WO2022085619A1 - 非熱可塑性ポリイミドフィルム、複層ポリイミドフィルム、及び金属張積層板 - Google Patents

非熱可塑性ポリイミドフィルム、複層ポリイミドフィルム、及び金属張積層板 Download PDF

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WO2022085619A1
WO2022085619A1 PCT/JP2021/038393 JP2021038393W WO2022085619A1 WO 2022085619 A1 WO2022085619 A1 WO 2022085619A1 JP 2021038393 W JP2021038393 W JP 2021038393W WO 2022085619 A1 WO2022085619 A1 WO 2022085619A1
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thermoplastic polyimide
polyimide film
residue
acid dianhydride
mol
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English (en)
French (fr)
Japanese (ja)
Inventor
嵩浩 佐藤
誠二 細貝
真理 宇野
敬介 大熊
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Kaneka Corp
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Kaneka Corp
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Priority to KR1020237014946A priority Critical patent/KR20230090330A/ko
Priority to CN202180072102.2A priority patent/CN116419849A/zh
Priority to JP2022557512A priority patent/JP7791097B2/ja
Publication of WO2022085619A1 publication Critical patent/WO2022085619A1/ja
Priority to US18/137,757 priority patent/US20230265252A1/en
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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
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • 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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/16—Polyester-imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
    • B32B2379/08—Polyimides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate

Definitions

  • the present invention relates to a non-thermoplastic polyimide film, a multi-layer polyimide film, and a metal-clad laminate.
  • FPC flexible printed wiring boards
  • a polyimide film (polyimide layer) that exhibits a low dielectric loss tangent is known as a material used for a circuit board that can be adapted to high frequency (see, for example, Patent Documents 1 to 4).
  • Patent Documents 1 to 4 still have room for improvement in reducing the dielectric loss tangent.
  • the present invention has been made in view of the above subject, and an object thereof is to provide a non-thermoplastic polyimide film capable of reducing dielectric positivity, a multilayer polyimide film using the non-thermoplastic polyimide film, and a metal-clad laminate. To provide.
  • the first non-thermoplastic polyimide film according to the present invention contains a non-thermoplastic polyimide.
  • the non-thermoplastic polyimide has 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride residue and 4,4'-oxydiphthalic acid anhydride residue as tetracarboxylic acid dianhydride residue. It also has a p-phenylenediamine residue and a 1,3-bis (4-aminophenoxy) benzene residue as diamine residues.
  • the content of the 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride residue with respect to the total tetracarboxylic acid dianhydride residue constituting the non-thermoplastic polyimide was set to A 1 mol%, and the non-thermocarboxylic acid dianhydride residue was used.
  • the content of the 4,4'-oxydiphthalic acid anhydride residue with respect to the total tetracarboxylic acid dianhydride residue constituting the thermoplastic polyimide is set to A 2 mol%, and the total diamine residue constituting the non-plastic polyimide is used.
  • the content of the p-phenylenediamine residue with respect to B was 1 mol%, and the content of the 1,3-bis (4-aminophenoxy) benzene residue with respect to all the diamine residues constituting the non-thermoplastic polyimide was set.
  • B is 2 mol%, the relationship of A 1 + A 2 ⁇ 80, B 1 + B 2 ⁇ 80, and (A 1 + B 1 ) / (A 2 + B 2 ) ⁇ 3.50 is satisfied.
  • the A 1 , the A 2 , the B 1 and the B 2 are 1.60 ⁇ (A 1 + B 1 ) / (A 2 + B). 2 ) Satisfy the relationship of ⁇ 3.50.
  • the non-thermoplastic polyimide further has a pyromellitic acid dianhydride residue as a tetracarboxylic acid dianhydride residue.
  • the content of the pyromellitic acid dianhydride residue in the total tetracarboxylic acid dianhydride residue constituting the non-thermoplastic polyimide is determined. It is 3 mol% or more and 12 mol% or less.
  • the total amount of substance of the tetracarboxylic acid dianhydride residue constituting the non-thermoplastic polyimide is set to the diamine residue constituting the non-thermoplastic polyimide.
  • the amount of substance ratio divided by the total amount of substance of the group is 0.95 or more and 1.05 or less.
  • the non-thermoplastic polyimide film contains a crystal portion having a lamellar structure and an amorphous portion sandwiched between the crystal portions, and is X.
  • the lamellar period obtained by the ray scattering method is 15 nm or more.
  • the second non-thermoplastic polyimide film according to the present invention contains a crystal portion containing a non-thermoplastic polyimide and having a lamellar structure, and an amorphous portion sandwiched between the crystal portions, and is subjected to an X-ray scattering method.
  • the obtained lamellar cycle is 15 nm or more.
  • the multilayer polyimide film according to the present invention comprises a first or second non-thermoplastic polyimide film according to the present invention and an adhesive layer containing a thermoplastic polyimide arranged on at least one side of the non-thermoplastic polyimide film.
  • the adhesive layer is arranged on both sides of the non-thermoplastic polyimide film.
  • the first metal-clad laminate according to the present invention has a first or second non-thermoplastic polyimide film according to the present invention and a metal layer arranged on at least one side of the non-thermoplastic polyimide film.
  • the second metal-clad laminate according to the present invention has a multi-layer polyimide film according to the present invention and a metal layer arranged on the main surface of at least one of the adhesive layers of the multi-layer polyimide film.
  • non-thermoplastic polyimide film capable of reducing dielectric loss tangent
  • a multilayer polyimide film using the non-thermoplastic polyimide film and a metal-clad laminate.
  • the "structural unit” means a repeating unit constituting the polymer.
  • the "polyimide” is a polymer containing a structural unit represented by the following general formula (1) (hereinafter, may be referred to as “structural unit (1)").
  • X 1 represents a tetracarboxylic acid dianhydride residue (a tetravalent organic group derived from tetracarboxylic acid dianhydride), and X 2 is a diamine residue (divalent derived from diamine). Represents an organic group).
  • the content of the structural unit (1) with respect to all the structural units constituting the polyimide is, for example, 50 mol% or more and 100 mol% or less, preferably 60 mol% or more and 100 mol% or less, and more preferably 70 mol% or more. It is 100 mol% or less, more preferably 80 mol% or more and 100 mol% or less, still more preferably 90 mol% or more and 100 mol% or less, and may be 100 mol%.
  • linear expansion coefficient is a linear expansion coefficient at a temperature of 50 ° C to 250 ° C, unless otherwise specified.
  • the method for measuring the coefficient of linear expansion is the same as or similar to the embodiment described later.
  • the "relative permittivity” is the relative permittivity at a frequency of 10 GHz, a temperature of 23 ° C., and a relative humidity of 50%.
  • the "dielectric loss tangent” is a dielectric loss tangent at a frequency of 10 GHz, a temperature of 23 ° C., and a relative humidity of 50%.
  • the method for measuring the relative permittivity and the dielectric loss tangent is the same as or similar to the embodiment described later.
  • Non-thermoplastic polyimide refers to a polyimide that retains its film shape (flat film shape) when it is fixed to a metal fixing frame in the state of a film and heated at a heating temperature of 380 ° C. for 1 minute. ..
  • the "thermoplastic polyimide” refers to a polyimide that does not retain its film shape when it is fixed to a metal fixing frame in a film state and heated at a heating temperature of 380 ° C. for 1 minute.
  • the "main surface" of a layered material refers to a surface orthogonal to the thickness direction of the layered material.
  • the "lamellar cycle” refers to the distance between the centers of gravity of adjacent crystal portions (crystal portions having a lamellar structure) in a film containing a crystal portion having a lamellar structure and an amorphous portion sandwiched between the crystal portions. Amorphous parts (intermediate layer) that could not be crystallized exist between adjacent crystal parts, and a higher-order structure is formed in the film in which some of the amorphous parts are confined in the laminated lamellar structure. There is.
  • the lamellar period is determined by high-order structural analysis of the film using an X-ray scattering method (specifically, an ultra-small angle X-ray scattering method). The method for measuring the lamella cycle is the same as or similar to the embodiment described later.
  • Tetracarboxylic acid dianhydride may be referred to as "acid dianhydride”.
  • the non-thermoplastic polyimide contained in the non-thermoplastic polyimide film may be simply referred to as "non-thermoplastic polyimide”.
  • the thermoplastic polyimide contained in the adhesive layer may be simply referred to as "thermoplastic polyimide”.
  • Non-thermoplastic polyimide film F1 includes a non-thermoplastic polyimide.
  • the non-thermoplastic polyimide has 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride residue and 4,4'-oxydiphthalic acid anhydride residue as tetracarboxylic acid dianhydride residue.
  • a diamine residue it has a p-phenylenediamine residue and a 1,3-bis (4-aminophenoxy) benzene residue.
  • the content of 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride residue in the total tetracarboxylic acid dianhydride residue constituting the non-thermoplastic polyimide is A 1 mol%, and the non-thermoplastic polyimide is used.
  • the content of 4,4'-oxydiphthalic acid anhydride residue to all tetracarboxylic acid anhydride residues constituting the above is A 2 mol%, and p-phenylenediamine to all diamine residues constituting the non-thermoplastic polyimide.
  • BPDA 4,4'-biphenyltetracarboxylic acid dianhydride
  • ODPA 4,4'-Oxydiphthalic anhydride
  • P-phenylenediamine may be referred to as "PDA”.
  • 1,3-Bis (4-aminophenoxy) benzene may be referred to as "TPE-R”.
  • Pyromellitic acid dianhydride may be referred to as "PMDA”.
  • BTDA 3,3', 4,4'-benzophenone tetracarboxylic dianhydride
  • BTDA p-phenylene bis (trimellitic acid monoesteric acid anhydride)
  • TMHQ trimellitic acid monoesteric acid anhydride
  • a 1 + A 2 ⁇ 80 means that the total content of the BPDA residue and the ODPA residue with respect to the total tetracarboxylic acid dianhydride residue constituting the non-thermoplastic polyimide is 80. It means that it is more than mol%.
  • B 1 + B 2 ⁇ 80 means that the total content of the PDA residue and the TPE-R residue with respect to all the diamine residues constituting the non-thermoplastic polyimide is 80 mol% or more.
  • both the BPDA residue and the PDA residue are residues having a rigid structure.
  • the ODPA residue and the TPE-R residue are both residues having a bent structure.
  • “(A 1 + B 1 ) / (A 2 + B 2 )” is the abundance ratio of the residue having a rigid structure to the residue having a bent structure.
  • “(A 1 + B 1 ) / (A 2 + B 2 )” may be described as "rigidity / bending ratio”.
  • the dielectric loss tangent can be reduced. The reason is presumed as follows.
  • the total content of the BPDA residue and the ODPA residue with respect to all the tetracarboxylic acid dianhydride residues constituting the non-thermoplastic polyimide is 80 mol% or more and is non-thermal.
  • the total content of the PDA residue and the TPE-R residue with respect to all the diamine residues constituting the plastic polyimide is 80 mol% or more.
  • the rigidity / bending ratio is 3.50 or less.
  • a residue having a rigid structure and a residue having a bent structure are present in a balance suitable for obtaining a stable lamellar structure, so that a crystal having a lamellar structure is present.
  • the packing property of the part tends to be high.
  • the amorphous part confined in the laminated lamellar structure has a higher density than the amorphous part outside the laminated lamellar structure because the orientation is higher due to the adjacent lamellar structure. Therefore, it is considered that the amorphous portion confined in the laminated lamellar structure contributes less to the dielectric relaxation than the amorphous portion outside the laminated lamellar structure.
  • the "dielectric relaxation” is a phenomenon in which the dipoles of molecules fluctuate and energy is released when an external field such as an electric field is applied to the resin. In order to reduce the dielectric loss tangent, it is necessary to form a high-order structure in which dielectric relaxation is unlikely to occur.
  • the present inventors consider that by increasing the lamellar cycle and increasing the proportion of amorphous portions confined in the laminated lamellar structure, it is possible to form a higher-order structure in which dielectric relaxation is less likely to occur and reduce dielectric loss tangent. rice field.
  • the non-thermoplastic polyimide film F1 since the packing property of the crystal portion having a lamellar structure tends to be high, the distance between the adjacent crystal portions tends to be long, and the lamellar cycle tends to be long. Therefore, according to the non-thermoplastic polyimide film F1, the dielectric loss tangent can be reduced.
  • the rigidity / bending ratio is preferably 1.60 or more, and more preferably 1.70 or more.
  • the non-thermoplastic polyimide contained in the non-thermoplastic polyimide film F1 may have other acid dianhydride residues in addition to the BPDA residue and the ODPA residue.
  • the acid dianhydride (monomer) for forming other acid dianhydride residues include PMDA, BTDA, TMHQ, 2, 3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid dianhydride, 2, 2', 3,3'-benzophenone tetracarboxylic acid dianhydride, 3,4'-oxydiphthalic acid anhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 3,4,9 , 10-Pery
  • the other acid dianhydride residue may be one or more selected from the group consisting of PMDA residue, BTDA residue and TMHQ residue. preferable.
  • PMDA residues are preferable as other acid dianhydride residues.
  • the total content of the BPDA residue and the ODPA residue with respect to the total acid dianhydride residue constituting the non-thermoplastic polyimide is 83 mol. % Or more, preferably 85 mol% or more, 88 mol% or more, 90 mol% or more, 92 mol% or more, or 100 mol%.
  • the total content of the BPDA residue, the ODPA residue and the PMDA residue with respect to the dianhydride residue is preferably 85 mol% or more, more preferably 90 mol% or more, and even 100 mol%. I do not care.
  • the content of the BPDA residue with respect to the total acid dianhydride residue constituting the non-thermoplastic polyimide should be 20 mol% or more and 70 mol% or less. It is preferably 25 mol% or more and 65 mol% or less.
  • the content of the ODPA residue with respect to the total acid dianhydride residue constituting the non-thermoplastic polyimide should be 20 mol% or more and 70 mol% or less. It is preferably 30 mol% or more and 60 mol% or less.
  • the content of PMDA residues in the total acid dianhydride residues constituting the non-thermoplastic polyimide is 1 mol%. It is preferably 15 mol% or more, and more preferably 3 mol% or more and 12 mol% or less.
  • the content of the BTDA residue with respect to the total acid dianhydride residue constituting the non-thermoplastic polyimide should be 1 mol% or more and 5 mol% or less. It is preferably 2 mol% or more and 4 mol% or less.
  • the content of TMHQ residues with respect to the total acid dianhydride residues constituting the non-thermoplastic polyimide should be 4 mol% or more and 8 mol% or less. It is preferably present, and more preferably 5 mol% or more and 7 mol% or less.
  • the non-thermoplastic polyimide contained in the non-thermoplastic polyimide film F1 may have other diamine residues in addition to the PDA residue and the TPE-R residue.
  • diamine (monomer) for forming other diamine residues include 1,4-bis (4-aminophenoxy) benzene, 4, 4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenyl ether, 3,4'-Diaminodiphenyl ether, 1,5-diaminonaphthalene, 4,4'-diaminodiphenyldiethylsilane, 4,4'
  • the total content of the PDA residue and the TPE-R residue with respect to all the diamine residues constituting the non-thermoplastic polyimide is 85 mol%.
  • the above is preferable, 90 mol% or more is more preferable, 95 mol% or more is further preferable, and 100 mol% may be used.
  • the content of PDA residues with respect to all diamine residues constituting the non-thermoplastic polyimide should be 70 mol% or more and 98 mol% or less. It is more preferably 80 mol% or more and 95 mol% or less.
  • the content of TPE-R residues with respect to all diamine residues constituting the non-thermoplastic polyimide is 2 mol% or more and 30 mol% or less. It is preferably 5 mol% or more and 20 mol% or less.
  • the total amount of substance of the acid dianhydride residue constituting the non-thermoplastic polyimide is determined, and the total substance of the diamine residue constituting the non-thermoplastic polyimide is used.
  • the substance amount ratio divided by the amount is preferably 0.95 or more and 1.05 or less, more preferably 0.97 or more and 1.03 or less, and preferably 0.99 or more and 1.01 or less. More preferred.
  • the non-thermoplastic polyimide film F1 may contain components (additives) other than the non-thermoplastic polyimide.
  • a dye, a surfactant, a leveling agent, a plasticizer, a silicone, a filler, a sensitizer and the like can be used as the additive.
  • the content of the non-thermoplastic polyimide in the non-thermoplastic polyimide film F1 is, for example, 70% by weight or more, preferably 80% by weight or more, preferably 90% by weight, based on the total amount of the non-thermoplastic polyimide film F1. The above is more preferable, and it may be 100% by weight.
  • non-thermoplastic polyimide film F1 which can further reduce the dielectric loss tangent and has a small coefficient of linear expansion
  • Condition 1 The non-thermoplastic polyimide has only PDA residues and TPE-R residues as diamine residues, and the rigidity / bending ratio is 1.60 or more and 3.50 or less.
  • Condition 2 The non-thermoplastic polyimide satisfying the above condition 1 further has a PMDA residue as an acid dianhydride residue.
  • Condition 3 The total content of the BPDA residue, the ODPA residue, and the PMDA residue with respect to the total acid dianhydride residue satisfying the above condition 2 and constituting the non-thermoplastic polyimide is 90 mol% or more and 100 mol. % Or less.
  • Condition 4 The content of PMDA residue with respect to the total acid dianhydride residue satisfying the above condition 3 and constituting the non-thermoplastic polyimide is 3 mol% or more and 12 mol% or less.
  • the non-thermoplastic polyimide contained in the non-thermoplastic polyimide film F1 is obtained by imidizing the polyamic acid as a precursor thereof.
  • any known method or a method in which they are combined can be used.
  • a diamine is usually reacted with a tetracarboxylic acid dianhydride in an organic solvent. It is preferable that the amount of substance of diamine and the amount of substance of tetracarboxylic acid dianhydride in the reaction are substantially the same.
  • a desired polyamic acid (with diamine) can be obtained by adjusting the amount of each diamine and the amount of each tetracarboxylic acid dianhydride.
  • a polymer with tetracarboxylic acid dianhydride can be obtained.
  • the mole fraction of each residue in the polyimide formed from the polyamic acid is consistent with, for example, the mole fraction of each monomer (diamine and tetracarboxylic acid dianhydride) used in the synthesis of the polyamic acid.
  • the temperature condition of the reaction between the diamine and the tetracarboxylic acid dianhydride, that is, the synthetic reaction of the polyamic acid is not particularly limited, but is, for example, in the range of 10 ° C. or higher and 150 ° C. or lower.
  • the reaction time of the polyamic acid synthesis reaction is, for example, in the range of 10 minutes or more and 30 hours or less.
  • any method of adding a monomer may be used for producing the polyamic acid. The following methods can be mentioned as a typical method for producing a polyamic acid.
  • Examples of the method for producing a polyamic acid include a method of polymerizing by the following steps (Aa) and (Ab) (hereinafter, may be referred to as "A polymerization method").
  • a polymerization method A step of reacting a diamine and an acid dianhydride in an organic solvent in an excess of diamine to obtain a prepolymer having amino groups at both ends
  • A-b Step (A).
  • a diamine having a structure different from that used in (a) was additionally added, and an acid dianhydride having a structure different from that used in the step (Aa) was added to the diamine and the acid dianhydride in all the steps. Step of adding and polymerizing so that
  • B polymerization method A method of polymerizing by the following steps (Ba) and the step (Bb) (hereinafter, may be referred to as “B polymerization method”) can also be mentioned.
  • B-a) A step of reacting a diamine and an acid dianhydride in an organic solvent with an excess of the acid dianhydride to obtain a prepolymer having an acid anhydride group at both ends (B-b).
  • An acid dianhydride having a structure different from that used in the step (BA) is additionally added, and a diamine having a structure different from that used in the step (BA) is added to the diamine in all the steps. Step of adding and polymerizing acid dianhydride so as to be substantially equimolar
  • a polymerization method for setting the order of addition so that a specific diamine or a specific acid dianhydride selectively reacts with an arbitrary or specific diamine, or an arbitrary or specific acid dianhydride (for example, the above-mentioned A polymerization method). , B polymerization method, etc.) is described as sequence polymerization in this specification.
  • a polymerization method in which the order of addition of diamine and acid dianhydride is not set (a polymerization method in which monomers react arbitrarily with each other) is described as random polymerization in the present specification.
  • step (Aa), steps (BA), etc.) are used.
  • step (Ab), step (Bb), etc. is described as “2nd sequence polymerization step”.
  • sequence polymerization is preferable as the polymerization method of the polyamic acid.
  • a method of obtaining a non-thermoplastic polyimide from a polyamic acid solution containing a polyamic acid and an organic solvent may be adopted.
  • the organic solvent that can be used in the polyamic acid solution include urea-based solvents such as tetramethylurea and N, N-dimethylethylurea; sulfoxide-based solvents such as dimethylsulfoxide; and diphenylsulfones and tetramethylsulfones.
  • N N-dimethylacetamide
  • N N-dimethylformamide
  • N N-diethylacetamide
  • N-methyl-2-pyrrolidone hexamethylphosphate
  • Amid solvents such as triamide; ester solvents such as ⁇ -butyrolactone; alkyl halide solvents such as chloroform and methylene chloride; aromatic hydrocarbon solvents such as benzene and toluene; phenol solvents such as phenol and cresol; cyclo Ketone-based solvents such as pentanone; ether-based solvents such as tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, dimethyl ether, diethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, and p-cresol methyl ether can be mentioned.
  • the reaction solution solution after the reaction
  • the organic solvent in the polyamic acid solution is the organic solvent used in the reaction in the above polymerization method.
  • a solid polyamic acid obtained by removing the solvent from the reaction solution may be dissolved in an organic solvent to prepare a polyamic acid solution.
  • Additives such as dyes, surfactants, leveling agents, plasticizers, silicones, fillers and sensitizers may be added to the polyamic acid solution.
  • concentration of the polyamic acid in the polyamic acid solution is not particularly limited, and is, for example, 5% by weight or more and 35% by weight or less, preferably 8% by weight or more and 30% by weight or less, based on the total amount of the polyamic acid solution.
  • concentration of polyamic acid is 5% by weight or more and 35% by weight or less, an appropriate molecular weight and solution viscosity can be obtained.
  • the method for obtaining the non-thermoplastic polyimide film F1 using the polyamic acid solution is not particularly limited, and various known methods can be applied.
  • the non-thermoplastic polyimide film F1 is subjected to the following steps i) to iii). There is a method to obtain.
  • the method for obtaining the non-thermoplastic polyimide film F1 through steps i) to iii) is roughly classified into a thermal imidization method and a chemical imidization method.
  • the thermal imidization method is a method in which a polyamic acid solution is applied as a dope solution on a support and heated to proceed with imidization without using a dehydration ring closure agent or the like.
  • the chemical imidization method is a method of promoting imidization by using a polyamic acid solution to which at least one of a dehydration ring closure agent and a catalyst is added as a dope solution. Either method may be used, but the chemical imidization method is more productive.
  • the dehydration ring closure agent an acid anhydride typified by acetic anhydride is preferably used.
  • the catalyst tertiary amines such as aliphatic tertiary amines, aromatic tertiary amines, and heterocyclic tertiary amines (more specifically, isoquinoline and the like) are preferably used.
  • the dehydration ring closure agent and the catalyst may be added directly without being dissolved in an organic solvent, or those dissolved in an organic solvent may be added.
  • the reaction may proceed rapidly before at least one of the dehydration ring closure agent and the catalyst diffuses, and a gel may be formed. Therefore, it is preferable to add a solution (imidization accelerator) obtained by dissolving at least one of the dehydration ring closure agent and the catalyst in an organic solvent to the polyamic acid solution.
  • the method of applying the dope solution onto the support is not particularly limited, and a method using a conventionally known coating device such as a die coater, a comma coater (registered trademark), a reverse coater, or a knife coater is adopted. can.
  • step ii) As the support to which the dope liquid is applied in step i), a glass plate, aluminum foil, an endless stainless belt, a stainless drum, or the like is preferably used.
  • the drying conditions (heating conditions) of the coating film are set according to the thickness of the finally obtained film and the production rate, and the dried polyamic acid film (gel film) is peeled off from the support.
  • the drying temperature of the coating film is, for example, 50 ° C. or higher and 200 ° C. or lower.
  • the drying time for drying the coating film is, for example, 1 minute or more and 100 minutes or less.
  • step iii) for example, water, a residual solvent, an imidization accelerator, etc. are removed from the gel film by fixing the end portion of the gel film and heat-treating it while avoiding shrinkage during curing.
  • the remaining polyamic acid is completely imidized to obtain a non-thermoplastic polyimide film F1 containing a non-thermoplastic polyimide.
  • the heating conditions are appropriately set according to the thickness of the finally obtained film and the production rate.
  • the heating conditions of the step iii) the maximum temperature is, for example, 370 ° C. or higher and 420 ° C. or lower, and the heating time at the maximum temperature is, for example, 10 seconds or longer and 180 seconds or lower.
  • Step iii) can be performed under air, under reduced pressure, or in an inert gas such as nitrogen.
  • the heating device that can be used in the step iii) is not particularly limited, and examples thereof include a hot air circulation oven and a far infrared oven.
  • non-thermoplastic polyimide film F1 can reduce dielectric loss tangent, for example, a material for a high-frequency circuit board (more specifically, a core layer of a multi-layer polyimide film and an insulating layer of a metal-clad laminate). Etc.).
  • the lamella period of the non-thermoplastic polyimide film F1 is preferably 15 nm or more, more preferably 20 nm or more, and more preferably 23 nm or more.
  • the upper limit of the lamella cycle of the non-thermoplastic polyimide film F1 is not particularly limited, but is, for example, 60 nm.
  • the lamella cycle of the non-thermoplastic polyimide film F1 is, for example, the content of each residue constituting the non-thermoplastic polyimide and the heating conditions (more specifically, the maximum temperature and the heating time at the maximum temperature) in the above step iii). Etc.) can be adjusted by changing at least one of them.
  • the relative permittivity of the non-thermoplastic polyimide film F1 is 3.60 or less.
  • the dielectric loss tangent of the non-thermoplastic polyimide film F1 is preferably 0.0050 or less, more preferably 0.0040 or less, and less than 0.0030. Is more preferable.
  • the linear expansion coefficient of the non-thermoplastic polyimide film F1 is preferably 25 ppm / K or less, more preferably 18 ppm / K or less. It is more preferably 16 ppm / K or less.
  • the thickness of the non-thermoplastic polyimide film F1 is not particularly limited, but is, for example, 5 ⁇ m or more and 50 ⁇ m or less.
  • the thickness of the non-thermoplastic polyimide film F1 can be measured using a laser holo gauge.
  • non-thermoplastic polyimide film F2 the non-thermoplastic polyimide film according to the second embodiment of the present invention.
  • the description of the content overlapping with the first embodiment may be omitted.
  • the differences from the first embodiment non-thermoplastic polyimide film F1 will be mainly described.
  • the non-thermoplastic polyimide film F2 contains a crystal portion containing non-thermoplastic polyimide and having a lamellar structure, and an amorphous portion sandwiched between the crystal portions, and the lamellar period obtained by the X-ray scattering method is 15 nm. That is all.
  • the non-thermoplastic polyimide film F2 can reduce the dielectric loss tangent by having the above-mentioned configuration.
  • the non-thermoplastic polyimide film F2 is not particularly limited as long as the above configuration is satisfied. However, in the second embodiment, in order to easily adjust the lamella cycle to 15 nm or more, it is preferable to satisfy the following conditions A, and it is more preferable to satisfy the following conditions A and B.
  • Condition A The non-thermoplastic polyimide has a BPDA residue and an ODPA residue as a tetracarboxylic acid dianhydride residue, and has a PDA residue and a TPE-R residue as a diamine residue.
  • the content of the BPDA residue with respect to the total tetracarboxylic acid dianhydride residue constituting the non-thermoplastic polyimide is A 1 mol%, and the content with respect to the total tetracarboxylic acid dianhydride residue constituting the non-thermoplastic polyimide is set.
  • the content of ODPA residues is A 2 mol%
  • the content of PDA residues with respect to all diamine residues constituting the non-thermoplastic polyimide is B 1 mol%
  • the content of PDA residues is B 1 mol% with respect to all diamine residues constituting the non-thermoplastic polyimide.
  • non-thermoplastic polyimide film> section [non-thermoplastic polyimide] section, [non-thermoplastic polyimide film F1 manufacturing method] section]. , And [including the section [Physical properties of non-thermoplastic polyimide film F1]).
  • the multilayer polyimide film according to the third embodiment has a non-thermoplastic polyimide film F1 or a non-thermoplastic polyimide film F2 and an adhesive layer containing a thermoplastic polyimide.
  • non-thermoplastic polyimide film F1 or non-thermoplastic polyimide film F2 may be referred to as "specific non-thermoplastic polyimide film”.
  • FIG. 1 is a cross-sectional view showing an example of a multilayer polyimide film according to a third embodiment.
  • the multilayer polyimide film 10 is an adhesion containing a thermoplastic polyimide disposed on at least one side (one main surface) of the specific non-thermoplastic polyimide film 11 and the specific non-thermoplastic polyimide film 11. It has a layer 12.
  • the adhesive layer 12 is provided only on one side of the specific non-thermoplastic polyimide film 11, but it is adhered to both sides (both main surfaces) of the specific non-thermoplastic polyimide film 11.
  • the layer 12 may be provided.
  • the two adhesive layers 12 may contain the same type of polyimide or may contain different types of polyimides. Further, the thicknesses of the two adhesive layers 12 may be the same or different.
  • the "multi-layer polyimide film 10" includes a film in which the adhesive layer 12 is provided on only one side of the specific non-thermoplastic polyimide film 11 and an adhesive layer 12 on both sides of the specific non-thermoplastic polyimide film 11. Is included with the film provided with.
  • the thickness of the multilayer polyimide film 10 (total thickness of each layer) is, for example, 6 ⁇ m or more and 60 ⁇ m or less.
  • the thickness of the multilayer polyimide film 10 is preferably 7 ⁇ m or more and 60 ⁇ m or less, and 10 ⁇ m or more and 60 ⁇ m or less. Is more preferable.
  • the thickness of the multilayer polyimide film 10 can be measured using a laser holo gauge.
  • the thickness of the adhesive layer 12 (when two adhesive layers 12 are provided, the thickness of each adhesive layer 12). Is preferably 1 ⁇ m or more and 15 ⁇ m or less. Further, in order to easily adjust the linear expansion coefficient of the multilayer polyimide film 10, the thickness ratio between the specific non-thermoplastic polyimide film 11 and the adhesive layer 12 (thickness of the specific non-thermoplastic polyimide film 11 / adhesive layer 12). The thickness) is preferably 55/45 or more and 95/5 or less. When two adhesive layers 12 are provided, the thickness of the adhesive layer 12 is the total thickness of the adhesive layer 12.
  • the adhesive layers 12 are provided on both sides of the specific non-thermoplastic polyimide film 11, and the same type of polyimide is provided on both sides of the specific non-thermoplastic polyimide film 11. It is more preferable that the adhesive layer 12 containing the above is provided.
  • the thicknesses of the two adhesive layers 12 are the same in order to suppress the warp of the multi-layer polyimide film 10. ..
  • the thickness of the other adhesive layer 12 is in the range of 40% or more and less than 100% when the thickness of the thicker adhesive layer 12 is used as a reference. , The warp of the multi-layer polyimide film 10 can be suppressed.
  • the thermoplastic polyimide contained in the adhesive layer 12 has an acid dianhydride residue and a diamine residue.
  • the acid dianhydride (monomer) for forming the acid dianhydride residue in the thermoplastic polyimide is an acid dianhydride for forming the acid dianhydride residue in the non-thermoplastic polyimide described above (monomer).
  • the same compound as the monomer) can be mentioned.
  • the acid dianhydride residue contained in the thermoplastic polyimide and the acid dianhydride residue contained in the non-thermoplastic polyimide may be of the same type or different types from each other.
  • the diamine residue of the thermoplastic polyimide is preferably a diamine residue having a bent structure.
  • the content of the diamine residue having a bent structure is preferably 50 mol% or more, preferably 70 mol% or more, based on the total diamine residue constituting the thermoplastic polyimide. % Or more is more preferable, 80 mol% or more is further preferable, and 100 mol% may be used.
  • the diamine (monomer) for forming a diamine residue having a bent structure include 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, and 1,3.
  • BAPP 2,2-bis [4- (4-aminophenoxy) phenyl] propane
  • thermoplastic polyimide has one or more selected from the group consisting of BPDA residues and PMDA residues, and BAPP residues.
  • the adhesive layer 12 may contain a component (additive) other than the thermoplastic polyimide.
  • a component (additive) other than the thermoplastic polyimide for example, a dye, a surfactant, a leveling agent, a plasticizer, a silicone, a filler, a sensitizer and the like can be used.
  • the content of the thermoplastic polyimide in the adhesive layer 12 is, for example, 70% by weight or more, preferably 80% by weight or more, and more preferably 90% by weight or more, based on the total amount of the adhesive layer 12. , 100% by weight.
  • the adhesive layer 12 may be described as, for example, a polyamic acid solution containing a polyamic acid which is a precursor of the thermoplastic polyimide (hereinafter, “thermoplastic polyamic acid solution”) on at least one surface of the specific non-thermoplastic polyimide film 11. ) Is applied, and then heated (drying and imidization of polyamic acid) to form the film.
  • thermoplastic polyamic acid solution a polyamic acid solution containing a polyamic acid which is a precursor of the thermoplastic polyimide (hereinafter, “thermoplastic polyamic acid solution”) on at least one surface of the specific non-thermoplastic polyimide film 11.
  • thermoplastic polyamic acid solution a solution containing thermoplastic polyimide (thermoplastic polyimide solution) is used to form a coating film made of the thermoplastic polyimide solution on at least one side of the specific non-thermoplastic polyimide film 11.
  • the coating film may be dried to form the adhesive layer 12.
  • a layer containing polyamic acid which is a precursor of the non-thermoplastic polyimide of the specific non-thermoplastic polyimide film 11, and a precursor of the thermoplastic polyimide are used on the support.
  • the obtained laminate may be heated to form the specific non-thermoplastic polyimide film 11 and the adhesive layer 12 at the same time.
  • a metal-clad laminate a laminate of a multilayer polyimide film 10 and a metal foil
  • the above-mentioned coating step and heating step are repeated a plurality of times, or a plurality of coating films are formed by coextrusion or continuous coating (continuous casting) at one time.
  • the heating method is preferably used. It is also possible to perform various surface treatments such as corona treatment and plasma treatment on the outermost surface of the multilayer polyimide film 10.
  • metal-clad laminate M1 has a specific non-thermoplastic polyimide film and a metal layer arranged on at least one side (one main surface) of the specific non-thermoplastic polyimide film.
  • the description of the contents overlapping with the first embodiment and the second embodiment may be omitted.
  • a first plating layer is formed on one side or both sides of a specific non-thermoplastic polyimide film by a dry plating method, and then a wet plating method (electroless plating method, electrolytic plating) is performed on the first plating layer. It is obtained by forming a second plating layer by a method or the like).
  • the dry plating method include a PVD method (more specifically, a vacuum vapor deposition method, a sputtering method, an ion plating method, etc.), a CVD method, and the like.
  • the thickness (total thickness) of the metal layer composed of the first plating layer and the second plating layer is, for example, 1 ⁇ m or more and 50 ⁇ m or less.
  • the method for obtaining the metal-clad laminate M1 includes, for example, polyamic acid which is a precursor of a non-thermoplastic polyimide (specifically, a non-thermoplastic polyimide possessed by a specific non-thermoplastic polyimide film).
  • a method of heating the coating film formed on the metal foil after applying the solution on the metal foil (hereinafter, may be referred to as “coating method”) can also be mentioned.
  • coating method By heating the coating film, the solvent is removed and imidized on the metal foil, and the metal-clad laminate M1 is a laminate of the specific non-thermoplastic polyimide film and the metal layer made of the metal foil. Is obtained.
  • the coating device for coating the solution containing polyamic acid on the metal foil is not particularly limited, and examples thereof include a die coater, a comma coater (registered trademark), a reverse coater, and a knife coater.
  • the heating device for heating the coating film is also not particularly limited, and for example, a hot air circulation oven, a far infrared oven, or the like can be used.
  • the metal foil that can be used in the coating method is not particularly limited.
  • a metal foil made of copper, stainless steel, nickel, aluminum, an alloy of these metals, or the like is preferably used.
  • copper foil such as rolled copper foil and electrolytic copper foil is often used, but the copper foil is also preferably used in the fourth embodiment.
  • the metal foil one that has been subjected to surface treatment or the like according to the purpose and whose surface roughness or the like has been adjusted can be used. Further, a rust preventive layer, a heat resistant layer, an adhesive layer and the like may be formed on the surface of the metal foil.
  • the thickness of the metal foil is not particularly limited, and may be any thickness as long as it can exhibit sufficient functions depending on the intended use. In order to easily realize the thinning of the FPC while ensuring the handleability, the thickness of the metal foil is preferably 5 ⁇ m or more and 50 ⁇ m or less.
  • metal-clad laminate M2 has a multi-layer polyimide film according to a third embodiment and a metal layer arranged on the main surface of at least one adhesive layer of the multi-layer polyimide film.
  • the description of the contents overlapping with the first embodiment, the second embodiment, and the third embodiment may be omitted.
  • FIG. 2 is a cross-sectional view showing an example of the metal-clad laminate M2.
  • the metal-clad laminate 20 has a multi-layer polyimide film 10 and a metal layer 13 (metal foil) arranged on the main surface 12a of the adhesive layer 12 of the multi-layer polyimide film 10.
  • a thermal roll laminating device having a pair or more of metal rolls or a continuous processing method using a double belt press (DBP) can be adopted.
  • the specific configuration of the means for performing the thermal roll laminating is not particularly limited, but in order to improve the appearance of the obtained metal-clad laminate 20, protection is provided between the pressure surface and the metal foil. It is preferable to arrange the material.
  • the double-sided metal-clad laminate (shown) is formed by laminating metal foils on both sides (both main surfaces) of the multi-layer polyimide film 10. Z) is obtained.
  • the metal foil to be the metal layer 13 is not particularly limited, and any metal foil can be used.
  • a metal foil made of copper, stainless steel, nickel, aluminum, an alloy of these metals, or the like is preferably used.
  • copper foil such as rolled copper foil and electrolytic copper foil is often used, but the copper foil is also preferably used in the fifth embodiment.
  • the metal foil one that has been subjected to surface treatment or the like according to the purpose and whose surface roughness or the like has been adjusted can be used.
  • a rust preventive layer, a heat resistant layer, an adhesive layer and the like may be formed on the surface of the metal foil.
  • the thickness of the metal foil is not particularly limited, and may be any thickness as long as it can exhibit sufficient functions depending on the intended use.
  • the thickness of the metal foil is preferably 5 ⁇ m or more and 50 ⁇ m or less in order to easily realize the thinning of the FPC while suppressing the generation of wrinkles when the multi-layer polyimide film 10 is bonded.
  • the lamella cycle was calculated by the following method using the software "SmartLab Studio II (Powder XRD)" and "2DP" manufactured by Rigaku.
  • the two-dimensional SAXS image obtained by the above procedure and the blank thereof were circularly averaged by the software "2DP” manufactured by Rigaku Corporation to obtain a one-dimensional SAXS pattern and a blank SAXS pattern, respectively.
  • the background of the one-dimensional SAXS pattern was removed by using the blank SAXS pattern as the background data. When the background was removed, the X-ray scattering intensity ratio was calculated from the direct beam intensities of both, and the intensity was corrected.
  • the separation peak of 2 ⁇ ⁇ 1 ° was identified as the peak derived from the lamella cycle, and the lamella cycle d was calculated from the scattering vector q of the peak derived from the lamella cycle.
  • the relative permittivity and the dielectric loss tangent of the polyimide film were measured by a network analyzer ("8719C” manufactured by Hewlett-Packard Co., Ltd.) and a cavity resonator permittivity measuring device ("CP531" manufactured by EM Lab Co., Ltd.). Specifically, first, the polyimide film was cut into 2 mm ⁇ 100 mm, and a sample for measuring the relative permittivity and the dielectric loss tangent was prepared. Next, the measurement sample was left to stand in an atmosphere having a temperature of 23 ° C.
  • the temperature was 23 ° C. and the relative humidity was 50. %
  • the relative permittivity and the dielectric tangent were measured under the condition of the measurement frequency of 10 GHz.
  • the dielectric loss tangent was less than 0.0030, it was evaluated that "the dielectric loss tangent could be reduced”.
  • the dielectric loss tangent was 0.0030 or more, it was evaluated that "the dielectric loss tangent could not be reduced”.
  • Example 1 After putting 164.2 g of DMF, 3.0 g of TPE-R and 6.4 g of PDA in a glass flask with a capacity of 500 mL, the contents of the flask were stirred and the flask was filled with 12.2 g of BPDA. And 7.9 g of ODPA were added. The flask contents were then stirred for 30 minutes. Next, while stirring the contents of the flask, the PMDA solution (solvent: DMF, dissolution amount of PMDA: 0.5 g, concentration of PMDA: 7.9% by weight) prepared in advance was added to the viscosity of the contents of the flask.
  • solvent solvent
  • dissolution amount of PMDA 0.5 g
  • concentration of PMDA 7.9% by weight
  • the addition was continued to the flask for a predetermined time at an addition rate that did not increase sharply. Then, when the viscosity of the flask contents at a temperature of 23 ° C. reached 1500 poisons, the addition of the PMDA solution was stopped, and the flask contents were further stirred for 1 hour to obtain a polyamic acid solution P1.
  • the obtained polyamic acid solution P1 had a solid content concentration of 15% by weight.
  • the obtained polyamic acid solution P1 had a viscosity of 1500 to 2000 poise at a temperature of 23 ° C.
  • the obtained gel film was peeled off from the aluminum foil, fixed to a metal fixing frame, placed in a hot air circulation oven preheated to a temperature of 300 ° C., and heated at a heating temperature of 300 ° C. for 56 seconds.
  • the heated film is placed in a far-infrared (IR) oven preheated to a temperature of 380 ° C. and heated at a heating temperature of 380 ° C. for 49 seconds to imidize the polyamic acid in the gel film, and then the metal.
  • IR far-infrared
  • the polyimide film obtained by the same procedure as above was fixed to a metal fixing frame and heated at a heating temperature of 380 ° C. for 1 minute using an IR oven, the shape of the polyimide film (film shape) was maintained. rice field. Therefore, the polyimide contained in the polyimide film of Example 1 was a non-thermoplastic polyimide. That is, the polyimide film of Example 1 was a non-thermoplastic polyimide film.
  • the polyimide films obtained by the same procedure as below are fixed to metal fixing frames, respectively, and the heating temperature is heated using an IR oven. When heated at 380 ° C.
  • the shape of the polyimide film was maintained. Therefore, the polyimides contained in the polyimide films of Examples 2 to 37 and Comparative Examples 1 to 8 were all non-thermoplastic polyimides. That is, the polyimide films of Examples 2 to 37 and Comparative Examples 1 to 8 were all non-thermoplastic polyimide films.
  • Example 2 After putting 164.1 g of DMF, 2.5 g of TPE-R and 6.7 g of PDA in a glass flask with a capacity of 500 mL, 12.4 g of BPDA was placed in the flask while stirring the contents of the flask. And 8.0 g of ODPA. The flask contents were then stirred for 30 minutes. Next, while stirring the contents of the flask, the PMDA solution (solvent: DMF, dissolution amount of PMDA: 0.5 g, concentration of PMDA: 7.8% by weight) prepared in advance was added to the viscosity of the contents of the flask. The addition was continued to the flask for a predetermined time at an addition rate that did not increase sharply.
  • solvent solvent
  • dissolution amount of PMDA 0.5 g
  • concentration of PMDA 7.8% by weight
  • the obtained polyamic acid solution P2 had a solid content concentration of 15% by weight.
  • the obtained polyamic acid solution P2 had a viscosity of 1500 to 2000 poise at a temperature of 23 ° C.
  • the obtained gel film was peeled off from the aluminum foil, fixed to a metal fixing frame, placed in a hot air circulation oven preheated to a temperature of 300 ° C., and heated at a heating temperature of 300 ° C. for 56 seconds. Next, the heated film is placed in an IR oven preheated to a temperature of 380 ° C. and heated at a heating temperature of 380 ° C. for 49 seconds to imidize the polyamic acid in the gel film, and then a fixed frame made of metal.
  • the polyimide film of Example 2 (thickness: 17 ⁇ m) was obtained.
  • Example 3 After putting 164.1 g of DMF, 2.5 g of TPE-R and 6.7 g of PDA in a glass flask with a capacity of 500 mL, 12.5 g of BPDA is placed in the flask while stirring the contents of the flask. , 7.4 g of ODPA and 0.5 g of PMDA were added. The flask contents were then stirred for 30 minutes. Next, while stirring the contents of the flask, the PMDA solution (solvent: DMF, dissolution amount of PMDA: 0.5 g, concentration of PMDA: 7.8% by weight) prepared in advance was added to the viscosity of the contents of the flask.
  • solvent solvent
  • dissolution amount of PMDA 0.5 g
  • concentration of PMDA 7.8% by weight
  • the addition was continued to the flask for a predetermined time at an addition rate that did not increase sharply. Then, when the viscosity of the flask contents at a temperature of 23 ° C. reached 1500 poisons, the addition of the PMDA solution was stopped, and the flask contents were further stirred for 1 hour to obtain a polyamic acid solution P3.
  • the obtained polyamic acid solution P3 had a solid content concentration of 15% by weight.
  • the obtained polyamic acid solution P3 had a viscosity of 1500 to 2000 poise at a temperature of 23 ° C.
  • the obtained gel film was peeled off from the aluminum foil, fixed to a metal fixing frame, placed in a hot air circulation oven preheated to a temperature of 300 ° C., and heated at a heating temperature of 300 ° C. for 56 seconds. Next, the heated film is placed in an IR oven preheated to a temperature of 380 ° C. and heated at a heating temperature of 380 ° C. for 49 seconds to imidize the polyamic acid in the gel film, and then a fixed frame made of metal.
  • the polyimide film of Example 3 (thickness: 17 ⁇ m) was obtained.
  • Example 4 After putting 164.1 g of DMF, 2.5 g of TPE-R and 6.7 g of PDA in a glass flask with a capacity of 500 mL, 12.4 g of BPDA was placed in the flask while stirring the contents of the flask. , 7.4 g of ODPA and 0.7 g of BTDA. The flask contents were then stirred for 30 minutes. Next, while stirring the contents of the flask, the PMDA solution (solvent: DMF, dissolution amount of PMDA: 0.5 g, concentration of PMDA: 7.8% by weight) prepared in advance was added to the viscosity of the contents of the flask.
  • solvent solvent
  • dissolution amount of PMDA 0.5 g
  • concentration of PMDA 7.8% by weight
  • the addition was continued to the flask for a predetermined time at an addition rate that did not increase sharply. Then, when the viscosity of the flask contents at a temperature of 23 ° C. reached 1500 poisons, the addition of the PMDA solution was stopped, and the flask contents were further stirred for 1 hour to obtain a polyamic acid solution P4.
  • the obtained polyamic acid solution P4 had a solid content concentration of 15% by weight.
  • the obtained polyamic acid solution P4 had a viscosity of 1500 to 2000 poise at a temperature of 23 ° C.
  • the obtained gel film was peeled off from the aluminum foil, fixed to a metal fixing frame, placed in a hot air circulation oven preheated to a temperature of 300 ° C., and heated at a heating temperature of 300 ° C. for 56 seconds. Next, the heated film is placed in an IR oven preheated to a temperature of 380 ° C. and heated at a heating temperature of 380 ° C. for 49 seconds to imidize the polyamic acid in the gel film, and then a fixed frame made of metal.
  • the polyimide film of Example 4 (thickness: 17 ⁇ m) was obtained.
  • Example 5 (1st sequence polymerization step) After putting 164.0 g of DMF and 6.9 g of PDA in a glass flask with a capacity of 500 mL, 12.5 g of BPDA and 5.5 g of ODPA are placed in the flask while stirring the contents of the flask. I put it in. The flask contents were then stirred for 30 minutes.
  • the obtained polyamic acid solution P5 had a solid content concentration of 15% by weight.
  • the obtained polyamic acid solution P5 had a viscosity of 1500 to 2000 poise at a temperature of 23 ° C.
  • the obtained gel film was peeled off from the aluminum foil, fixed to a metal fixing frame, placed in a hot air circulation oven preheated to a temperature of 350 ° C., heated at a heating temperature of 350 ° C. for 19 seconds, and subsequently heated.
  • the polyimide film of Example 5 was separated from the metal fixing frame. Thickness: 17 ⁇ m) was obtained.
  • Example 6 Examples 8 to 37, Comparative Examples 1 to 3, Comparative Example 5 and Comparative Example 6
  • the ratios of Example 6, Examples 8 to 37, Comparative Examples 1 to 3, Comparative Example 5 and Comparative Example 6 were set by the same method as in Example 5 except that the ratios were as shown in Tables 1 to 10 described later. Polyimide films (thickness: 17 ⁇ m in each case) were obtained.
  • the total amount of substance of the acid dianhydride and the diamine was the same as that of Example 5.
  • Example 7 (1st sequence polymerization step) After putting 161.4 g of DMF and 7.4 g of PDA in a glass flask with a capacity of 500 mL, 12.7 g of BPDA and 6.7 g of ODPA were placed in the flask while stirring the contents of the flask. I put it in. The flask contents were then stirred for 30 minutes.
  • the obtained polyamic acid solution P7 had a solid content concentration of 15% by weight.
  • the obtained polyamic acid solution P7 had a viscosity of 1500 to 2000 poise at a temperature of 23 ° C.
  • the obtained gel film was peeled off from the aluminum foil, fixed to a metal fixing frame, placed in a hot air circulation oven preheated to a temperature of 350 ° C., heated at a heating temperature of 350 ° C. for 19 seconds, and subsequently heated.
  • the polyimide film of Example 7 was separated from the metal fixing frame. Thickness: 17 ⁇ m) was obtained.
  • Comparative Example 4 Types of monomers used in the 1st sequence polymerization step and their ratios (charge ratio), types of monomers used in the 2nd sequence polymerization step and their ratios (charge ratio), heating conditions in the film forming process, and weight of the imidization accelerator
  • the polyimide films of Comparative Example 4, Comparative Example 7 and Comparative Example 8 were obtained by the same method as in Example 7 except that the ratios were as shown in Tables 5 and 10 described later. rice field.
  • the total amount of substance of the acid dianhydride and the diamine was the same as that of Example 7.
  • Examples 1 to 37 and Comparative Examples 1 to 8 the types and ratios of the monomers used in the 1st sequence polymerization step (charge ratio), the types and ratios of the monomers used in the 2nd sequence polymerization step (charge ratio), and The rigidity / bending ratios are shown in Tables 1 to 5. Further, for Examples 1 to 37 and Comparative Examples 1 to 8, the weight ratio of the imidization accelerator, the heating conditions in the film forming process, the relative permittivity, the dielectric loss tangent, the lamella cycle, and the CTE are shown in Tables 6 to 10. show.
  • the numerical values in the column of "diamine” are the total amount of diamine used (in the case of sequence polymerization, the total amount of diamine used in the 1st sequence polymerization step and the diamine used in the 2nd sequence polymerization step. The content of each diamine (unit: mol%) with respect to the total amount).
  • the numerical values in the column of "acid dianhydride” are the total amount of acid dianhydride used (in the case of sequence polymerization, the total amount of acid dianhydride used in the 1st sequence polymerization step and the 2nd sequence.
  • each acid dianhydride (unit: mol%) with respect to the total amount of the acid dianhydride used in the polymerization step.
  • "-" indicates the component (PDA, TPE-R, m-TB, ODA, TPE-Q, BAPP, BPDA, It means that PMDA, TMHQ, BTDA, ODPA or BISDA) was not used.
  • the mole fraction of each residue in the polyimide contained in the obtained polyimide film was the mole fraction of each monomer used (diamine and tetracarboxylic acid dianhydride).
  • the total amount of substance of the tetracarboxylic acid dianhydride residue constituting the polyimide contained in the obtained polyimide film is the diamine constituting the polyimide.
  • the substance amount ratio divided by the total substance amount of the residue was 0.99 or more and 1.01 or less.
  • the non-thermoplastic polyimides contained in the polyimide films of Examples 1 to 37 had a BPDA residue, an ODPA residue, a PDA residue, and a TPE-R residue.
  • the total content of the BPDA residue and the ODPA residue with respect to the total tetracarboxylic acid dianhydride residue constituting the non-thermoplastic polyimide was 80 mol% or more.
  • the total content of the PDA residue and the TPE-R residue with respect to all the diamine residues constituting the non-thermoplastic polyimide was 80 mol% or more.
  • the rigidity / bending ratio was 3.50 or less.
  • the lamella cycle was 15 nm or more.
  • the dielectric loss tangent was less than 0.0030. Therefore, the polyimide films of Examples 1 to 37 were able to reduce the dielectric loss tangent.
  • the non-thermoplastic polyimide contained in the polyimide films of Comparative Examples 1, 3, 4 and 6 did not have a TPE-R residue.
  • the non-thermoplastic polyimide contained in the polyimide film of Comparative Example 1 did not have a BPDA residue and an ODPA residue.
  • the total content of the BPDA residue and the ODPA residue with respect to the total tetracarboxylic acid dianhydride residue constituting the non-thermoplastic polyimide was less than 80 mol%.
  • the rigidity / bending ratio exceeded 3.50.
  • the lamella cycle was less than 15 nm.
  • Comparative Examples 1 to 8 the dielectric loss tangent was 0.0030 or more. Therefore, the polyimide films of Comparative Examples 1 to 8 could not reduce the dielectric loss tangent.
  • Multi-layer polyimide film 11 Specified non-thermoplastic polyimide film (non-thermoplastic polyimide film) 12: Adhesive layer 13: Metal layer 20: Metal-clad laminate

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WO2023162745A1 (ja) * 2022-02-24 2023-08-31 株式会社カネカ ポリアミド酸、ポリイミド、非熱可塑性ポリイミドフィルム、複層ポリイミドフィルム及び金属張積層板
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