-6 to Reference Example B-10 Example B-20 to Example B-36 and Reference Example B-6 to Reference Example B-10 were the same as Example B-19 except that the polyamic acid solutions shown in Table 10 to Table 13 were used. Double-sided copper-clad laminates B-2 to B-23 were obtained. Cast surface side peel strength and pressure-bonded surface side peel strength of the obtained double-sided copper clad laminates B-2 to B-23 were determined. Tables 10 to 13 show the measurement results.
  • the reaction vessel contained 616.159 parts by weight of m-TB (2.902 mole part) and 94.275 parts by weight of TPE-R (0.322 mole part) and the solid content concentration after polymerization. DMAc in an amount of 15% by weight was added and dissolved by stirring at room temperature. Next, after adding 415.723 parts by weight of PMDA (1.906 parts by mole) and 373.843 parts by weight of BPDA (1.271 parts by weight), the polymerization reaction was continued by stirring at room temperature for 3 hours, A polyamic acid solution C-3 was prepared. The solution viscosity of the polyamic acid solution C-3 was 31,500 cps.
  • Example C-1 A polyamic acid solution C-1 was uniformly applied to one side (surface roughness Rz; 0.6 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 25 ⁇ m, and then heat-dried at 120 ° C. The solvent was removed. Furthermore, stepwise heat treatment from 120 ° C. to 360 ° C. was performed within 30 minutes to complete imidization.
  • the copper foil was etched away using an aqueous ferric chloride solution, and polyimide film C-1 (CTE; 18.1 ppm / K, Tg; 322 ° C., moisture absorption rate: 0.57 wt%, HAZE; 74.5 %, Film elongation; 48%, dielectric constant; 3.42, dielectric loss tangent; 0.0028).
  • CTE 18.1 ppm / K, Tg; 322 ° C.
  • moisture absorption rate 0.57 wt%, HAZE; 74.5 %, Film elongation; 48%, dielectric constant; 3.42, dielectric loss tangent; 0.0028.
  • Example C-2 to Example C-9 and Reference Example C-1 to Reference Example C-2 Polyimide films C-2 to C-11 were prepared in the same manner as in Example C-1, except that the polyamic acid solution shown in Table 14 and Table 15 was used.
  • CTE, Tg, moisture absorption, HAZE, film elongation, dielectric constant and dielectric loss tangent were determined. These measurement results are shown in Tables 14 and 15.
  • Example C-10 A polyimide film C-12 (CTE; 10.2 ppm) was prepared in the same manner as in Example C-1, except that the polyamic acid solution C-11 was used and stepwise heat treatment was performed from 120 ° C. to 360 ° C. in 5 hours. / K, Tg: 307 ° C., moisture absorption: 0.61 wt%, HAZE: 74.2%, film elongation: 41%).
  • Example C-11 A polyamic acid solution C-15 was uniformly applied to one side (surface roughness Rz; 0.6 ⁇ m) of an electrolytic copper foil having a thickness of 12 ⁇ m so that the thickness after curing was about 2 to 3 ⁇ m, and then at 120 ° C. The solvent was removed by heating to dryness. Next, the polyamic acid solution C-1 was uniformly applied thereon so that the thickness after curing was about 21 ⁇ m, and dried by heating at 120 ° C. to remove the solvent. Further, the polyamic acid solution C-15 was uniformly applied thereon so that the thickness after curing was about 2 to 3 ⁇ m, and then dried by heating at 120 ° C. to remove the solvent.
  • a stepwise heat treatment from 120 ° C. to 360 ° C. was performed in 30 minutes to complete imidization, and a metal-clad laminate C-11 was prepared. Inconveniences such as swelling of the polyimide layer in the metal-clad laminate C-11 were not confirmed.
  • Example C-12 to Example C-17 Metal-clad laminates C-12 to C-17 were prepared in the same manner as in Example C-11 except that the polyamic acid solutions C-2 to C-7 were used instead of the polyamic acid solution C-1. . In any of the metal-clad laminates C-12 to C-17, problems such as swelling of the polyimide layer were not confirmed.
  • Example C-3 A metal-clad laminate was prepared in the same manner as in Example C-11 except that the stepwise heat treatment from 120 ° C. to 360 ° C. in Example C-11 was performed in 15 minutes, but it was confirmed that the polyimide layer was swollen. It was done.
  • Example C-18 to Example C-20 The procedure was carried out except that the polyamic acid solutions C-4 to C-6 were used in place of the polyamic acid solution C-1 in Example C-11, and stepwise heat treatment was performed from 120 ° C. to 360 ° C. in 15 minutes.
  • metal-clad laminates C-18 to C-20 were prepared. In any of the metal-clad laminates C-18 to C-20, defects such as swelling of the polyimide layer were not confirmed.
  • Example C-6 In place of the polyamic acid solution C-1 in Example C-11, the polyamic acid solutions C-2, C-3, and C-7 were used, and stepwise heat treatment was performed from 120 ° C. to 360 ° C. in 15 minutes. Except for the above, a metal-clad laminate was prepared in the same manner as in Example C-11. In any of the metal-clad laminates, swelling was confirmed in the polyimide layer.
  • Example C-21 to Example C-26 Polyimide films C-13 to C-18 were prepared in the same manner as in Example C-1, except that the polyamic acid solution shown in Table 16 was used. For polyimide films C-13 to C-18, CTE, Tg, dielectric constant and dielectric loss tangent were determined. These measurement results are shown in Table 16.
  • Example C-27 to Example C-30 The procedure was carried out except that the polyamic acid solutions C-15 to C-18 were used instead of the polyamic acid solution C-1 in Example C-11, and stepwise heat treatment was performed from 120 ° C. to 360 ° C. in 15 minutes.
  • metal-clad laminates C-27 to C-30 were prepared. In any of the metal-clad laminates C-27 to C-30, defects such as swelling of the polyimide layer were not confirmed.
  • Example C-31 to Example C-32 Polyimide films C-19 to C-20 were prepared in the same manner as in Example C-1, except that the polyamic acid solution shown in Table 17 was used. For the polyimide films C-19 to C-20, the CTE, Tg, dielectric constant and dielectric loss tangent were determined. These measurement results are shown in Table 17.

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