WO2020262450A1 - Resin film, metal-clad laminate and method for producing same - Google Patents
Resin film, metal-clad laminate and method for producing same Download PDFInfo
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- WO2020262450A1 WO2020262450A1 PCT/JP2020/024769 JP2020024769W WO2020262450A1 WO 2020262450 A1 WO2020262450 A1 WO 2020262450A1 JP 2020024769 W JP2020024769 W JP 2020024769W WO 2020262450 A1 WO2020262450 A1 WO 2020262450A1
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- 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
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- 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
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- 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
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- 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
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- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- 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
- B32B7/023—Optical properties
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- 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
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- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- 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
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- 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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- 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
- C08G73/14—Polyamide-imides
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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
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- 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
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- 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
- B32B2307/306—Resistant to heat
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- 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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- 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
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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
- 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
Definitions
- the present invention relates to a highly transparent resin film (insulating resin layer) having excellent heat resistance, adhesiveness, and flexibility, and a metal-clad laminate formed by laminating the resin film.
- Polyimide is a heat-resistant resin obtained by ring-closing the polyamic acid synthesized by the condensation reaction of tetracarboxylic acid anhydride and diamine as raw materials.
- the rigidity of the molecular chain, resonance stabilization, and strong chemical bond Therefore, it has excellent resistance to thermal decomposition, high durability against chemical changes such as oxidation or hydrolysis, and excellent flexibility, mechanical properties, and electrical properties.
- Polyimide is widely used for the insulating resin layer of a flexible printed circuit board (FPC) generally used for electronic devices.
- FPC flexible printed circuit board
- the insulating resin layer of a commercially available copper-clad laminate generally used for FPC is made of a totally aromatic polyimide resin, and exhibits a yellowish brown color due to the formation of charge transfer complexes in and between molecules, which is colorless. It is difficult to apply to transparent FPC applications where transparency is required.
- Patent Document 1 proposes a colorless and transparent semi-alicyclic polyimide formed from an alicyclic diamine and an aromatic acid dianhydride
- Patent Document 2 proposes an alicyclic diamine and an alicyclic diamine.
- a colorless and transparent total alicyclic polyimide composed of an acid anhydride has been proposed.
- the glass transition temperature of the obtained polyimide is about 280 ° C.
- the heat resistance is insufficient, and it is difficult to apply it to a main component as an insulating layer of FPC.
- the colorless transparent polyimide suppresses the formation of a charge transfer complex, there is also a problem that it is difficult to satisfy the low thermal expansion required for FPC.
- Patent Document 3 and Patent Document 4 disclose a laminate of a metal and polyimide having a fluorinated polyimide as an insulating resin layer, and the laminate shown here focuses on the transparency of the insulating layer. Although it is excellent in transparency, it has insufficient control over the coefficient of thermal expansion of the insulating layer and other characteristics, has low adhesion to a smooth metal layer, and is a laminate for wiring boards suitable for FPC applications. It did not fully satisfy the characteristics as.
- Patent Document 5 aims to have transparency and improve the adhesive force with a smooth metal layer, but the polyimide that adheres to the metal layer is still colored, and the transparency of the entire polyimide layer is inferior. The characteristics as a metal-clad laminate suitable for transparent FPC applications were not sufficiently satisfied.
- the metal-clad laminate used for FPC is composed of an insulating resin layer including a thin metal foil and a polyimide layer, and if the difference in thermal expansion coefficient (CTE) between the metal foil and the insulating resin layer is significantly different, the substrate warps. And curl occur, and when mounting electronic components, there is a problem that the dimensions change and accurate mounting becomes impossible.
- a metal-clad laminate having an insulating resin layer having excellent transparency is excellent in visibility from the insulating resin layer side when mounting a semiconductor element on a wiring board, so that a photocurable resin is interposed in the wiring board. It is advantageous for light irradiation from the insulating resin layer side when joining semiconductor elements, and it can be expected to be used for transparent FPC applications.
- An object of the present invention is to provide a resin film and a metal-clad laminate for a wiring substrate, which have excellent heat resistance, dimensional stability represented by a coefficient of thermal expansion, flexibility, adhesiveness, and high transparency. is there.
- the present inventors have decided to use a specific polyimide for the insulating resin layer of the wiring board laminate or the FPC and to have an appropriate layer structure, and to obtain the thickness of the polyimide layer.
- a specific polyimide for the insulating resin layer of the wiring board laminate or the FPC and to have an appropriate layer structure, and to obtain the thickness of the polyimide layer.
- the present invention is a resin film having a plurality of polyimide layers.
- the filling, At least one of the polyimide layers contains a polyimide layer (P1),
- the polyimide constituting the polyimide layer (P1) contains an acid anhydride residue derived from an acid anhydride component and a diamine residue derived from a diamine component.
- the polyimide contains 50 mol% or more of an acid anhydride residue derived from an aromatic tetracarboxylic acid anhydride represented by the following general formula (1) with respect to the total acid anhydride residue, and is a total diamine.
- X represents a divalent group selected from single bond, -O-, or -C (CF 3 ) 2- .
- R is independently an alkyl group or an alkoxy group which may be substituted with a halogen atom or a halogen atom having 1 to 6 carbon atoms, or a monovalent hydrocarbon group having 1 to 6 carbon atoms.
- n 1 is an integer of 0 to 3 and n 2 is an integer of 0 to 4.
- the polyimide layer (P1) is located on the outermost layer.
- the resin film of the present invention preferably satisfies the condition c) that the coefficient of thermal expansion (CTE) is within the range of 10 ppm / K or more and 30 ppm / K or less.
- the polyimide layer (P1) is in the range of 1% or more and less than 50% with respect to the total thickness.
- the resin film of the present invention preferably satisfies the condition d) HAZE of 5% or less.
- the resin film of the present invention preferably satisfies the condition e) that the YI is 10 or less when the thickness is 10 ⁇ m.
- the resin film of the present invention preferably satisfies the condition f) that the YI is 30 or less when the thickness is 50 ⁇ m.
- the polyimide constituting the main layer of the polyimide layer is an aromatic tetracarboxylic acid anhydride containing a diamine residue and / or a fluorine atom derived from an aromatic diamine compound containing a fluorine atom. It is preferred to include acid anhydride residues derived from.
- the polyimide constituting the main layer of the polyimide layer contains 50 mol% or more of diamine residues derived from the diamine compound represented by the following general formula (A1) with respect to all diamine residues. Is preferable.
- the substituent X represents an alkyl element group having 1 to 3 carbon atoms independently substituted with a fluorine atom, and m and n independently represent an integer of 1 to 4.
- the present invention is a metal-clad laminate comprising an insulating resin layer having a plurality of polyimide layers and a metal layer laminated on at least one surface of the insulating resin layer. It is a metal-clad laminate characterized in that the insulating resin layer is made of the resin film.
- the polyimide layer in contact with the metal layer of the insulating resin layer is the polyimide layer (P1).
- the thickness of the metal layer is preferably in the range of 1 ⁇ m or more and 20 ⁇ m or less.
- the ten-point average roughness Rzjis of the surface of the metal layer in contact with the insulating resin layer is in the range of 0.01 ⁇ m or more and 0.5 ⁇ m or less.
- the 180 ° peel strength between the insulating resin layer and the metal layer is 0.5 kN / m or more.
- the metal-clad laminate of the present invention A metal-clad laminate comprising an insulating resin layer and a metal layer laminated on at least one surface of the insulating resin layer.
- the insulating resin layer is composed of a single layer or a plurality of polyimide layers, and the following conditions a to g; a) The thickness must be within the range of 5 ⁇ m or more and 20 ⁇ m or less; b) The coefficient of thermal expansion (CTE) is in the range of 10 ppm / K or more and 30 ppm / K or less; c) The total light transmittance is 80% or more; d) YI is 10 or less; e) HAZE is 3% or less; f) The glass transition temperature (Tg) is 280 ° C or higher; g) Tensile strength is 100 MPa or more; It is characterized by satisfying.
- the method for producing a metal-clad laminate of the present invention comprises producing a metal-clad laminate comprising an insulating resin layer having a plurality of polyimide layers and a metal layer laminated on at least one surface of the insulating resin layer. It's a method
- the insulating resin layer comprises the resin film according to claim 1. It is characterized by including a step of superimposing the surface of the polyimide layer (P1) on the resin film and the metal layer and thermocompression bonding.
- the resin film and the metal-clad laminate of the present invention have excellent heat resistance, dimensional stability, adhesiveness, flexibility and high transparency, they are particularly used as an insulating material for manufacturing electronic components such as FPCs. It is suitably used for transparent FPCs that require colorless transparency with mounting of semiconductor elements. Further, the resin film and the metal-clad laminate of the present invention can be applied to display devices such as liquid crystal display devices, organic EL display devices, touch panels, color filters, electronic papers, and their components.
- the resin film of the present invention needs to satisfy that the thickness is within the range of 5 ⁇ m or more and 200 ⁇ m or less, and the total light transmittance in the visible region is 80% or more.
- the plurality of polyimide layers may have a two-layer structure of a polyimide layer (P1) and another polyimide layer, preferably three layers, and the polyimide layer (P1) may be arranged as an outer layer. More preferably, the two outer layers of the three layers except the inner layer may be made into a polyimide layer (P1).
- a two-layer structure in which polyimide layers other than the polyimide layer (P1) and the polyimide layer (P1) are laminated in this order may be formed from the cast surface side.
- the polyimide layer (P1), the polyimide layer other than the polyimide layer (P1), and the polyimide layer (P1) may be laminated in this order from the cast surface side to form a three-layer structure.
- the "cast surface” referred to here refers to the surface on the support side when forming the polyimide layer.
- the support may be a metal layer of a metal-clad laminate, or may be a support for forming a gel film or the like.
- the surface opposite to the cast surface is described as a "laminated surface", but unless otherwise specified, a metal layer may or may not be laminated on the laminated surface.
- the polyimide constituting the polyimide layer (P1) is preferably a thermoplastic polyimide, which improves the adhesiveness as a resin film and can be used with a base material such as a metal layer or another resin layer. It is preferably applied as an adhesive layer. Therefore, a resin film having a polyimide layer (P1) on the surface layer portion is the most preferable embodiment.
- a preferred embodiment of the resin film of the present invention has a thermoplastic polyimide layer (P1) and a non-thermoplastic polyimide layer composed of a non-thermoplastic polyimide, and at least one of the non-thermoplastic polyimide layers is formed.
- a polyimide layer (P1) to be a thermoplastic polyimide layer are preferable. That is, the polyimide layer (P1) may be provided on one side or both sides of the non-thermoplastic polyimide layer.
- 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 a polyimide layer having a coefficient of thermal expansion (CTE) preferably in the range of 1 ppm / K or more and 25 ppm / K or less, and more preferably in the range of 3 ppm / K or more and 25 ppm / K or less.
- the highly thermally expandable polyimide layer has a CTE of preferably 35 ppm / K or more, more preferably 35 ppm / K or more and 80 ppm / K or less, and further preferably 35 ppm / K or more and 70 ppm / K or less.
- the polyimide layer can be a polyimide layer having a desired CTE by appropriately changing the combination of raw materials used, the thickness, and the drying / curing conditions.
- the non-thermoplastic polyimide is generally a polyimide that does not soften or show adhesiveness even when heated, but in the present invention, it is measured at 30 ° C. using a dynamic viscoelasticity measuring device (DMA).
- DMA dynamic viscoelasticity measuring device
- thermoplastic polyimide having a storage elastic modulus of 1.0 ⁇ 10 9 Pa or more and a storage elastic modulus of 1.0 ⁇ 10 8 Pa or more at 360 ° C.
- the thermoplastic polyimide is generally a polyimide in which the glass transition temperature (Tg) can be clearly confirmed, but in the present invention, the storage elastic modulus at 30 ° C. measured using DMA is 1.0 ⁇ 10. 9 is less than Pa, the storage modulus at 360 ° C. refers to polyimide is less than 1.0 ⁇ 10 8 Pa.
- the CTE of the resin film of the present invention is preferably in the range of 10 ppm / K or more and 30 ppm / K or less. By controlling within such a range, deformation such as curl can be suppressed, and high dimensional stability can be ensured.
- CTE is an average value of the coefficients of thermal expansion in the length direction (MD direction) and the width direction (TD direction) of the resin film.
- the thickness of the entire polyimide layer is in the range of 5 ⁇ m or more and 200 ⁇ m or less, but the thickness of each layer is preferably in the range of 7 ⁇ m or more and 50 ⁇ m or less for the inner layer and 1 ⁇ m or more and 5 ⁇ m or less for the outer layer. More preferably, the inner layer is in the range of 7 ⁇ m or more and 20 ⁇ m or less, and the outer layer is in the range of 1 ⁇ m or more and 3 ⁇ m or less. From another viewpoint, the thickness of the outer layer is preferably in the range of 1% or more and less than 50%, more preferably in the range of 1% or more and 20% or less of the thickness of the entire polyimide layer.
- the resin film of the present invention has a total light transmittance of 80% or more in the visible region from the viewpoint of transparency.
- the light transmittance at a wavelength of 450 nm is preferably 70% or more, more preferably 80% or more.
- the thickness of the entire resin film is 20 ⁇ m. More preferably, the total light transmittance is 85% or more.
- the resin film of the present invention preferably has a HAZE (turbidity) of 5% or less, more preferably 2% or less. If HAZE exceeds 5%, for example, light scattering is likely to occur. Further, HAZE depends on the surface profile of the resin film, and even if it is a low profile resin film, it has a polyimide layer (P1), so that both adhesive strength and transparency can be achieved, for example, a fine metal layer. Can be suitably used for bonding with a circuit board or a glass base material for laminating.
- HAZE turbidity
- the YI yellowness
- the thickness of the resin film of the present invention is 10 ⁇ m
- the YI yellowness
- the thickness of the resin film of the present invention is 50 ⁇ m
- the YI is preferably 30 or less.
- the polyimide layer is composed of a polyimide containing an acid anhydride residue and a diamine residue, and the polyimide constituting at least one polyimide layer (P1) is derived from an acid anhydride component.
- P1 polyimide constituting at least one polyimide layer (P1) is derived from an acid anhydride component.
- it contains 50 mol% or more of an acid anhydride residue derived from the aromatic tetracarboxylic acid anhydride represented by the general formula (1), preferably 70 mol% or more, more preferably 90 mol% or more. It is easy to develop heat resistance and low polyimide in such a range.
- the total diamine residue contained in the polyimide contains 50 mol% or more of the diamine residue derived from the aromatic diamine compound represented by the general formula (2).
- low retardation means that the thickness direction retardation at a thickness of 10 ⁇ m is 200 nm or less.
- the aromatic tetracarboxylic dianhydride represented by the general formula (1) imparts flexibility to the polyimide and reduces interactions such as ⁇ - ⁇ stacking between polymer chains, resulting in an aromatic tetracarboxylic dian residue. It is considered that the obtained polyimide can be made almost colorless and transparent in order to make the charge transfer (CT) between the group and the aromatic diamine residue less likely to occur.
- the aromatic diamine compound represented by the general formula (2) has two or more benzene rings, and has an amino group directly linked to at least two benzene rings and a divalent linking group Z, whereby the polyimide molecule.
- the degree of freedom of the chain is increased and it has high flexibility, which contributes to the improvement of the flexibility of the polyimide molecular chain and promotes the increase in toughness.
- the acid anhydride residue represents a tetravalent group derived from a tetracarboxylic dianhydride
- the diamine residue is a divalent group derived from a diamine compound. Represents that.
- the acid anhydride residue contained in the polyimide constituting the polyimide layer (P1) is an acid anhydride residue derived from the aromatic tetracarboxylic dianhydride represented by the general formula (1).
- X represents a divalent group selected from single bond, —O—, or —C (CF 3 ) 2- .
- aromatic tetracarboxylic dianhydride represented by the formula (1) examples include 4,4'-oxydiphthalic acid dianhydride (ODPA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride. (BPDA), 2,2-bis (3,4-dicarboxyphenyl) -hexafluoropropanedianhydride (6FDA) can be mentioned.
- ODPA 4,4'-oxydiphthalic acid dianhydride
- BPDA 4,4'-biphenyltetracarboxylic dianhydride
- 6FDA 2,2-bis (3,4-dicarboxyphenyl) -hexafluoropropanedianhydride
- These aromatic tetracarboxylic dianhydrides are preferable because they can impart strength and flexibility to the polyimide film, are excellent in heat resistance and transparency, and can control CTE within an appropriate range. Of these, ODPA and 6FDA are particularly preferable.
- the diamine residue contained in the polyimide constituting the polyimide layer (P1) is a diamine residue derived from the aromatic diamine compound represented by the general formula (2).
- Z is independently -O-, -S-, -CH 2- , -CH (CH 3 )-, -C (CH 3 ) 2- , -CO-, -COO-, -SO. It represents a divalent group selected from 2-, -NH- or -NHCO-, preferably -O-.
- n 2 represents an integer from 0 to 4, preferably 0 or 1.
- R is a substituent, which is an alkyl group or an alkoxy group which may be independently substituted with a halogen atom or a halogen atom having 1 to 6 carbon atoms, or a monovalent hydrocarbon group or an alkoxy group having 1 to 6 carbon atoms.
- n 1 independently represents an integer of 0 to 3, preferably 0 or 1.
- "independently” means that, in the above formula (2), a plurality of substituents R, a divalent group Z, and an integer n 1 may be the same or different.
- the hydrogen atom in the two terminal amino groups may be substituted, for example, -NR 3 R 4 (where R 3 and R 4 are independently alkyl groups and the like. It may mean any substituent). The same applies to other diamine compounds.
- Z is independently -O-, -S-, -CH 2- , -CH (CH 3 )-or -NH. Indicates a divalent group selected from-.
- Examples of the aromatic amine compound represented by the formula (2) include 3,3'-diaminodiphenylmethane, 3,3'-diaminodiphenylpropane, 3,3'-diaminodiphenylsulfide, and 3,3'-diaminodiphenyl.
- acid anhydride residues may be contained as long as the object of the present invention is not impaired.
- it contains other acid anhydride residues, it is 50 mol% or less of the total acid anhydride residues, preferably less than 30 mol%, more preferably less than 10 mol%.
- acid anhydride residues include, for example, pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride.
- pyromellitic dianhydride or 3,3 is possible because it is possible to give strength and flexibility to the polyimide film, the coefficient of thermal expansion (CTE) of the polyimide film does not increase too much, and it can be controlled within an appropriate range.
- Acid anhydride residues derived from', 4,4'-biphenyltetracarboxylic dianhydride are preferred.
- a diamine residue derived from another diamine compound may be contained as long as the object of the present invention is not impaired.
- it is 50 mol% or less of the total diamine residues, preferably less than 30 mol%, more preferably less than 10 mol%.
- diamine residues include, for example, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFMB), bis [4- (aminophenoxy) phenyl] sulfone (BAPS), 4, 6-Dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,4-diaminomethicylene, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,5,3', 5 '-Tetramethyl-4,4'-diaminodiphenylmethane, 2,4-toluenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4, 4'-diaminodiphenylethane, 3,3'-diaminodiphen
- toughness and thermal expansion are obtained by selecting the types of the acid anhydride residue and the diamine residue and the molar ratio of each of two or more kinds of the acid anhydride residue or the diamine residue.
- the property, adhesiveness, glass transition temperature (Tg), etc. can be controlled.
- a polyimide constituting a main polyimide layer (hereinafter, may be referred to as “polyimide layer (A)" is used so that the total light transmittance is 80% or more.
- the main polyimide may include diamine residues derived from aromatic diamine compounds containing fluorine atoms and / or acid anhydride residues derived from aromatic tetracarboxylic acid anhydrides containing fluorine atoms. preferable.
- “main” means having the largest thickness among the plurality of polyimide layers constituting the resin film, and preferably 50% or more, more preferably 60% or more, based on the total thickness of the resin film. It means having the thickness of.
- the main polyimide constituting the polyimide layer (A) preferably contains a fluorine-containing diamine residue. Since the fluorine-containing diamine residue has a group containing a bulky fluorine atom, it reduces interactions such as ⁇ - ⁇ stacking between polymer chains, and the aromatic tetracarboxylic acid residue and the aromatic diamine residue It is considered that the polyimide can be made almost colorless and transparent in order to make the charge transfer (CT) between the two less likely to occur.
- CT charge transfer
- fluorine-containing diamine residue examples include 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl (TFMB) and 1,4-bis (4-amino-2-trifluoromethylphenoxy) benzene.
- A1 residue a diamine residue derived from a diamine compound represented by the following general formula (A1) (hereinafter, may be referred to as "A1 residue").
- the substituent X represents an alkyl element group having 1 to 3 carbon atoms independently substituted with a fluorine atom, and m and n independently represent an integer of 1 to 4.
- the A1 residue is an aromatic diamine residue and has a biphenyl skeleton in which two benzene rings are connected by a single bond, so that an ordered structure can be easily formed and the orientation of the molecular chain in the in-plane direction can be easily formed. Since it is promoted, it is possible to suppress an increase in CTE of the polyimide layer (A), which is the main layer, and improve dimensional stability.
- the main polyimide constituting the polyimide layer (A) preferably contains 50 mol parts or more of A1 residues with respect to 100 mol parts in total of all diamine residues, and 50 mol parts or more 100 parts. It is more preferable to contain it in the range of the molar portion or less.
- A1 residue is 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl (TFMB), 3,4-diamino-2,2'-bis (trifluoromethyl).
- TFMB 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl
- examples thereof include diamine residues derived from diamine compounds such as biphenyl.
- the main polyimide constituting the polyimide layer (A) may contain a diamine residue derived from a diamine component generally used for the synthesis of polyimide as a diamine residue other than the above.
- the main polyimide constituting the polyimide layer (A) preferably contains a fluorine-containing acid anhydride residue. Since the fluorine-containing acid anhydride residue has a group containing a bulky fluorine atom, it reduces interactions such as ⁇ - ⁇ stacking between polymer chains, and the aromatic tetracarboxylic acid residue and the aromatic diamine residue. It is considered that the polyimide can be made almost colorless and transparent in order to make the charge transfer (CT) between the group and the group less likely to occur.
- CT charge transfer
- Fluorine-containing acid anhydride residues include acid anhydride residues derived from acid anhydride components such as 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA). Can be mentioned.
- the main polyimide constituting the polyimide layer (A) controls the CTE of the polyimide layer (A) within the above range, and therefore is represented by the following formula (B1). It preferably contains a tetravalent acid anhydride residue derived from (PMDA) (hereinafter, may be referred to as "PMDA residue").
- the PMDA residue is preferably contained in an amount of 50 mol parts or more, more preferably 60 mol parts or more and 100 mol parts or less, based on a total of 100 mol parts of the total acid anhydride residue. If the PMDA residue is less than 50 mol parts, the CTE of the polyimide layer (A) becomes high and the dimensional stability decreases.
- the main polyimide constituting the polyimide layer (A) contains an acid anhydride residue derived from an acid anhydride component generally used for the synthesis of polyimide as an acid anhydride residue other than the above. You may. Aromatic tetracarboxylic acid residues are preferred as such acid anhydride residues. It may also contain an alicyclic tetracarboxylic dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, fluorenilidenbis dianhydride, 1,2,4,5.
- -Ignore acid residues derived from alicyclic tetracarboxylic dianhydrides such as cyclohexanetetracarboxylic dianhydride and cyclotanone bisspironorbornanetetracarboxylic dianhydride are preferred.
- the polyimide of the present embodiment can be produced by reacting the above-mentioned acid anhydride and diamine in a solvent to generate polyamic acid, and then heating and closing the ring.
- the acid anhydride component and the diamine component are dissolved in an organic solvent in approximately equimolar amounts, and the mixture is stirred at a temperature in the range of 0 ° C. or higher and 100 ° C. or lower for 30 minutes to 24 hours to carry out a polymerization reaction to cause a polyimide precursor.
- Polyamic acid is obtained.
- the reaction component is dissolved in an organic solvent so that the precursor produced is in the range of 5% by weight or more and 30% by weight or less, preferably 10% by weight or more and 20% by weight or less.
- organic solvent used in the polymerization reaction include N, N-dimethylformamide, N, N-dimethylacetamide (DMAC), N-methyl-2-pyrrolidone, 2-butanone, dimethyl sulfoxide, dimethyl sulfate, cyclohexanone, and dioxane. , Tetrahydrofuran, jiglime, triglime, ⁇ -petitolactate and the like.
- Two or more of these solvents can be used in combination, and aromatic hydrocarbons such as xylene and toluene can also be used in combination.
- the amount of such an organic solvent used is not particularly limited, but the concentration of the polyamic acid solution (polyimide precursor solution) obtained by the polymerization reaction is about 5% by weight to 30% by weight. It is preferable to adjust the amount to be used.
- the polyimide of the present embodiment may use an end sealant.
- the terminal encapsulant monoamines or dicarboxylic acids are preferable.
- the amount of the end-capping agent to be introduced is preferably in the range of 0.0001 mol or more and 0.1 mol or less, and particularly 0.001 mol or more and 0.05 mol or less with respect to 1 mol of the acid anhydride component. Within the range is preferred.
- the monoamine terminal encapsulant include methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, and aniline.
- dicarboxylic acids are preferable, and a part thereof may be ring-closed.
- phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, cyclopentane-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid and the like are recommended.
- phthalic acid and phthalic anhydride can be preferably used.
- the synthesized polyamic acid is usually advantageous to be used as a reaction solvent solution, but can be concentrated, diluted or replaced with another organic solvent if necessary.
- polyamic acid is generally excellent in solvent solubility and is therefore used advantageously.
- the method for imidizing the polyamic acid is not particularly limited, and for example, a heat treatment such as heating in the solvent under a temperature condition of 80 ° C. or higher and 400 ° C. or lower for 1 hour to 24 hours is preferably adopted. ..
- the weight average molecular weight of the polyamic acid is preferably in the range of 10,000 or more and 400,000 or less, and more preferably in the range of 50,000 or more and 350,000 or less. If the weight average molecular weight is less than 10,000, the strength of the film is lowered and the film tends to be brittle. On the other hand, when the weight average molecular weight exceeds 400,000, the viscosity is excessively increased, and defects such as uneven film thickness and streaks tend to occur during the coating operation.
- the resin film of the present embodiment has a plurality of polyimide layers, and at least one polyimide layer may be a film (sheet) composed of the polyimide of the present embodiment and made of an insulating resin, and may be a copper foil.
- a film of an insulating resin laminated on a base material such as a resin sheet such as a glass plate, a polyimide film, a polyamide film, or a polyester film.
- the method for forming the resin film of the present embodiment is not particularly limited, but for example, [1] a method of applying a polyamic acid solution to a supporting base material, drying it, and then imidizing it to produce a resin film (hereinafter referred to as a method). (Casting method), [2] A method of applying a polyamic acid solution to the supporting base material, drying it, peeling the polyamic acid gel film from the supporting base material, and imidizing the support base material to produce a resin film. Further, since the resin film produced in the present embodiment is composed of a plurality of polyimide layers, as an embodiment of the production method, for example, [3] a support base material is coated with a polyamic acid solution and dried.
- the support substrate is simultaneously coated and dried with a laminated structure of polyamic acid by multi-layer extrusion, and then imidization is performed. Examples thereof include a method (hereinafter referred to as a multilayer extrusion method).
- the method of applying the polyimide solution (or polyamic acid solution) on the substrate is not particularly limited, and for example, it can be applied with a coater such as a comma, a die, a knife, or a lip.
- a method of repeatedly applying a polyimide solution (or a polyamic acid solution) to the substrate and drying the substrate is preferable.
- the resin film of the present embodiment may contain an inorganic filler in the polyimide layer, if necessary, as long as the object of the present invention is not impaired.
- an inorganic filler in the polyimide layer, if necessary, as long as the object of the present invention is not impaired.
- Specific examples thereof include silicon dioxide, aluminum oxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride and calcium fluoride. These can be used alone or in admixture of two or more.
- the metal-clad laminate of the present invention will be described below.
- the metal-clad laminate of the present invention has a metal layer on at least one surface of the insulating resin layer, that is, on one side or both sides.
- the insulating resin layer has two or more polyimide resin layers, and at least one layer is the above-mentioned polyimide layer (P1).
- the metal layer (M1) and the metal layer (M2) are laminated on the insulating resin layer composed of the polyimide layer (P1) and the main polyimide layer (P2).
- the following configurations 1 to 4 are exemplified.
- the polyimide layer (P1) in contact with at least one surface of the metal layer (M1) or the metal layer (M2) is preferably the adhesive layer.
- the total thickness of the main polyimide layer (P2) is preferably 50% or more with respect to the thickness of the insulating resin layer.
- the insulating resin layer is composed of a single layer or a plurality of polyimide layers, but it is preferable to have a plurality of polyimide layers.
- a plurality of polyimide layers it is possible to form an insulating resin layer having excellent physical properties such as heat resistance, adhesiveness, flexibility, and transparency.
- the plurality of polyimide layers may have a two-layer structure of a polyimide layer (P1) and another polyimide layer, preferably three layers, and the polyimide layer (P1) may be arranged as an outer layer. More preferably, the two outer layers of the three layers except the inner layer may be made into a polyimide layer (P1).
- a two-layer structure in which polyimide layers other than the polyimide layer (P1) and the polyimide layer (P1) are laminated in this order may be formed from the cast surface side.
- the polyimide layer (P1), the polyimide layer other than the polyimide layer (P1), and the polyimide layer (P1) may be laminated in this order from the cast surface side to form a three-layer structure.
- the "cast surface” referred to here refers to the surface on the support side when forming the polyimide layer.
- the support may be a metal layer of a metal-clad laminate, or may be a support for forming a gel film or the like.
- the surface opposite to the cast surface is described as a "laminated surface", but unless otherwise specified, a metal layer may or may not be laminated on the laminated surface.
- the polyimide constituting the polyimide layer (P1) is preferably a thermoplastic polyimide, which improves the adhesiveness as an insulating resin layer and is preferably applied as an adhesive layer with a metal layer. Therefore, the insulating resin layer in which the polyimide layer (P1) is directly laminated on the metal layer is the most preferable embodiment.
- a preferred embodiment of the insulating resin layer has a thermoplastic polyimide layer (P1) and a non-thermoplastic polyimide layer composed of a non-thermoplastic polyimide, and at least one of the non-thermoplastic polyimide layers is thermoplastic.
- a polyimide layer (P1) to be a polyimide layer are preferable. That is, the polyimide layer (P1) may be provided on one side or both sides of the non-thermoplastic polyimide layer.
- 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 a polyimide layer having a coefficient of thermal expansion (CTE) preferably in the range of 1 ppm / K or more and 25 ppm / K or less, and more preferably in the range of 3 ppm / K or more and 25 ppm / K or less.
- the highly thermally expandable polyimide layer has a CTE of preferably 35 ppm / K or more, more preferably 35 ppm / K or more and 80 ppm / K or less, and further preferably 35 ppm / K or more and 70 ppm / K or less.
- the polyimide layer can be a polyimide layer having a desired CTE by appropriately changing the combination of raw materials used, the thickness, and the drying / curing conditions.
- the non-thermoplastic polyimide is generally a polyimide that does not soften or show adhesiveness even when heated, but in the present invention, it is measured at 30 ° C. using a dynamic viscoelasticity measuring device (DMA).
- DMA dynamic viscoelasticity measuring device
- thermoplastic polyimide having a storage elastic modulus of 1.0 ⁇ 10 9 Pa or more and a storage elastic modulus of 1.0 ⁇ 10 8 Pa or more at 350 ° C.
- the thermoplastic polyimide is generally a polyimide in which the glass transition temperature (Tg) can be clearly confirmed, but in the present invention, the storage elastic modulus at 30 ° C. measured using DMA is 1.0 ⁇ 10. 9 is less than Pa, the storage modulus at 350 ° C. refers to polyimide is less than 1.0 ⁇ 10 8 Pa.
- the thickness of the insulating resin layer is within the range of 5 ⁇ m or more and 20 ⁇ m or less. By controlling within such a range, high transparency and colorlessness can be improved. Further, if the thickness of the insulating resin layer does not reach the above lower limit value, there may be problems such as the electrical insulation cannot be guaranteed and the handling becomes difficult due to the deterioration of the handling property. On the other hand, when the thickness of the insulating resin layer exceeds the above upper limit value, the dimensional change before and after etching becomes large, the yellow to tan coloring becomes strong, and the visibility of the insulating resin layer deteriorates.
- the thickness of the insulating resin layer is preferably in the range of 5 ⁇ m or more and 12 ⁇ m or less.
- the polyimide layer (P1) in contact with the metal layer When the thickness is T1 and the thickness of the main polyimide layer (hereinafter, sometimes referred to as "polyimide layer (A)") is T2, the thickness of T1 is preferably in the range of 1 ⁇ m or more and 4 ⁇ m or less, and the thickness of T2 is It is preferably in the range of 4 ⁇ m or more and 19 ⁇ m or less. From another viewpoint, the thickness of T1 is preferably 20% or less with respect to the thickness of the insulating resin layer.
- main means having the largest thickness among the plurality of polyimide layers constituting the insulating resin layer, preferably 60% or more, more preferably 70% with respect to the thickness of the insulating resin layer. It means having the above thickness.
- the main polyimide layer is preferably composed of non-thermoplastic polyimide.
- the insulating resin layer has a heat resistance with a glass transition temperature (Tg) of 280 ° C. or higher. It is preferably 350 ° C. or higher, more preferably 380 ° C. or higher.
- the thermal decomposition temperature (1% weight loss temperature, Td1) is preferably 350 ° C. or higher, more preferably 450 ° C. or higher.
- the coefficient of thermal expansion (CTE) of the insulating resin layer is in the range of 10 ppm / K or more and 30 ppm / K or less. By controlling within such a range, deformation such as curl can be suppressed, and high dimensional stability can be ensured.
- CTE is an average value of the coefficients of thermal expansion of the insulating resin layer in the MD direction and the TD direction.
- the insulating resin layer has a total light transmittance of 80% or more in the visible region.
- the light transmittance at a wavelength of 450 nm is preferably 70% or more, more preferably 80% or more.
- the thickness of the insulating resin layer is 20 ⁇ m. More preferably, the total light transmittance is 85% or more.
- the YI of the insulating resin layer is 10 or less, preferably 5 or less, and more preferably 3.5 or less.
- the thickness of the insulating resin layer is 20 ⁇ m.
- the HAZE of the insulating resin layer is 3% or less, preferably 2% or less. By controlling within such a range, the visibility of the insulating resin layer can be improved. If HAZE exceeds 3%, for example, light scattering is likely to occur. Further, HAZE depends on the surface profile of the insulating resin layer, and even if it is a low profile insulating resin layer, it has both adhesive strength and transparency, and can be suitably used for a circuit board in which fine metal layers are laminated, for example. ..
- the tensile strength of the insulating resin layer is 100 MPa or more, preferably 150 MPa or more, and more preferably 200 MPa or more. By controlling within such a range, the strength of the insulating resin layer can be improved. If the tensile strength is less than 100 MPa, the insulating resin layer is likely to be torn or broken.
- the method for forming the insulating resin layer in the metal-clad laminate of the present embodiment is not particularly limited.
- a support base material is coated with a polyamic acid solution, dried, and then imidized to form a resin film.
- Method of manufacturing (hereinafter, casting method)
- the insulating resin layer is composed of a plurality of polyimide layers
- a solution of polyamic acid is repeatedly applied to and dried on the supporting base material a plurality of times, and then Method of imidization (hereinafter, sequential coating method), [4] Method of coating and drying a laminated structure of polyamic acid on a supporting substrate by multi-layer extrusion, and then imidization (hereinafter, multi-layer extrusion method). ) And so on.
- the method of applying the polyimide solution (or polyamic acid solution) on the substrate is not particularly limited, and for example, it can be applied with a coater such as a comma, a die, a knife, or a lip.
- a method of repeatedly applying a polyimide solution (or a polyamic acid solution) to the substrate and drying the substrate is preferable.
- the polyimide layer of the present embodiment may contain an inorganic filler in the polyimide layer, if necessary, as long as the object of the present invention is not impaired.
- an inorganic filler include silicon dioxide, aluminum oxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride and calcium fluoride. These can be used alone or in admixture of two or more.
- the material of the metal layer in the metal-clad laminate of the present embodiment is not particularly limited, but for example, copper, stainless steel, iron, nickel, berylium, aluminum, zinc, indium, silver, gold, tin, and zirconium. , Tantal, titanium, lead, magnesium, manganese and alloys thereof. Among these, copper, iron or nickel metal elements are preferable. In selecting these metal layers, it is necessary to select the metal layers so as to exhibit the characteristics required for the purpose of use, such as the light transmittance of the polyimide layer and the adhesiveness with the polyimide layer.
- the thickness of the metal layer is not particularly limited, but is preferably 100 ⁇ m or less, and more preferably 1 ⁇ m or more and 20 ⁇ m or less.
- a resin film composed of the polyimide of the present embodiment is prepared, metal is sputtered onto the resin film to form a seed layer, and then the metal layer is formed by plating, for example. It may be prepared by forming.
- the metal-clad laminate of the present embodiment may be prepared by preparing a resin film composed of the polyimide of the present embodiment and laminating a metal foil on the resin film by a method such as thermocompression bonding. Good.
- the surface of the resin film may be subjected to a modification treatment such as plasma treatment in order to enhance the adhesiveness between the resin film and the metal layer.
- a coating liquid containing the polyamic acid of the present embodiment is cast on a metal layer, dried to form a coating film, and then heat-treated to imidize the polyimide. It may be prepared by a method of forming a layer (cast method).
- the coating liquid containing the polyamic acid of the present embodiment may be cast directly on the metal layer, or may be cast after forming a coating film containing another polyamic acid.
- the transparency of the insulating resin layer may be directly applied on the polyimide layer of the single-sided metal-clad laminate obtained by the above method, or if necessary. It can be obtained by forming an adhesive layer that does not hinder and then laminating the metal layer by means such as heat pressure bonding.
- the hot press temperature when the metal layer is heat-pressed is not particularly limited, but it is desirable that the temperature is equal to or higher than the glass transition temperature of the polyimide layer adjacent to the metal layer to be used.
- the hot press pressure is preferably in the range of 1 kg / m 2 or more and 500 kg / m 2 or less, although it depends on the type of press equipment used.
- the ten-point average roughness Rzjis of the surface of the metal layer is preferably 0.5 ⁇ m or less, more preferably 0.01 ⁇ m or more. It is preferably in the range of 0.3 ⁇ m or less, and more preferably in the range of 0.01 ⁇ m or more and 0.2 ⁇ m or less. In particular, by setting the ten-point average roughness Rzjis of the surface of the metal layer to 0.2 ⁇ m or less, the HAZE of the insulating resin layer can be lowered, which is a more preferable embodiment. Further, from the viewpoint of adhesiveness to the insulating resin layer, the insulating resin layer in contact with the metal layer is preferably a cast surface.
- the 180 ° peel strength between the insulating resin layer and the metal layer in the metal-clad laminate of the present embodiment is preferably 0.5 kN / m or more.
- the total light transmittance, CTE and peel intensity are measured under the conditions described in the examples, and the values not particularly described are the measured values at room temperature (23 ° C.).
- the metal-clad laminate of the present embodiment is mainly useful as a circuit board material such as FPC and a member such as a mask used in the process of manufacturing electronic components. That is, a patterned metal-clad laminate can be obtained by processing the metal layer of the metal-clad laminate of the present embodiment into a pattern by a conventional method. This patterned metal-clad laminate can be used in addition to circuit boards such as FPCs, active elements such as transistors and diodes, and electronic circuits including passive devices such as resistors, capacitors, and inductors, as well as pressure and temperature.
- circuit boards such as FPCs, active elements such as transistors and diodes, and electronic circuits including passive devices such as resistors, capacitors, and inductors, as well as pressure and temperature.
- Sensor elements that sense light, humidity, etc., light emitting elements, liquid crystal displays, electrophoresis displays, self-luminous displays and other image display elements, wireless and wired communication elements, arithmetic elements, storage elements, MEMS elements, solar cells, thin film transistors, etc. It is available as.
- YI 100 ⁇ (1.2879X-1.0592Z) / Y ⁇ ⁇ ⁇ (1)
- X, Y and Z Tristimulus value of the test piece
- the YI (T10) of the polyimide film at a thickness of 10 ⁇ m was calculated by substituting the value of YI calculated by the above formula (1) into the following formula (2).
- YI (T10) YI / T ⁇ 10 ... (2)
- T Polyimide film thickness ( ⁇ m)
- CTE coefficient of thermal expansion
- Td1 Measurement of thermal decomposition temperature (Td1)
- TG thermogravimetric analysis
- APB 1,3-bis (3-aminophenoxy) benzene
- TPE-R 1,3-bis (4-aminophenoxy) benzene
- TFMB 2,2'-bis (trifluoromethyl) -4,4'-diamino Biphenyl
- BAPS Bis [4- (aminophenoxy) phenyl] sulfone
- AAPBZI 5-amino-2- (4-aminophenyl) benzoimidazole
- PMDA pyromellitic dianhydride
- 6FDA 2,2-bis (3,4-bis) Dicarboxyphenyl) -Hexafluoropropane dianhydride
- Benzene 3,3', 4,4'-biphenyltetracarboxylic dianhydride
- ODPA 4,4'-oxydiphthalic acid dianhydride
- CBDA 1,2,3 4-Cyclobutanetetracarboxylic dianhydride
- Reference example 1 The polyamic acid solution A was uniformly applied onto glass (E-XG, thickness 0.5 mm) so that the cured thickness was 10 ⁇ m, and then heated and dried at 100 ° C. to remove the solvent. Next, a stepwise heat treatment was performed from 100 ° C. to 360 ° C. to complete imidization, a polyimide layer a was formed on the glass, and a polyimide layer / glass laminate 1a was prepared.
- the glass side was irradiated with a 308 nm laser, and the polyimide layer and the glass were peeled off by laser lift-off (LLO) to prepare a single-layer polyimide film A.
- the measurement results of the polyimide film A are as follows. HAZE; 0.4%, total light transmittance (TT); 89%, light transmittance (T400); 74%, light transmittance (T430); 86%, light transmittance (T450); 88% , YI; 2.1, CTE; 7 ppm / K, thermal decomposition temperature (Td1); 503 ° C., glass transition temperature (Tg); 214 ° C., tensile elongation; 9.9%, tensile strength; 105 MPa
- Reference examples 2 to 16 Single-layer polyimide films B to P were prepared in the same manner as in Reference Example 1 except that the polyamic acid solution shown in Table 2 was used.
- polyimide films B to N HAZE, T.I. T. , T400, T430, T450, YI, CTE, Td1, Tg, tensile elongation, and tensile strength were determined. The results of these measurements are shown in Table 2.
- Example 1 Diluted solution (viscosity) of polyamic acid solution D on copper foil 1 (electrolytic copper foil, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., trade name; CF-T9DA-SV-12, thickness: 12 ⁇ m, Rzjis; 0.01 ⁇ m). (3000 cP) was uniformly applied so that the thickness after curing was 1.5 ⁇ m, and then heat-dried at 125 ° C. to remove the solvent. Next, a diluted solution of polyamic acid solution F (viscosity; 20000 cP was uniformly applied onto the solution so that the thickness after curing was 17 ⁇ m, and then heat-dried at 125 ° C. to remove the solvent.
- polyamic acid solution F viscosity; 20000 cP was uniformly applied onto the solution so that the thickness after curing was 17 ⁇ m, and then heat-dried at 125 ° C. to remove the solvent.
- a diluted solution (viscosity; 3000 cP) of the polyamic acid solution D was uniformly applied so that the thickness after curing was 1.5 ⁇ m, and then heat-dried at 125 ° C. to remove the solvent.
- a stepwise heat treatment is performed from 125 ° C. to 360 ° C. to complete imidization, and an insulating resin layer 1 having a thickness of 20 ⁇ m composed of a polyimide layer D / a polyimide layer F / a polyimide layer D is formed.
- the metal-clad laminate 1 was prepared. The peel strength of the metal-clad laminate 1 was 1.2 kN / m.
- the copper foil was etched and removed using an aqueous ferric chloride solution to prepare a polyimide film 1.
- HAZE, T.I. T. , T400, T430, T450, YI (T10) , CTE, Td1 and Tg were determined. The results of these measurements are shown in Table 3.
- YI (T10) indicates the yellowness obtained by converting the thickness of the polyimide film into 10 ⁇ m.
- Examples 2-4 In order to prepare the metal-clad laminates 2 to 4 in the same manner as in Example 1, as shown in Table 3, the type of polyamic acid and the thickness after the heat treatment were changed to form the insulating resin layers 2 to 4. Metal-clad laminates 2-45 were prepared.
- the copper foils of the metal-clad laminates 2 to 4 were removed by etching using an aqueous ferric chloride solution to prepare polyimide films 2 to 4.
- T. , T400, T430, T450, YI (T10) , CTE, Td1 and Tg are shown in Table 3.
- Example 5 A metal-clad laminate 5 was prepared in the same manner as in Example 1 except that the polyamic acid L was used instead of the polyamic acid solution F in Example 1.
- the prepared metal laminate 5 is cut to a size of 15 cm ⁇ 15 cm, a copper foil 1 cut to a size of 15 cm ⁇ 15 cm is superposed on the insulating resin layer surface of the laminate, and pressed at 340 ° C./30 min with a press machine.
- a double-sided metal-clad laminate 5 was prepared.
- the copper foil was partially etched to form a circuit pattern with a width of 1 mm copper foil. When the 180 ° peel strength was measured, the peel strength on the press side was 1.1 kN / m. Further, double-sided copper foil etching was performed to prepare a transparent polyimide film 5.
- the total light transmittance of the polyimide film 5 was 86%.
- the measurement results of the physical properties are also shown in Table 3.
- Example 6 Diluted solution (viscosity) of polyamic acid solution O on copper foil 2 (electrolytic copper foil, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., trade name; CF-T9DA-SV-12, thickness: 12 ⁇ m, Rzjis; 0.8 ⁇ m). 6160 cP) was uniformly applied so that the thickness after curing was 1.5 ⁇ m, and then heat-dried at 125 ° C. to remove the solvent. Next, a diluted solution of polyamic acid solution F (viscosity; 36000 cP was uniformly applied onto the solution so that the thickness after curing was 7 ⁇ m, and then heat-dried at 125 ° C. to remove the solvent.
- polyamic acid solution F viscosity; 36000 cP was uniformly applied onto the solution so that the thickness after curing was 7 ⁇ m, and then heat-dried at 125 ° C. to remove the solvent.
- a diluted solution (viscosity; 3700 cP) of the polyamic acid solution D was uniformly applied so that the thickness after curing was 1.5 ⁇ m, and then heat-dried at 125 ° C. to remove the solvent.
- a stepwise heat treatment is performed from 125 ° C. to 360 ° C. to complete imidization, and an insulating resin layer 6 having a thickness of 10 ⁇ m composed of a polyimide layer O / a polyimide layer F / a polyimide layer D is formed.
- the single-sided metal-clad laminate 6 was prepared.
- the peel strength of the polyamic acid-coated surface of the single-sided metal-clad laminate 6 was 1.2 kN / m.
- copper foil 2 electrolytic copper foil, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., trade name; CF-T9DA-SV-12, thickness; 12 ⁇ m, Rzjis; 0
- CF-T9DA-SV-12 thickness; 12 ⁇ m, Rzjis; 0
- the peel strength of the heat-pressed copper foil and the single-sided metal-clad laminate 6 was 1.1 kN / m.
- a copper foil was etched and removed from the obtained double-sided metal-clad laminate 6 with an aqueous ferric chloride solution to prepare a polyimide film 6.
- HAZE, T.I. T. , T400, T430, T450, YI (T10), CTE, Td1 and Tg were determined. The results of these measurements are shown in Table 3.
- YI (T10) indicates the yellowness obtained by converting the thickness of the polyimide film into 10 ⁇ m.
- Examples 7-9 In order to prepare the double-sided metal-clad laminates 7 to 9 in the same manner as in Example 6, the insulating resin layers 7 to 9 are formed by changing the type of polyamic acid and the thickness after heat treatment as shown in Table 3. , Double-sided metal-clad laminates 7 to 9 were prepared. The copper foils of the metal-clad laminates 7 to 9 were etched and removed using an aqueous ferric chloride solution to prepare polyimide films 7 to 9. HAZE, T.I. of each polyimide film. T. , T400, T430, T450, YI (T10), CTE, Td1 and Tg are shown in Table 3.
- Comparative Examples 1-2 In order to prepare the metal-clad laminates C1 and C2 in the same manner as in Example 1, as shown in Table 4, the insulating resin layers C1 and C2 were formed by changing the type of polyamic acid and the thickness after heat treatment. Metal-clad laminates C1 and C2 were prepared. The copper foils of the metal-clad laminates C1 and C2 were etched and removed using an aqueous ferric chloride solution to prepare polyimide films C1 and C2. HAZE, T.I. of each polyimide film. T. , T400, T430, T450, YI ( T10 ), CTE, Td1 and Tg are shown in Table 4.
- Comparative Example 3 Using a diluted solution of polyamic acid solution G (viscosity; 20000 cP), the mixture was uniformly applied onto the copper foil 1 so that the thickness after curing was 20 ⁇ m, and then heated and dried at 125 ° C. to remove the solvent. Then, a stepwise heat treatment was performed from 125 ° C. to 360 ° C. to complete imidization, an insulating resin layer of the polyimide layer G was formed, and a metal-clad laminate C3 was prepared. The peel strength of the metal-clad laminate C3 was 0.4 kN / m.
- polyamic acid solution G viscosity; 20000 cP
- Example 10 Polyamic acid solution D on copper foil 3 (electrolytic copper foil, manufactured by Nippon Denki Co., Ltd., peelable (P) copper foil, thickness; 2 ⁇ m (ultra-thin copper foil) + 18 ⁇ m (carrier copper foil), Rz; 1.1 ⁇ m)
- the diluted solution (viscosity; 3000 cP) of No. 1 was uniformly applied so that the thickness after curing was 1.0 ⁇ m, and then heat-dried at 125 ° C. to remove the solvent.
- a diluted solution of polyamic acid solution F viscosity; 20000 cP was uniformly applied onto the solution so that the thickness after curing was 10 ⁇ m, and then heat-dried at 125 ° C.
- a diluted solution (viscosity; 3000 cP) of the polyamic acid solution D was uniformly applied so that the thickness after curing was 1.0 ⁇ m, and then heat-dried at 125 ° C. to remove the solvent.
- a stepwise heat treatment is performed from 125 ° C. to 360 ° C. to complete imidization, and an insulating resin layer 10 having a thickness of 12 ⁇ m composed of a polyimide layer D / a polyimide layer F / a polyimide layer D is formed.
- the metal-clad laminate 10 was prepared. The peel strength of the metal-clad laminate 10 was 1.2 kN / m.
- the copper foil was etched and removed using an aqueous ferric chloride solution to prepare a polyimide film 10.
- HAZE, T.I. T. , T400, T430, T450, YI (T10) , CTE, Td1, Tg, peel strength, tensile elongation, tensile strength and warpage of the laminate were determined. The results of these measurements are shown in Table 5.
- YI (T10) indicates the yellowness obtained by converting the thickness of the polyimide film into 10 ⁇ m.
- the copper foil thickness in Table 5 indicates the thickness of the ultrathin copper foil excluding the carrier copper foil (the same applies to the following examples).
- Examples 11-16 In order to prepare the metal-clad laminates 11 to 16 in the same manner as in Example 1, as shown in Table 5, the type of polyamic acid and the thickness after the heat treatment were changed to form the insulating resin layers 11 to 16. Metal-clad laminates 11 to 16 were prepared.
- Example 12 instead of the copper foil 3, the copper foil 4 (electrolytic copper foil, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., trade name; CF-T9DA-SV-9, thickness; 9 ⁇ m, Rz; 0.8 ⁇ m) was used.
- the copper foil 4 electrolytic copper foil, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., trade name; CF-T9DA-SV-9, thickness; 9 ⁇ m, Rz; 0.8 ⁇ m
- Examples 13, 15 and 16 a double-sided metal-clad laminate was used instead of a single-sided metal-clad laminate.
- a single-sided metal-clad laminate is cut into a size of 15 cm x 15 cm, a copper foil of the same type as the copper foil used as a base material is laminated on the opposite side (laminated surface) of the insulating resin layer, and the temperature is 240 ° C./ Pressing was performed for 30 minutes to prepare double-sided metal-clad laminates 13, 15 and 16.
- the copper foils of the metal-clad laminates 11 to 16 were removed by etching using an aqueous ferric chloride solution to prepare polyimide films 11 to 16.
- T. , T400, T430, T450, YI (T10) , CTE, Td1, Tg, peel strength, tensile elongation, tensile strength and warpage of the laminate are shown in Table 5.
- Comparative Examples 4-5 In order to prepare the metal-clad laminates C4 and C5 in the same manner as in Example 10, as shown in Table 6, the type of polyamic acid and the thickness after the heat treatment were changed to form the insulating resin layers C4 and C5. Metal-clad laminates C4 and C5 were prepared. The copper foils of the metal-clad laminates C4 and C5 were etched and removed using an aqueous ferric chloride solution to prepare polyimide films C4 and C5. HAZE, T.I. of each polyimide film. T. , T400, T430, T450, YI, CTE, Td1, Tg, peel strength, tensile elongation, tensile strength and the measurement results of the warp of the laminated body are shown in Table 6.
- the resin film and metal-clad laminate of the present invention are preferably used as an insulating material for manufacturing electronic components such as FPCs, particularly for transparent FPCs that require colorless transparency accompanied by mounting of semiconductor elements. Further, the resin film of the present invention can be applied to display devices such as liquid crystal display devices, organic EL display devices, touch panels, color filters, electronic papers, and their components.
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Abstract
Description
下記の条件a及びb;
a)厚みが5μm以上200μm以下の範囲内であること;
b)全光線透過率が80%以上であること;
を満たし、
前記ポリイミド層の少なくとも1層がポリイミド層(P1)を含有し、
前記ポリイミド層(P1)を構成しているポリイミドは、酸無水物成分から誘導される酸無水物残基と、ジアミン成分から誘導されるジアミン残基と、を含有しており、
前記ポリイミドは、全酸無水物残基に対し、下記の一般式(1)で表される芳香族テトラカルボン酸無水物から誘導される酸無水物残基を50モル%以上含有し、全ジアミン残基に対し、下記の一般式(2)で表わされる芳香族ジアミン化合物から誘導されるジアミン残基を50モル%以上含有することを特徴とする樹脂フィルム。
[式(1)中、Xは単結合、-O-、又は-C(CF3)2-から選ばれる2価の基を示す。]
[式(2)中、Rは独立に、ハロゲン原子、又は炭素数1~6のハロゲン原子で置換されてもよいアルキル基若しくはアルコキシ基、又は炭素数1~6の1価の炭化水素基若しくはアルコキシ基で置換されてもよいフェニル基若しくはフェノキシ基を示し、Zは独立に-O-、-S-、-CH2-、-CH(CH3)-、-C(CH3)2-、-CO-、-COO-、-SO2-、-NH-又は-NHCO-から選ばれる2価の基を示し、n1は0~3の整数、n2は0~4の整数を示す。] That is, the present invention is a resin film having a plurality of polyimide layers.
The following conditions a and b;
a) The thickness must be within the range of 5 μm or more and 200 μm or less;
b) The total light transmittance is 80% or more;
The filling,
At least one of the polyimide layers contains a polyimide layer (P1),
The polyimide constituting the polyimide layer (P1) contains an acid anhydride residue derived from an acid anhydride component and a diamine residue derived from a diamine component.
The polyimide contains 50 mol% or more of an acid anhydride residue derived from an aromatic tetracarboxylic acid anhydride represented by the following general formula (1) with respect to the total acid anhydride residue, and is a total diamine. A resin film characterized by containing 50 mol% or more of a diamine residue derived from an aromatic diamine compound represented by the following general formula (2) with respect to the residue.
[In formula (1), X represents a divalent group selected from single bond, -O-, or -C (CF 3 ) 2- . ]
[In the formula (2), R is independently an alkyl group or an alkoxy group which may be substituted with a halogen atom or a halogen atom having 1 to 6 carbon atoms, or a monovalent hydrocarbon group having 1 to 6 carbon atoms. Indicates a phenyl or phenoxy group that may be substituted with an alkoxy group, where Z is independently -O-, -S-, -CH 2- , -CH (CH 3 )-, -C (CH 3 ) 2- , It represents a divalent group selected from -CO-, -COO-, -SO 2- , -NH- or -NHCO-, where n 1 is an integer of 0 to 3 and n 2 is an integer of 0 to 4. ]
[一般式(A1)中、置換基Xは独立にフッ素原子で置換されている炭素数1~3のアルキル素基を示し、m及びnは独立に1~4の整数を示す。] Further, in the resin film of the present invention, the polyimide constituting the main layer of the polyimide layer is an aromatic tetracarboxylic acid anhydride containing a diamine residue and / or a fluorine atom derived from an aromatic diamine compound containing a fluorine atom. It is preferred to include acid anhydride residues derived from. The polyimide constituting the main layer of the polyimide layer contains 50 mol% or more of diamine residues derived from the diamine compound represented by the following general formula (A1) with respect to all diamine residues. Is preferable.
[In the general formula (A1), the substituent X represents an alkyl element group having 1 to 3 carbon atoms independently substituted with a fluorine atom, and m and n independently represent an integer of 1 to 4. ]
前記絶縁樹脂層が上記樹脂フィルムからなることを特徴とする金属張積層体である。 The present invention is a metal-clad laminate comprising an insulating resin layer having a plurality of polyimide layers and a metal layer laminated on at least one surface of the insulating resin layer.
It is a metal-clad laminate characterized in that the insulating resin layer is made of the resin film.
絶縁樹脂層と、前記絶縁樹脂層の少なくとも一方の面に積層された金属層と、を備えた金属張積層体であって、
前記絶縁樹脂層が、単層又は複数層のポリイミド層からなり、下記の条件a~g;
a)厚みが5μm以上20μm以下の範囲内であること;
b)熱膨張係数(CTE)が10ppm/K以上30ppm/K以下の範囲内であること;
c)全光線透過率が80%以上であること;
d)YIが10以下であること;
e)HAZEが3%以下であること;
f)ガラス転移温度(Tg)が280℃以上であること;
g)引張強度が100MPa以上であること;
を満たすことを特徴とする。 The metal-clad laminate of the present invention
A metal-clad laminate comprising an insulating resin layer and a metal layer laminated on at least one surface of the insulating resin layer.
The insulating resin layer is composed of a single layer or a plurality of polyimide layers, and the following conditions a to g;
a) The thickness must be within the range of 5 μm or more and 20 μm or less;
b) The coefficient of thermal expansion (CTE) is in the range of 10 ppm / K or more and 30 ppm / K or less;
c) The total light transmittance is 80% or more;
d) YI is 10 or less;
e) HAZE is 3% or less;
f) The glass transition temperature (Tg) is 280 ° C or higher;
g) Tensile strength is 100 MPa or more;
It is characterized by satisfying.
前記絶縁樹脂層が請求項1に記載の樹脂フィルムからなり、
前記樹脂フィルムにおける前記ポリイミド層(P1)の面と前記金属層と重ね合わせて熱圧着する工程を含むことを特徴とする。 The method for producing a metal-clad laminate of the present invention comprises producing a metal-clad laminate comprising an insulating resin layer having a plurality of polyimide layers and a metal layer laminated on at least one surface of the insulating resin layer. It's a method
The insulating resin layer comprises the resin film according to claim 1.
It is characterized by including a step of superimposing the surface of the polyimide layer (P1) on the resin film and the metal layer and thermocompression bonding.
本発明の樹脂フィルムは、透明性の観点から、厚みが5μm以上200μm以下の範囲内にあり、可視領域の全光線透過率が80%以上であることを満たす必要がある。 Hereinafter, the resin film of the present invention will be described.
From the viewpoint of transparency, the resin film of the present invention needs to satisfy that the thickness is within the range of 5 μm or more and 200 μm or less, and the total light transmittance in the visible region is 80% or more.
ここで、非熱可塑性ポリイミドとは、一般に加熱しても軟化、接着性を示さないポリイミドのことであるが、本発明では、動的粘弾性測定装置(DMA)を用いて測定した、30℃における貯蔵弾性率が1.0×109Pa以上であり、360℃における貯蔵弾性率が1.0×108Pa以上であるポリイミドをいう。また、熱可塑性ポリイミドとは、一般にガラス転移温度(Tg)が明確に確認できるポリイミドのことであるが、本発明では、DMAを用いて測定した、30℃における貯蔵弾性率が1.0×109Pa未満であり、360℃における貯蔵弾性率が1.0×108Pa未満であるポリイミドをいう。 Further, the non-thermoplastic polyimide layer constitutes a low thermal expansion polyimide layer, and the thermoplastic polyimide layer constitutes a high thermal expansion polyimide layer. Here, the low thermal expansion polyimide layer is a polyimide layer having a coefficient of thermal expansion (CTE) preferably in the range of 1 ppm / K or more and 25 ppm / K or less, and more preferably in the range of 3 ppm / K or more and 25 ppm / K or less. Say. The highly thermally expandable polyimide layer has a CTE of preferably 35 ppm / K or more, more preferably 35 ppm / K or more and 80 ppm / K or less, and further preferably 35 ppm / K or more and 70 ppm / K or less. Refers to a layer. The polyimide layer can be a polyimide layer having a desired CTE by appropriately changing the combination of raw materials used, the thickness, and the drying / curing conditions.
Here, the non-thermoplastic polyimide is generally a polyimide that does not soften or show adhesiveness even when heated, but in the present invention, it is measured at 30 ° C. using a dynamic viscoelasticity measuring device (DMA). A polyimide having a storage elastic modulus of 1.0 × 10 9 Pa or more and a storage elastic modulus of 1.0 × 10 8 Pa or more at 360 ° C. Further, the thermoplastic polyimide is generally a polyimide in which the glass transition temperature (Tg) can be clearly confirmed, but in the present invention, the storage elastic modulus at 30 ° C. measured using DMA is 1.0 × 10. 9 is less than Pa, the storage modulus at 360 ° C. refers to polyimide is less than 1.0 × 10 8 Pa.
Rは置換基であり、独立に、ハロゲン原子、又は炭素数1~6のハロゲン原子で置換されてもよいアルキル基若しくはアルコキシ基、又は炭素数1~6の1価の炭化水素基若しくはアルコキシ基で置換されてもよいフェニル基若しくはフェノキシ基を示す。n1は独立に0~3の整数を示し、好ましくは0又は1である。ここで、「独立に」とは、上記式(2)において、複数の置換基R、2価の基Z、さらに整数n1が、同一でもよいし、異なっていてもよいことを意味する。なお、上記式(2)において、末端の二つのアミノ基における水素原子は置換されていてもよく、例えば-NR3R4(ここで、R3,R4は、独立してアルキル基などの任意の置換基を意味する)であってもよい。他のジアミン化合物についても同様である。
ただし、一般式(1)中、Xが単結合である場合、式(2)において、Zは独立に-O-、-S-、-CH2-、-CH(CH3)-又は-NH-から選ばれる2価の基を示す。 In equation (2), Z is independently -O-, -S-, -CH 2- , -CH (CH 3 )-, -C (CH 3 ) 2- , -CO-, -COO-, -SO. It represents a divalent group selected from 2-, -NH- or -NHCO-, preferably -O-. n 2 represents an integer from 0 to 4, preferably 0 or 1.
R is a substituent, which is an alkyl group or an alkoxy group which may be independently substituted with a halogen atom or a halogen atom having 1 to 6 carbon atoms, or a monovalent hydrocarbon group or an alkoxy group having 1 to 6 carbon atoms. Indicates a phenyl or phenoxy group that may be substituted with. n 1 independently represents an integer of 0 to 3, preferably 0 or 1. Here, "independently" means that, in the above formula (2), a plurality of substituents R, a divalent group Z, and an integer n 1 may be the same or different. In the above formula (2), the hydrogen atom in the two terminal amino groups may be substituted, for example, -NR 3 R 4 (where R 3 and R 4 are independently alkyl groups and the like. It may mean any substituent). The same applies to other diamine compounds.
However, in the general formula (1), when X is a single bond, in the formula (2), Z is independently -O-, -S-, -CH 2- , -CH (CH 3 )-or -NH. Indicates a divalent group selected from-.
本実施の形態のポリイミドは、上記酸無水物及びジアミンを溶媒中で反応させ、ポリアミド酸を生成したのち加熱閉環させることにより製造できる。例えば、酸無水物成分とジアミン成分をほぼ等モルで有機溶媒中に溶解させて、0℃以上100℃以下の範囲内の温度で30分乃至24時間撹拌し重合反応させることでポリイミドの前駆体であるポリアミド酸が得られる。反応にあたっては、生成する前駆体が有機溶媒中に5重量%以上30重量%以下の範囲内、好ましくは10重量%以上20重量%以下の範囲内となるように反応成分を溶解する。重合反応に用いる有機溶媒としては、例えば、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド(DMAC)、N-メチル-2-ピロリドン、2-ブタノン、ジメチルスホキシド、硫酸ジメチル、シクロヘキサノン、ジオキサン、テトラヒドロフラン、ジグライム、トリグライム、γ‐プチロラクト等が挙げられる。これらの溶媒を2種以上併用して使用することもでき、更にはキシレン、トルエンのような芳香族炭化水素の併用も可能である。また、このような有機溶剤の使用量としては特に制限されるものではないが、重合反応によって得られるポリアミド酸溶液(ポリイミド前駆体溶液)の濃度が5重量%乃至30重量%程度になるような使用量に調整して用いることが好ましい。 Next, a method for synthesizing the polyimides constituting the plurality of polyimide layers will be described.
The polyimide of the present embodiment can be produced by reacting the above-mentioned acid anhydride and diamine in a solvent to generate polyamic acid, and then heating and closing the ring. For example, the acid anhydride component and the diamine component are dissolved in an organic solvent in approximately equimolar amounts, and the mixture is stirred at a temperature in the range of 0 ° C. or higher and 100 ° C. or lower for 30 minutes to 24 hours to carry out a polymerization reaction to cause a polyimide precursor. Polyamic acid is obtained. In the reaction, the reaction component is dissolved in an organic solvent so that the precursor produced is in the range of 5% by weight or more and 30% by weight or less, preferably 10% by weight or more and 20% by weight or less. Examples of the organic solvent used in the polymerization reaction include N, N-dimethylformamide, N, N-dimethylacetamide (DMAC), N-methyl-2-pyrrolidone, 2-butanone, dimethyl sulfoxide, dimethyl sulfate, cyclohexanone, and dioxane. , Tetrahydrofuran, jiglime, triglime, γ-petitolactate and the like. Two or more of these solvents can be used in combination, and aromatic hydrocarbons such as xylene and toluene can also be used in combination. The amount of such an organic solvent used is not particularly limited, but the concentration of the polyamic acid solution (polyimide precursor solution) obtained by the polymerization reaction is about 5% by weight to 30% by weight. It is preferable to adjust the amount to be used.
本発明の金属張積層体は、絶縁樹脂層の少なくとも一方の面、すなわち、片側又は両側に金属層を有する。そして、絶縁樹脂層は2層以上のポリイミド樹脂層を有し、少なくとも一層が上述したポリイミド層(P1)である。 The metal-clad laminate of the present invention will be described below.
The metal-clad laminate of the present invention has a metal layer on at least one surface of the insulating resin layer, that is, on one side or both sides. The insulating resin layer has two or more polyimide resin layers, and at least one layer is the above-mentioned polyimide layer (P1).
構成2;M1/P1/P2/P1
構成3;M1/P1/P2/P1/M2
構成4;M1/P1/P2/P1/P2/P1/M2 Configuration 1; M1 / P1 / P2
Configuration 2; M1 / P1 / P2 / P1
Configuration 3; M1 / P1 / P2 / P1 / M2
Configuration 4; M1 / P1 / P2 / P1 / P2 / P1 / M2
ここで、非熱可塑性ポリイミドとは、一般に加熱しても軟化、接着性を示さないポリイミドのことであるが、本発明では、動的粘弾性測定装置(DMA)を用いて測定した、30℃における貯蔵弾性率が1.0×109Pa以上であり、350℃における貯蔵弾性率が1.0×108Pa以上であるポリイミドをいう。また、熱可塑性ポリイミドとは、一般にガラス転移温度(Tg)が明確に確認できるポリイミドのことであるが、本発明では、DMAを用いて測定した、30℃における貯蔵弾性率が1.0×109Pa未満であり、350℃における貯蔵弾性率が1.0×108Pa未満であるポリイミドをいう。 Further, the non-thermoplastic polyimide layer constitutes a low thermal expansion polyimide layer, and the thermoplastic polyimide layer constitutes a high thermal expansion polyimide layer. Here, the low thermal expansion polyimide layer is a polyimide layer having a coefficient of thermal expansion (CTE) preferably in the range of 1 ppm / K or more and 25 ppm / K or less, and more preferably in the range of 3 ppm / K or more and 25 ppm / K or less. Say. The highly thermally expandable polyimide layer has a CTE of preferably 35 ppm / K or more, more preferably 35 ppm / K or more and 80 ppm / K or less, and further preferably 35 ppm / K or more and 70 ppm / K or less. Refers to a layer. The polyimide layer can be a polyimide layer having a desired CTE by appropriately changing the combination of raw materials used, the thickness, and the drying / curing conditions.
Here, the non-thermoplastic polyimide is generally a polyimide that does not soften or show adhesiveness even when heated, but in the present invention, it is measured at 30 ° C. using a dynamic viscoelasticity measuring device (DMA). A polyimide having a storage elastic modulus of 1.0 × 10 9 Pa or more and a storage elastic modulus of 1.0 × 10 8 Pa or more at 350 ° C. Further, the thermoplastic polyimide is generally a polyimide in which the glass transition temperature (Tg) can be clearly confirmed, but in the present invention, the storage elastic modulus at 30 ° C. measured using DMA is 1.0 × 10. 9 is less than Pa, the storage modulus at 350 ° C. refers to polyimide is less than 1.0 × 10 8 Pa.
主たるポリイミド層は、非熱可塑性ポリイミドで構成することが好ましい。 In order to maintain the dimensional stability of the metal-clad laminate of the present embodiment, high transparency and colorlessness of the insulating resin layer, and improve the adhesiveness with the metal layer, the polyimide layer (P1) in contact with the metal layer When the thickness is T1 and the thickness of the main polyimide layer (hereinafter, sometimes referred to as "polyimide layer (A)") is T2, the thickness of T1 is preferably in the range of 1 μm or more and 4 μm or less, and the thickness of T2 is It is preferably in the range of 4 μm or more and 19 μm or less. From another viewpoint, the thickness of T1 is preferably 20% or less with respect to the thickness of the insulating resin layer. Here, "main" means having the largest thickness among the plurality of polyimide layers constituting the insulating resin layer, preferably 60% or more, more preferably 70% with respect to the thickness of the insulating resin layer. It means having the above thickness.
The main polyimide layer is preferably composed of non-thermoplastic polyimide.
特に、樹脂フィルムにおけるポリイミド層(P1)の面と金属層と重ね合わせて熱圧着する工程を含むことが望ましい。 The method for forming the insulating resin layer in the metal-clad laminate of the present embodiment is not particularly limited. For example, [1] a support base material is coated with a polyamic acid solution, dried, and then imidized to form a resin film. Method of manufacturing (hereinafter, casting method), [2] A method of applying a polyamic acid solution to a supporting base material, drying it, peeling the polyamic acid gel film from the supporting base material, and imidizing it to produce a resin film. And so on. When the insulating resin layer is composed of a plurality of polyimide layers, as an embodiment of the manufacturing method thereof, for example, [3] a solution of polyamic acid is repeatedly applied to and dried on the supporting base material a plurality of times, and then Method of imidization (hereinafter, sequential coating method), [4] Method of coating and drying a laminated structure of polyamic acid on a supporting substrate by multi-layer extrusion, and then imidization (hereinafter, multi-layer extrusion method). ) And so on. The method of applying the polyimide solution (or polyamic acid solution) on the substrate is not particularly limited, and for example, it can be applied with a coater such as a comma, a die, a knife, or a lip. When forming the multilayer polyimide layer, a method of repeatedly applying a polyimide solution (or a polyamic acid solution) to the substrate and drying the substrate is preferable.
In particular, it is desirable to include a step of superimposing the surface of the polyimide layer (P1) on the resin film and the metal layer and thermocompression bonding.
ポリイミドフィルム(50mm×50mm)を、島津製作所社製のUV-3600分光光度計にて光透過率及びYIを測定した。
1)光透過率
JIS Z 8722に準拠して、波長が400nm、430nm及び450nmの光におけるそれぞれの光透過率(T400、T430及びT450)を算出した。
2)YI
JIS Z 8722に準拠して、下記式(1)で表される計算式に基づいて算出した。
YI=100×(1.2879X-1.0592Z)/Y ・・・(1)
X、Y及びZ:試験片の三刺激値
厚みが10μmにおけるポリイミドフィルムのYI(T10)は、上記式(1)で算出されたYIの値を下記式(2)に代入して算出した。
YI(T10)=YI/T×10 ・・・(2)
T:ポリイミドフィルムの厚み(μm) [Calculation of light transmittance and YI (yellowness)]
The light transmittance and YI of the polyimide film (50 mm × 50 mm) were measured with a UV-3600 spectrophotometer manufactured by Shimadzu Corporation.
1) Light transmittance The light transmittances (T400, T430 and T450) of light having wavelengths of 400 nm, 430 nm and 450 nm were calculated in accordance with JIS Z 8722.
2) YI
It was calculated based on the formula represented by the following formula (1) in accordance with JIS Z 8722.
YI = 100 × (1.2879X-1.0592Z) / Y ・ ・ ・ (1)
X, Y and Z: Tristimulus value of the test piece The YI (T10) of the polyimide film at a thickness of 10 μm was calculated by substituting the value of YI calculated by the above formula (1) into the following formula (2).
YI (T10) = YI / T × 10 ... (2)
T: Polyimide film thickness (μm)
ポリイミドフィルム(3mm×15mm)を、熱機械分析(TMA)装置にて5.0gの荷重を加えながら10℃/minの昇温速度で30℃から280℃まで昇温し、次いで、250℃から100℃までの降温し、降温時におけるポリイミドフィルムの伸び量(線膨張)から熱膨張係数を測定した。 [Measurement of coefficient of thermal expansion (CTE)]
The polyimide film (3 mm × 15 mm) was heated from 30 ° C. to 280 ° C. at a heating rate of 10 ° C./min while applying a load of 5.0 g using a thermomechanical analysis (TMA) device, and then from 250 ° C. The temperature was lowered to 100 ° C., and the coefficient of thermal expansion was measured from the amount of elongation (linear expansion) of the polyimide film when the temperature was lowered.
窒素雰囲気下で10~20mgの重さのポリイミドフィルムを、SEIKO社製の熱重量分析(TG)装置TG/DTA6200にて一定の速度で30℃から550℃まで昇温させたときの重量変化を測定し、200℃での重量をゼロとし、重量減少率が1%の時の温度を熱分解温度(Td1)とした。 [Measurement of thermal decomposition temperature (Td1)]
The weight change when a polyimide film weighing 10 to 20 mg in a nitrogen atmosphere is heated from 30 ° C. to 550 ° C. at a constant rate by a thermogravimetric analysis (TG) device TG / DTA6200 manufactured by SEIKO. The weight at 200 ° C. was set to zero, and the temperature when the weight loss rate was 1% was defined as the thermal decomposition temperature (Td1).
ポリイミドフィルム(50mm×50mm)を、日本電色工業社製のHAZE METER NDH500にて、全光線透過率(T.T.)及びHAZE(濁度)をJIS K 7136に準拠して測定した。 [Calculation of total light transmittance (TT) and HAZE (turbidity)]
A polyimide film (50 mm × 50 mm) was measured with HAZE METER NDH500 manufactured by Nippon Denshoku Kogyo Co., Ltd. in terms of total light transmittance (TT) and HAZE (turbidity) in accordance with JIS K 7136.
粘度は、恒温水槽付のコーンプレート式粘度計(トキメック社製)にて、合成例で得られたポリアミド酸溶液について25℃で測定した。 [Measurement of viscosity]
The viscosity was measured at 25 ° C. for the polyamic acid solution obtained in the synthetic example with a cone plate type viscometer (manufactured by Tokimec Co., Ltd.) equipped with a constant temperature water tank.
ポリイミドフィルム(10mm×22.6mm)を動的熱機械分析装置にて20℃から500℃まで5℃/分で昇温させたときの動的粘弾性を測定し、ガラス転移温度(Tanδ極大値:℃)を求めた。 [Measurement of glass transition temperature (Tg)]
The dynamic viscoelasticity when the polyimide film (10 mm × 22.6 mm) was heated from 20 ° C. to 500 ° C. at 5 ° C./min with a dynamic thermomechanical analyzer was measured, and the glass transition temperature (Tan δ maximum value) was measured. : ° C) was calculated.
テンションテスターを用い、積層体から得られた幅1mmの回路を有する試験サンプルの樹脂側を両面テープによりアルミ板に固定し、銅を180°方向に50mm/minの速度で剥離して、ピール強度を求めた。 [Measurement of peel strength]
Using a tension tester, the resin side of the test sample having a circuit with a width of 1 mm obtained from the laminate was fixed to an aluminum plate with double-sided tape, and copper was peeled off at a speed of 50 mm / min in the 180 ° direction to peel strength. Asked.
サンプルを約10mm角の大きさにカットし、試料台に両面テープで固定させ、軟X線を照射し、銅箔表面の静電気を除去した後、表面粗さを測定した。走査型プローブ顕微鏡(AFM、ブルカー・エイエックスエス社製、商品名:Dimension Icon型SPM)を用い、以下の測定条件にて銅箔表面の十点平均粗さRz(RzJis)を測定した。測定条件は、下記のとおり。
測定モード;タッピングモード
測定エリア;1μm×1μm
スキャンスピード;1Hz
プローブ;Buruker製、RTESP-300 [Measurement of surface roughness of copper foil]
The sample was cut into a size of about 10 mm square, fixed to a sample table with double-sided tape, irradiated with soft X-rays to remove static electricity on the surface of the copper foil, and then the surface roughness was measured. Using a scanning probe microscope (AFM, manufactured by Bruker AXS Co., Ltd., trade name: Dimension Icon type SPM), the ten-point average roughness Rz (RzJis) of the copper foil surface was measured under the following measurement conditions. The measurement conditions are as follows.
Measurement mode; Tapping mode Measurement area; 1 μm × 1 μm
Scan speed; 1Hz
Probe; RETSP-300, manufactured by Buruker
ポリイミドフィルムを12.7mm×150mmに切り出し、引張試験装置(TOYO精機製 STROGRAPHVE1D)を用いて、JIS K 7127に準拠して、室温で50mm/min、100Nで試験を行い、フィルムの引張強度及び引張伸度を測定した。 [Measurement of tensile strength and tensile elongation]
A polyimide film was cut into a size of 12.7 mm x 150 mm and tested using a tensile tester (STROGRAPHVE1D manufactured by TOYO Tires) at room temperature of 50 mm / min and 100 N in accordance with JIS K 7127, and the tensile strength and tensile strength of the film were increased. Elongation was measured.
反りの評価は、以下の方法で行った。10cm×10cmの金属層とポリイミド層の積層体を、水平な平面上にポリイミド層を上にして静置し、積層体の4隅の平面からの浮きの高さの平均を測定し、10mm以下を「良」、10mmを超える場合を「不可」とした。 [Measurement of warpage of laminated body]
The warp was evaluated by the following method. A 10 cm x 10 cm metal layer and a polyimide layer are placed on a horizontal plane with the polyimide layer facing up, and the average height of the floats from the four corners of the laminated body is measured and 10 mm or less. Was "good" and the case exceeding 10 mm was "impossible".
APB:1,3-ビス(3-アミノフェノキシ)ベンゼン
TPE-R:1,3-ビス(4-アミノフェノキシ)ベンゼン
TFMB:2,2'-ビス(トリフルオロメチル)-4,4'-ジアミノビフェニル
BAPS:ビス[4-(アミノフェノキシ)フェニル]スルホン
AAPBZI:5-アミノ-2-(4-アミノフェニル)ベンゾイミダゾール
PMDA:ピロメリット酸二無水物
6FDA:2,2-ビス(3,4-ジカルボキシフェニル)-ヘキサフルオロプロパン二無水物
BPDA:3,3',4,4'-ビフェニルテトラカルボン酸二無水物
ODPA:4,4’-オキシジフタル酸二無水物
CBDA:1,2,3,4-シクロブタンテトラカルボン酸二無水物
DMAc:N,N-ジメチルアセトアミド The abbreviations used in the examples and the like indicate the following compounds.
APB: 1,3-bis (3-aminophenoxy) benzene TPE-R: 1,3-bis (4-aminophenoxy) benzene TFMB: 2,2'-bis (trifluoromethyl) -4,4'-diamino Biphenyl BAPS: Bis [4- (aminophenoxy) phenyl] sulfone AAPBZI: 5-amino-2- (4-aminophenyl) benzoimidazole PMDA: pyromellitic dianhydride 6FDA: 2,2-bis (3,4-bis) Dicarboxyphenyl) -Hexafluoropropane dianhydride Benzene: 3,3', 4,4'-biphenyltetracarboxylic dianhydride ODPA: 4,4'-oxydiphthalic acid dianhydride CBDA: 1,2,3 4-Cyclobutanetetracarboxylic dianhydride DMAc: N, N-dimethylacetamide
ポリアミド酸溶液A~Pを合成するため、窒素気流下で、200mlのセパラブルフラスコの中に、表1で示した固形分濃度となるように溶剤のDMAcを加え、表1に示したジアミン成分及び酸無水物成分を攪拌しながら45℃、2時間加熱し溶解させた。その後、溶液を室温で2日間攪拌を続けて重合反応を行い、ポリアミド酸の粘稠な溶液A~Pを調製した。 Synthesis Examples 1 to 16
In order to synthesize the polyamic acid solutions A to P, the solvent DMAc was added to a 200 ml separable flask so as to have the solid content concentration shown in Table 1 under a nitrogen stream, and the diamine component shown in Table 1 was added. And the acid anhydride component was dissolved by heating at 45 ° C. for 2 hours with stirring. Then, the solution was stirred at room temperature for 2 days to carry out a polymerization reaction to prepare viscous solutions A to P of polyamic acid.
ガラス(E-XG、厚み0.5mm)の上に、ポリアミド酸溶液Aを硬化後の厚みが10μmとなるように均一に塗布した後、100℃で加熱乾燥し、溶媒を除去した。次に、100℃から360℃まで段階的な熱処理を行い、イミド化を完結し、ガラスの上にポリイミド層aを形成し、ポリイミド層/ガラスの積層体1aを調製した。 Reference example 1
The polyamic acid solution A was uniformly applied onto glass (E-XG, thickness 0.5 mm) so that the cured thickness was 10 μm, and then heated and dried at 100 ° C. to remove the solvent. Next, a stepwise heat treatment was performed from 100 ° C. to 360 ° C. to complete imidization, a polyimide layer a was formed on the glass, and a polyimide layer / glass laminate 1a was prepared.
HAZE;0.4%、全光線透過率(T.T.);89%、光透過率(T400);74%、光透過率(T430);86%、光透過率(T450);88%、YI;2.1、CTE;7ppm/K、熱分解温度(Td1);503℃、ガラス転移温度(Tg);214℃、引張伸度;9.9%、引張強度;105MPa The glass side was irradiated with a 308 nm laser, and the polyimide layer and the glass were peeled off by laser lift-off (LLO) to prepare a single-layer polyimide film A. The measurement results of the polyimide film A are as follows.
HAZE; 0.4%, total light transmittance (TT); 89%, light transmittance (T400); 74%, light transmittance (T430); 86%, light transmittance (T450); 88% , YI; 2.1, CTE; 7 ppm / K, thermal decomposition temperature (Td1); 503 ° C., glass transition temperature (Tg); 214 ° C., tensile elongation; 9.9%, tensile strength; 105 MPa
表2に示すポリアミド酸溶液を使用した他は、参考例1と同様にして、単層ポリイミドフィルムB~Pを調製した。ポリイミドフィルムB~Nについて、HAZE、T.T.、T400、T430、T450、YI、CTE、Td1、Tg、引張伸度、及び引張強度を求めた。これらの測定結果を表2に示す。 Reference examples 2 to 16
Single-layer polyimide films B to P were prepared in the same manner as in Reference Example 1 except that the polyamic acid solution shown in Table 2 was used. Regarding polyimide films B to N, HAZE, T.I. T. , T400, T430, T450, YI, CTE, Td1, Tg, tensile elongation, and tensile strength were determined. The results of these measurements are shown in Table 2.
銅箔1(電解銅箔、福田金属箔粉工業社製、商品名;CF-T9DA-SV-12、厚み;12μm、Rzjis;0.01μm)の上に、ポリアミド酸溶液Dの希釈溶液(粘度;3000cP)を硬化後の厚みが1.5μmとなるように均一に塗布した後、125℃で加熱乾燥し、溶媒を除去した。次に、その上にポリアミド酸溶液Fの希釈溶液(粘度;20000cPを硬化後の厚みが17μmとなるように均一に塗布した後、125℃で加熱乾燥し溶媒を除去した。更に、その上にポリアミド酸溶液Dの希釈溶液(粘度;3000cP)を硬化後の厚みが1.5μmとなるように均一に塗布した後、125℃で加熱乾燥し溶剤を除去した。このようにして、3層のポリアミド酸層を形成した後、125℃から360℃まで段階的な熱処理を行い、イミド化を完結し、ポリイミド層D/ポリイミド層F/ポリイミド層Dからなる厚みが20μmの絶縁樹脂層1を形成し、金属張積層体1を調製した。金属張積層体1におけるピール強度は、1.2kN/mであった。 Example 1
Diluted solution (viscosity) of polyamic acid solution D on copper foil 1 (electrolytic copper foil, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., trade name; CF-T9DA-SV-12, thickness: 12 μm, Rzjis; 0.01 μm). (3000 cP) was uniformly applied so that the thickness after curing was 1.5 μm, and then heat-dried at 125 ° C. to remove the solvent. Next, a diluted solution of polyamic acid solution F (viscosity; 20000 cP was uniformly applied onto the solution so that the thickness after curing was 17 μm, and then heat-dried at 125 ° C. to remove the solvent. A diluted solution (viscosity; 3000 cP) of the polyamic acid solution D was uniformly applied so that the thickness after curing was 1.5 μm, and then heat-dried at 125 ° C. to remove the solvent. After forming the polyamic acid layer, a stepwise heat treatment is performed from 125 ° C. to 360 ° C. to complete imidization, and an insulating resin layer 1 having a thickness of 20 μm composed of a polyimide layer D / a polyimide layer F / a polyimide layer D is formed. The metal-clad laminate 1 was prepared. The peel strength of the metal-clad laminate 1 was 1.2 kN / m.
実施例1と同様に、金属張積層体2~4を調製するため、表3で示したように、ポリアミド酸の種類と熱処理後の厚みを変えて、絶縁樹脂層2~4を形成し、金属張積層体2~45を調製した。 Examples 2-4
In order to prepare the metal-clad laminates 2 to 4 in the same manner as in Example 1, as shown in Table 3, the type of polyamic acid and the thickness after the heat treatment were changed to form the insulating resin layers 2 to 4. Metal-clad laminates 2-45 were prepared.
実施例1におけるポリアミド酸溶液Fの代わりに、ポリアミド酸Lを使用したこと以外、実施例1と同様にして、金属張積層体5を調製した。調製した金属積層体5を15cm×15cmにカットし、この積層体の絶縁樹脂層面に15cm×15cmのサイズにカットした銅箔1を重ね合わせ、プレス機にて、340℃/30minでプレスを行い、両面金属張積層体5を調製した。銅箔を部分的に銅箔エッチングして、1mm銅箔幅の回路パターンを形成した。180°ピール強度を測定したところ、プレス側のピール強度が1.1kN/mであった。また、両面銅箔エッチングを行い、透明なポリイミドフィルム5を調製した。ポリイミドフィルム5の全光線透過率が86%であった。その物性測定結果も表3に示す。 Example 5
A metal-clad laminate 5 was prepared in the same manner as in Example 1 except that the polyamic acid L was used instead of the polyamic acid solution F in Example 1. The prepared metal laminate 5 is cut to a size of 15 cm × 15 cm, a copper foil 1 cut to a size of 15 cm × 15 cm is superposed on the insulating resin layer surface of the laminate, and pressed at 340 ° C./30 min with a press machine. , A double-sided metal-clad laminate 5 was prepared. The copper foil was partially etched to form a circuit pattern with a width of 1 mm copper foil. When the 180 ° peel strength was measured, the peel strength on the press side was 1.1 kN / m. Further, double-sided copper foil etching was performed to prepare a transparent polyimide film 5. The total light transmittance of the polyimide film 5 was 86%. The measurement results of the physical properties are also shown in Table 3.
銅箔2(電解銅箔、福田金属箔粉工業社製、商品名;CF-T9DA-SV-12、厚み;12μm、Rzjis;0.8μm)の上に、ポリアミド酸溶液Oの希釈溶液(粘度;6160cP)を硬化後の厚みが1.5μmとなるように均一に塗布した後、125℃で加熱乾燥し、溶媒を除去した。次に、その上にポリアミド酸溶液Fの希釈溶液(粘度;36000cPを硬化後の厚みが7μmとなるように均一に塗布した後、125℃で加熱乾燥し溶媒を除去した。更に、その上にポリアミド酸溶液Dの希釈溶液(粘度;3700cP)を硬化後の厚みが1.5μmとなるように均一に塗布した後、125℃で加熱乾燥し溶剤を除去した。このようにして、3層のポリアミド酸層を形成した後、125℃から360℃まで段階的な熱処理を行い、イミド化を完結し、ポリイミド層O/ポリイミド層F/ポリイミド層Dからなる厚みが10μmの絶縁樹脂層6を形成し、片面金属張積層体6を調製した。片面金属張積層体6におけるポリアミド酸塗布面のピール強度は、1.2kN/mであった。 Example 6
Diluted solution (viscosity) of polyamic acid solution O on copper foil 2 (electrolytic copper foil, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., trade name; CF-T9DA-SV-12, thickness: 12 μm, Rzjis; 0.8 μm). 6160 cP) was uniformly applied so that the thickness after curing was 1.5 μm, and then heat-dried at 125 ° C. to remove the solvent. Next, a diluted solution of polyamic acid solution F (viscosity; 36000 cP was uniformly applied onto the solution so that the thickness after curing was 7 μm, and then heat-dried at 125 ° C. to remove the solvent. A diluted solution (viscosity; 3700 cP) of the polyamic acid solution D was uniformly applied so that the thickness after curing was 1.5 μm, and then heat-dried at 125 ° C. to remove the solvent. After forming the polyamic acid layer, a stepwise heat treatment is performed from 125 ° C. to 360 ° C. to complete imidization, and an insulating resin layer 6 having a thickness of 10 μm composed of a polyimide layer O / a polyimide layer F / a polyimide layer D is formed. The single-sided metal-clad laminate 6 was prepared. The peel strength of the polyamic acid-coated surface of the single-sided metal-clad laminate 6 was 1.2 kN / m.
得られた両面金属張積層体6を、塩化第二鉄水溶液を用いて、銅箔をエッチング除去して、ポリイミドフィルム6を調製した。ポリイミドフィルム1について、HAZE、T.T.、T400、T430、T450、YI(T10)、CTE、Td1及びTgを求めた。これらの測定結果を表3に示す。ここで、YI(T10)は、ポリイミドフィルムの厚みを10μmに換算した黄色度を示す。 Further, copper foil 2 (electrolytic copper foil, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., trade name; CF-T9DA-SV-12, thickness; 12 μm, Rzjis; 0) was added to the polyimide layer D of the obtained single-sided metal-clad laminate 6. 8.8 μm) was stacked and heat-pressed at 230 ° C. for 30 minutes at a pressure of 68 kg / m2 to obtain a double-sided metal-clad laminate 6. The peel strength of the heat-pressed copper foil and the single-sided metal-clad laminate 6 was 1.1 kN / m.
A copper foil was etched and removed from the obtained double-sided metal-clad laminate 6 with an aqueous ferric chloride solution to prepare a polyimide film 6. Regarding the polyimide film 1, HAZE, T.I. T. , T400, T430, T450, YI (T10), CTE, Td1 and Tg were determined. The results of these measurements are shown in Table 3. Here, YI (T10) indicates the yellowness obtained by converting the thickness of the polyimide film into 10 μm.
実施例6と同様に、両面金属張積層体7~9を調製するため、表3で示したように、ポリアミド酸の種類と熱処理後の厚みを変えて、絶縁樹脂層7~9を形成し、両面金属張積層体7~9を調製した。
塩化第二鉄水溶液を用いて、金属張積層体7~9の銅箔をエッチング除去して、ポリイミドフィルム7~9を調製した。各ポリイミドフィルムのHAZE、T.T.、T400、T430、T450、YI(T10)、CTE、Td1及びTgの測定結果を表3に示す。 Examples 7-9
In order to prepare the double-sided metal-clad laminates 7 to 9 in the same manner as in Example 6, the insulating resin layers 7 to 9 are formed by changing the type of polyamic acid and the thickness after heat treatment as shown in Table 3. , Double-sided metal-clad laminates 7 to 9 were prepared.
The copper foils of the metal-clad laminates 7 to 9 were etched and removed using an aqueous ferric chloride solution to prepare polyimide films 7 to 9. HAZE, T.I. of each polyimide film. T. , T400, T430, T450, YI (T10), CTE, Td1 and Tg are shown in Table 3.
実施例1と同様に、金属張積層体C1、C2を調製するため、表4で示したように、ポリアミド酸の種類と熱処理後の厚みを変えて、絶縁樹脂層C1、C2を形成し、金属張積層体C1、C2を調製した。
塩化第二鉄水溶液を用いて、金属張積層体C1、C2の銅箔をエッチング除去して、ポリイミドフィルムC1、C2を調製した。各ポリイミドフィルムのHAZE、T.T.、T400、T430、T450、YI(T10)、CTE、Td1及びTgの測定結果を表4に示す。 Comparative Examples 1-2
In order to prepare the metal-clad laminates C1 and C2 in the same manner as in Example 1, as shown in Table 4, the insulating resin layers C1 and C2 were formed by changing the type of polyamic acid and the thickness after heat treatment. Metal-clad laminates C1 and C2 were prepared.
The copper foils of the metal-clad laminates C1 and C2 were etched and removed using an aqueous ferric chloride solution to prepare polyimide films C1 and C2. HAZE, T.I. of each polyimide film. T. , T400, T430, T450, YI ( T10 ), CTE, Td1 and Tg are shown in Table 4.
ポリアミド酸溶液Gの希釈溶液(粘度;20000cP)を用いて、銅箔1の上に硬化後の厚みが20μmとなるように均一に塗布した後、125℃で加熱乾燥し溶媒を除去した。その後、125℃から360℃まで段階的な熱処理を行い、イミド化を完結し、ポリイミド層Gの絶縁樹脂層を形成し、金属張積層体C3を調製した。金属張積層体C3におけるピール強度は、0.4kN/mであった。 Comparative Example 3
Using a diluted solution of polyamic acid solution G (viscosity; 20000 cP), the mixture was uniformly applied onto the copper foil 1 so that the thickness after curing was 20 μm, and then heated and dried at 125 ° C. to remove the solvent. Then, a stepwise heat treatment was performed from 125 ° C. to 360 ° C. to complete imidization, an insulating resin layer of the polyimide layer G was formed, and a metal-clad laminate C3 was prepared. The peel strength of the metal-clad laminate C3 was 0.4 kN / m.
銅箔3(電解銅箔、日本電解社製、ピーラブル(P)銅箔、厚み;2μm(極薄銅箔)+18μm(キャリア銅箔)、Rz;1.1μm)の上に、ポリアミド酸溶液Dの希釈溶液(粘度;3000cP)を硬化後の厚みが1.0μmとなるように均一に塗布した後、125℃で加熱乾燥し、溶媒を除去した。次に、その上にポリアミド酸溶液Fの希釈溶液(粘度;20000cPを硬化後の厚みが10μmとなるように均一に塗布した後、125℃で加熱乾燥し溶媒を除去した。更に、その上にポリアミド酸溶液Dの希釈溶液(粘度;3000cP)を硬化後の厚みが1.0μmとなるように均一に塗布した後、125℃で加熱乾燥し溶剤を除去した。このようにして、3層のポリアミド酸層を形成した後、125℃から360℃まで段階的な熱処理を行い、イミド化を完結し、ポリイミド層D/ポリイミド層F/ポリイミド層Dからなる厚みが12μmの絶縁樹脂層10を形成し、金属張積層体10を調製した。金属張積層体10におけるピール強度は、1.2kN/mであった。 Example 10
Polyamic acid solution D on copper foil 3 (electrolytic copper foil, manufactured by Nippon Denki Co., Ltd., peelable (P) copper foil, thickness; 2 μm (ultra-thin copper foil) + 18 μm (carrier copper foil), Rz; 1.1 μm) The diluted solution (viscosity; 3000 cP) of No. 1 was uniformly applied so that the thickness after curing was 1.0 μm, and then heat-dried at 125 ° C. to remove the solvent. Next, a diluted solution of polyamic acid solution F (viscosity; 20000 cP was uniformly applied onto the solution so that the thickness after curing was 10 μm, and then heat-dried at 125 ° C. to remove the solvent. A diluted solution (viscosity; 3000 cP) of the polyamic acid solution D was uniformly applied so that the thickness after curing was 1.0 μm, and then heat-dried at 125 ° C. to remove the solvent. After forming the polyamic acid layer, a stepwise heat treatment is performed from 125 ° C. to 360 ° C. to complete imidization, and an insulating resin layer 10 having a thickness of 12 μm composed of a polyimide layer D / a polyimide layer F / a polyimide layer D is formed. The metal-clad laminate 10 was prepared. The peel strength of the metal-clad laminate 10 was 1.2 kN / m.
これらの測定結果を表5に示す。ここで、YI(T10)は、ポリイミドフィルムの厚みを10μmに換算した黄色度を示す。ピーラブル銅箔の場合、表5の銅箔厚みは、キャリア銅箔を除いた極薄銅箔の厚みを示す(以下の実施例でも同じ)。 The copper foil was etched and removed using an aqueous ferric chloride solution to prepare a polyimide film 10. Regarding the polyimide film 10, HAZE, T.I. T. , T400, T430, T450, YI (T10) , CTE, Td1, Tg, peel strength, tensile elongation, tensile strength and warpage of the laminate were determined.
The results of these measurements are shown in Table 5. Here, YI (T10) indicates the yellowness obtained by converting the thickness of the polyimide film into 10 μm. In the case of peelable copper foil, the copper foil thickness in Table 5 indicates the thickness of the ultrathin copper foil excluding the carrier copper foil (the same applies to the following examples).
実施例1と同様に、金属張積層体11~16を調製するため、表5で示したように、ポリアミド酸の種類と熱処理後の厚みを変えて、絶縁樹脂層11~16を形成し、金属張積層体11~16を調製した。 Examples 11-16
In order to prepare the metal-clad laminates 11 to 16 in the same manner as in Example 1, as shown in Table 5, the type of polyamic acid and the thickness after the heat treatment were changed to form the insulating resin layers 11 to 16. Metal-clad laminates 11 to 16 were prepared.
一方、実施例13,15,16は、片面金属張積層体ではなく、両面金属張積層体とした。すなわち、片面金属張積層板を15cm×15cmにカットし、基材となる銅箔と同じ種類の銅箔を絶縁樹脂層の反対側(ラミネート面)に重ね合わせ、プレス機にて、240℃/30minでプレスを行い、両面金属張積層体13,15,16を調製した。 Here, in Examples 12 to 15, instead of the copper foil 3, the copper foil 4 (electrolytic copper foil, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., trade name; CF-T9DA-SV-9, thickness; 9 μm, Rz; 0.8 μm) was used.
On the other hand, in Examples 13, 15 and 16, a double-sided metal-clad laminate was used instead of a single-sided metal-clad laminate. That is, a single-sided metal-clad laminate is cut into a size of 15 cm x 15 cm, a copper foil of the same type as the copper foil used as a base material is laminated on the opposite side (laminated surface) of the insulating resin layer, and the temperature is 240 ° C./ Pressing was performed for 30 minutes to prepare double-sided metal-clad laminates 13, 15 and 16.
実施例10と同様に、金属張積層体C4、C5を調製するため、表6で示したように、ポリアミド酸の種類と熱処理後の厚みを変えて、絶縁樹脂層C4、C5を形成し、金属張積層体C4、C5を調製した。
塩化第二鉄水溶液を用いて、金属張積層体C4、C5の銅箔をエッチング除去して、ポリイミドフィルムC4、C5を調製した。各ポリイミドフィルムのHAZE、T.T.、T400、T430、T450、YI、CTE、Td1、Tg、ピール強度、引張伸度、引張強度及び積層体の反りの測定結果の測定結果を表6に示す。 Comparative Examples 4-5
In order to prepare the metal-clad laminates C4 and C5 in the same manner as in Example 10, as shown in Table 6, the type of polyamic acid and the thickness after the heat treatment were changed to form the insulating resin layers C4 and C5. Metal-clad laminates C4 and C5 were prepared.
The copper foils of the metal-clad laminates C4 and C5 were etched and removed using an aqueous ferric chloride solution to prepare polyimide films C4 and C5. HAZE, T.I. of each polyimide film. T. , T400, T430, T450, YI, CTE, Td1, Tg, peel strength, tensile elongation, tensile strength and the measurement results of the warp of the laminated body are shown in Table 6.
The resin film and metal-clad laminate of the present invention are preferably used as an insulating material for manufacturing electronic components such as FPCs, particularly for transparent FPCs that require colorless transparency accompanied by mounting of semiconductor elements. Further, the resin film of the present invention can be applied to display devices such as liquid crystal display devices, organic EL display devices, touch panels, color filters, electronic papers, and their components.
Claims (16)
- 複数のポリイミド層を有する樹脂フィルムであって、
下記の条件a及びb;
a)厚みが5μm以上200μm以下の範囲内であること;
b)全光線透過率が80%以上であること;
を満たし、
前記ポリイミド層の少なくとも1層がポリイミド層(P1)を含有し、前記ポリイミド層(P1)を構成しているポリイミドは、酸無水物成分から誘導される酸無水物残基と、ジアミン成分から誘導されるジアミン残基と、を含有しており、
前記ポリイミドは、全酸無水物残基に対し、下記の一般式(1)で表される芳香族テトラカルボン酸無水物から誘導される酸無水物残基を50モル%以上含有し、全ジアミン残基に対し、下記の一般式(2)で表わされる芳香族ジアミン化合物から誘導されるジアミン残基を50モル%以上含有することを特徴とする樹脂フィルム。
[式(1)中、Xは単結合、-O-、又は-C(CF3)2-から選ばれる2価の基を示す。]
[式(2)中、Rは独立に、ハロゲン原子、又は炭素数1~6のハロゲン原子で置換されてもよいアルキル基若しくはアルコキシ基、又は炭素数1~6の1価の炭化水素基若しくはアルコキシ基で置換されてもよいフェニル基若しくはフェノキシ基を示し、Zは独立に-O-、-S-、-CH2-、-CH(CH3)-、-C(CH3)2-、-CO-、-COO-、-SO2-、-NH-又は-NHCO-から選ばれる2価の基を示し、n1は0~3の整数、n2は0~4の整数を示す。] A resin film having a plurality of polyimide layers.
The following conditions a and b;
a) The thickness must be within the range of 5 μm or more and 200 μm or less;
b) The total light transmittance is 80% or more;
The filling,
At least one layer of the polyimide layer contains a polyimide layer (P1), and the polyimide constituting the polyimide layer (P1) is derived from an acid anhydride residue derived from an acid anhydride component and a diamine component. Contains diamine residues, which are
The polyimide contains 50 mol% or more of an acid anhydride residue derived from an aromatic tetracarboxylic acid anhydride represented by the following general formula (1) with respect to the total acid anhydride residue, and is a total diamine. A resin film characterized by containing 50 mol% or more of a diamine residue derived from an aromatic diamine compound represented by the following general formula (2) with respect to the residue.
[In formula (1), X represents a divalent group selected from single bond, -O-, or -C (CF 3 ) 2- . ]
[In the formula (2), R is independently an alkyl group or an alkoxy group which may be substituted with a halogen atom or a halogen atom having 1 to 6 carbon atoms, or a monovalent hydrocarbon group having 1 to 6 carbon atoms. Indicates a phenyl or phenoxy group that may be substituted with an alkoxy group, where Z is independently -O-, -S-, -CH 2- , -CH (CH 3 )-, -C (CH 3 ) 2- , It represents a divalent group selected from -CO-, -COO-, -SO 2- , -NH- or -NHCO-, where n 1 is an integer of 0 to 3 and n 2 is an integer of 0 to 4. ] - 前記ポリイミド層(P1)が最外層に位置することを特徴とする請求項1に記載の樹脂フィルム。 The resin film according to claim 1, wherein the polyimide layer (P1) is located on the outermost layer.
- 前記条件a及びbに加え、更に、下記の条件c;
c)熱膨張係数(CTE)が10ppm/K以上30ppm/K以下の範囲内であること;
を満たすことを特徴とする請求項1に記載の樹脂フィルム。 In addition to the above conditions a and b, the following condition c;
c) The coefficient of thermal expansion (CTE) is in the range of 10 ppm / K or more and 30 ppm / K or less;
The resin film according to claim 1, wherein the resin film meets the requirements. - 前記ポリイミド層(P1)が全体の厚みに対して1%以上50%未満の範囲内であることを特徴とする請求項1に記載の樹脂フィルム。 The resin film according to claim 1, wherein the polyimide layer (P1) is in the range of 1% or more and less than 50% with respect to the total thickness.
- 前記条件a及びbに加え、更に、下記の条件d;
d)HAZEが5%以下であること;
を満たすことを特徴とする請求項1に記載の樹脂フィルム。 In addition to the above conditions a and b, the following condition d;
d) HAZE is 5% or less;
The resin film according to claim 1, wherein the resin film meets the requirements. - 前記条件a及びbに加え、更に、下記の条件e;
e)厚みが10μmであるとき、YIが10以下であること;
を満たすことを特徴とする請求項1に記載の樹脂フィルム。 In addition to the above conditions a and b, the following condition e;
e) YI is 10 or less when the thickness is 10 μm;
The resin film according to claim 1, wherein the resin film meets the requirements. - 前記条件a及びbに加え、更に、下記の条件f;
f)厚みが50μmであるとき、YIが30以下であること;
を満たすことを特徴とする請求項1に記載の樹脂フィルム。 In addition to the above conditions a and b, the following condition f;
f) YI is 30 or less when the thickness is 50 μm;
The resin film according to claim 1, wherein the resin film meets the requirements. - 前記ポリイミド層の主たる層を構成するポリイミドが、フッ素原子を含む芳香族ジアミン化合物から誘導されるジアミン残基及び/又はフッ素原子を含む芳香族テトラカルボン酸無水物から誘導される酸無水物残基を含むことを特徴とする請求項1に記載の樹脂フィルム。 The polyimide constituting the main layer of the polyimide layer is a diamine residue derived from an aromatic diamine compound containing a fluorine atom and / or an acid anhydride residue derived from an aromatic tetracarboxylic acid anhydride containing a fluorine atom. The resin film according to claim 1, wherein the resin film comprises.
- 前記ポリイミド層の主たる層を構成しているポリイミドは、全ジアミン残基に対して、下記の一般式(A1)で表されるジアミン化合物から誘導されるジアミン残基を50モル%以上含有することを特徴とする請求項8に記載の樹脂フィルム。
[一般式(A1)中、置換基Xは独立にフッ素原子で置換されている炭素数1~3のアルキル素基を示し、m及びnは独立に1~4の整数を示す。] The polyimide constituting the main layer of the polyimide layer contains 50 mol% or more of diamine residues derived from the diamine compound represented by the following general formula (A1) with respect to all diamine residues. The resin film according to claim 8.
[In the general formula (A1), the substituent X represents an alkyl element group having 1 to 3 carbon atoms independently substituted with a fluorine atom, and m and n independently represent an integer of 1 to 4. ] - 複数層のポリイミド層を有する絶縁樹脂層と、前記絶縁樹脂層の少なくとも一方の面に積層された金属層と、を備えた金属張積層体であって、
前記絶縁樹脂層が請求項1に記載の樹脂フィルムからなることを特徴とする金属張積層体。 A metal-clad laminate comprising an insulating resin layer having a plurality of polyimide layers and a metal layer laminated on at least one surface of the insulating resin layer.
A metal-clad laminate characterized in that the insulating resin layer is made of the resin film according to claim 1. - 前記絶縁樹脂層の前記金属層に接するポリイミド層が前記ポリイミド層(P1)であることを特徴とする請求項10に記載の金属張積層体。 The metal-clad laminate according to claim 10, wherein the polyimide layer in contact with the metal layer of the insulating resin layer is the polyimide layer (P1).
- 前記金属層の厚みが1μm以上20μm以下の範囲内であることを特徴とする請求項10に記載の金属張積層体。 The metal-clad laminate according to claim 10, wherein the thickness of the metal layer is within the range of 1 μm or more and 20 μm or less.
- 前記金属層の前記絶縁樹脂層に接する表面の十点平均粗さRzjisが0.01μm以上0.5μm以下の範囲内であることを特徴とする請求項10に記載の金属張積層体。 The metal-clad laminate according to claim 10, wherein the ten-point average roughness Rzjis of the surface of the metal layer in contact with the insulating resin layer is within the range of 0.01 μm or more and 0.5 μm or less.
- 前記絶縁樹脂層と前記金属層との180°ピール強度が0.5kN/m以上であることを特徴とする請求項10に記載の金属張積層体。 The metal-clad laminate according to claim 10, wherein the 180 ° peel strength of the insulating resin layer and the metal layer is 0.5 kN / m or more.
- 絶縁樹脂層と、前記絶縁樹脂層の少なくとも一方の面に積層された金属層と、を備えた金属張積層体であって、
前記絶縁樹脂層が、単層又は複数層のポリイミド層からなり、下記の条件a~g;
a)厚みが5μm以上20μm以下の範囲内であること;
b)熱膨張係数(CTE)が10ppm/K以上30ppm/K以下の範囲内であること;
c)全光線透過率が80%以上であること;
d)YIが10以下であること;
e)HAZEが3%以下であること;
f)ガラス転移温度(Tg)が280℃以上であること;
g)引張強度が100MPa以上であること;
を満たすことを特徴とする金属積層体。 A metal-clad laminate comprising an insulating resin layer and a metal layer laminated on at least one surface of the insulating resin layer.
The insulating resin layer is composed of a single layer or a plurality of polyimide layers, and the following conditions a to g;
a) The thickness must be within the range of 5 μm or more and 20 μm or less;
b) The coefficient of thermal expansion (CTE) is in the range of 10 ppm / K or more and 30 ppm / K or less;
c) The total light transmittance is 80% or more;
d) YI is 10 or less;
e) HAZE is 3% or less;
f) The glass transition temperature (Tg) is 280 ° C or higher;
g) Tensile strength is 100 MPa or more;
A metal laminate characterized by satisfying. - 複数層のポリイミド層を有する絶縁樹脂層と、前記絶縁樹脂層の少なくとも一方の面に積層された金属層と、を備えた金属張積層体の製造方法であって、
前記絶縁樹脂層が請求項1に記載の樹脂フィルムからなり、
前記樹脂フィルムにおける前記ポリイミド層(P1)の面と前記金属層と重ね合わせて熱圧着する工程を含むことを特徴とする金属張積層体の製造方法。 A method for producing a metal-clad laminate comprising an insulating resin layer having a plurality of polyimide layers and a metal layer laminated on at least one surface of the insulating resin layer.
The insulating resin layer comprises the resin film according to claim 1.
A method for producing a metal-clad laminate, which comprises a step of superimposing the surface of the polyimide layer (P1) on the resin film and the metal layer and thermocompression bonding.
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