Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • 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
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1003—Preparatory processes
  • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
• • 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
• • 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
• • 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
• • 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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