WO2021049556A1 - フレキシブル電子デバイス用金属張積層板及びこれを用いたフレキシブル電子デバイス - Google Patents

フレキシブル電子デバイス用金属張積層板及びこれを用いたフレキシブル電子デバイス Download PDF

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Publication number
WO2021049556A1
WO2021049556A1 PCT/JP2020/034215 JP2020034215W WO2021049556A1 WO 2021049556 A1 WO2021049556 A1 WO 2021049556A1 JP 2020034215 W JP2020034215 W JP 2020034215W WO 2021049556 A1 WO2021049556 A1 WO 2021049556A1
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Prior art keywords
polyimide
metal
layer
clad laminate
flexible electronic
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PCT/JP2020/034215
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English (en)
French (fr)
Japanese (ja)
Inventor
王　宏遠
中塚　淳
俊夫 岩崎
翔平 河合
平石　克文
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel Chemical and Materials Co Ltd
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Priority to JP2021545582A priority Critical patent/JP7589156B2/ja
Priority to CN202080062210.7A priority patent/CN114391186A/zh
Priority to EP20862910.5A priority patent/EP4029690B1/en
Priority to KR1020227004912A priority patent/KR102805710B1/ko
Publication of WO2021049556A1 publication Critical patent/WO2021049556A1/ja
Anticipated expiration legal-status Critical
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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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/14—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by a layer differing constitutionally or physically in different parts, e.g. denser near its faces
    • B32B5/145—Variation across the thickness of the layer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
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    • H10K77/111—Flexible substrates
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    • 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
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    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
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    • H—ELECTRICITY
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    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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Definitions

  • the present invention relates to a metal-clad laminate for flexible electronic devices, which is useful as a material for various flexible electronic devices such as organic EL displays and organic EL lighting, and flexible electronic devices using the same.
  • Display devices and touch panels such as organic electroluminescence (organic EL) and liquid crystal devices are components of various displays, including large displays such as TVs and small and medium-sized displays such as mobile phones, personal computers, smartphones, and in-vehicle displays.
  • organic EL organic electroluminescence
  • liquid crystal devices are components of various displays, including large displays such as TVs and small and medium-sized displays such as mobile phones, personal computers, smartphones, and in-vehicle displays.
  • a thin film transistor is generally formed on a glass substrate which is a support substrate, and an electrode, an organic EL layer, and an electrode are sequentially formed on the thin film transistor (TFT), and these are formed by a glass substrate, a multilayer thin film, or the like. Made by tightly sealing.
  • a flexible substrate used in an organic EL device is required to have gas barrier properties, smoothness, and insulating properties as important properties.
  • Gas barrier property is a property required to prevent gas components such as water vapor from permeating when resin is used as a flexible substrate material, and affects the durability and reliability of organic EL devices used under various environmental conditions.
  • Smoothness is important for uniformly forming a plurality of organic EL layers, and smoothness equivalent to that of a glass substrate is required. Insulation is necessary to enable independent control of multiple organic EL elements formed on a flexible substrate, and if the insulation is insufficient, short circuits will occur between the elements, causing problems. Become.
  • stainless steel foil used as a flexible substrate material has excellent flexibility and gas barrier properties, smoothness and insulating properties cannot be guaranteed, so it is necessary to laminate a thin film of organic or inorganic material on the stainless steel foil.
  • a stainless foil with an insulating coating having a structure in which a methyl group-containing silica-based coating and a phenyl group-containing silica-based coating by a sol-gel method are laminated on a stainless foil has been proposed (for example, Patent Document 1 etc.).
  • Patent Document 1 it is stated that the combination of the methyl group-containing silica-based coating formed by the sol-gel method and the phenyl group-containing silica-based coating can alleviate the effects of flaws and foreign substances on the surface of the stainless steel foil and ensure smoothness. ing.
  • Patent Document 2 a laminate for an organic EL element in which a polyimide film is used instead of a stainless foil and an organic group-containing silica film is laminated by a sol-gel method has been proposed (for example, Patent Document 2).
  • the polyimide film is inferior in gas barrier property to the stainless steel foil, there is a concern in terms of ensuring the durability and reliability of the organic EL device used in various environments.
  • the film formed by the sol-gel method has excellent smoothness, the thickness must be suppressed to about 3 ⁇ m in order not to impair the flexibility, which is insufficient in terms of ensuring the insulating property.
  • the flexible substrate used for the flexible electronic device application needs to satisfy the three required characteristics of gas barrier property, smoothness and insulation property at the same time. Therefore, as a combination of the prior art, it is conceivable to improve all of the gas barrier property, the insulating property, and the smoothness by laminating the stainless steel foil, the polyimide insulating layer, and the sol-gel film.
  • the manufacturing process becomes complicated, and a demerit that it becomes difficult to control the coefficient of thermal expansion of each layer and warpage is likely to occur is expected. That is, when dissimilar materials having different physical properties such as metal, resin, and inorganic material are laminated in multiple layers and composited, the occurrence of warpage tends to be a problem.
  • an object of the present invention is for a flexible electronic device that can simultaneously secure the three required characteristics of gas barrier property, smoothness, and insulating property, suppress warpage, and have excellent adhesiveness between a metal layer and a polyimide insulating layer. It is to provide a metal-clad laminate.
  • the metal-clad laminate for a flexible electronic device of the present invention has a metal layer and a polyimide insulating layer including a single layer or a plurality of polyimide layers laminated on one side of the metal layer.
  • the polyimide insulating layer has the following conditions (a) to (f); (A) The thickness is within the range of 3 ⁇ m or more and 25 ⁇ m or less; (B) The thickness ratio to the metal layer is within the range of 0.1 or more and 0.5 or less; (C) The coefficient of thermal expansion is 25 ppm / K or less; (D) Humidity expansion coefficient is 30 ppm /% RH or less; (E) The arithmetic mean roughness (Ra) of the exposed surface that is not in contact with the metal layer is 1.0 nm or less; (F) The polyimide constituting the polyimide layer having an exposed surface that is not in contact with the metal layer is non-thermoplastic; It is characterized by satisfying.
  • the metal-clad laminate for flexible electronic devices of the present invention may have a ratio of the tensile elastic modulus of the polyimide insulating layer to the tensile elastic modulus of the metal layer in the range of 1/70 or more and 1/10 or less.
  • the metal-clad laminate for flexible electronic devices of the present invention may have a coefficient of thermal expansion of the metal layer in the range of 1 ppm / K or more and 25 ppm or less / K.
  • the metal-clad laminate for flexible electronic devices of the present invention may have a thickness of the metal layer in the range of 10 ⁇ m or more and 50 ⁇ m or less.
  • the polyimide insulating layer may be a single layer.
  • the metal-clad laminate for a flexible electronic device of the present invention may have a water vapor transmittance of 10 to 6 g / (m 2 ⁇ day) or less.
  • the metal-clad laminate for a flexible electronic device of the present invention is allowed to stand in an atmosphere of 23 ° C. and 50% humidity so that the convex surface of the central portion of 50 mm square after 24-hour humidity control is in contact with a flat surface.
  • the amount of warpage may be 10 mm or less.
  • the flexible electronic device of the present invention includes any of the above-mentioned metal-clad laminates for flexible electronic devices.
  • the metal-clad laminate for flexible electronic devices of the present invention is guaranteed to have gas barrier properties, smoothness, and insulating properties at the same time, and warpage is suppressed.
  • a notable advantage is warpage caused by fluctuations in environmental humidity.
  • FIG. 1 is a cross-sectional view in the thickness direction showing a schematic configuration of a metal-clad laminate 30 for a flexible electronic device according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view in the thickness direction showing a schematic configuration of the metal-clad laminate 30 for a flexible electronic device according to another embodiment of the present invention.
  • the metal-clad laminate 30 for a flexible electronic device includes a metal layer 10 and a polyimide insulating layer 20 laminated on one side of the metal layer 10.
  • the polyimide insulating layer 20 may be a single-layer polyimide layer, or as shown in FIG. 2, may be composed of a plurality of layers of polyimide layers.
  • the metal-clad laminate 30 for a flexible electronic device shown in FIG. 2 consists of a thermoplastic polyimide layer 21 in which the polyimide insulating layer 20 is in contact with the metal layer 10 and a non-thermoplastic polyimide layer 23 laminated on the thermoplastic polyimide layer 21. It has a two-layer structure.
  • the polyimide insulating layer 20 may be composed of three or more layers. Further, although not shown, the polyimide insulating layer 20 may be composed of two or more layers of non-thermoplastic polyimide.
  • Metal layer It is preferable to use a metal foil as the metal layer 10.
  • the material of the metal foil is not particularly limited, but for example, stainless steel, titanium, Invar, ordinary steel and the like are preferable.
  • As the stainless steel foil for example, austenitic SUS304 and SUS316 and ferrite-based SUS430 and SUS444 are preferable, and commercially available products can be used.
  • the coefficient of thermal expansion of the metal layer 10 is preferably in the range of 1 ppm / K or more and 25 ppm or less / K, and more preferably in the range of 5 ppm / K or more and 20 ppm / K or less from the viewpoint of suppressing warpage. If the coefficient of thermal expansion of the metal layer 10 is less than 1 ppm / K or exceeds 25 ppm / K, the difference in the coefficient of thermal expansion from that of the polyimide insulating layer 20 becomes large, warpage is likely to occur, and the amount of warpage becomes large. Tend.
  • the thickness of the metal layer 10 is preferably in the range of 10 ⁇ m or more and 100 ⁇ m or less, more preferably in the range of 10 ⁇ m or more and 50 ⁇ m or less, and more preferably 25 ⁇ m or more and 50 ⁇ m or less, from the viewpoint of balancing the strength and flexibility required for the supporting base material.
  • the range of is more preferable. If the thickness of the metal layer 10 is less than 10 ⁇ m, the mechanical strength becomes insufficient, and if it exceeds 100 ⁇ m, the flexibility tends to decrease.
  • the tensile elastic modulus of the metal layer 10 is preferably in the range of 100 GPa or more and 300 GPa, and more preferably in the range of 200 GPa or more and 250 GPa or less, from the viewpoint of balancing the strength and flexibility required as a supporting base material. If the tensile elastic modulus of the metal layer 10 is less than 100 GPa, the mechanical strength becomes insufficient. On the other hand, when the tensile elastic modulus of the metal layer 10 exceeds 300 GPa, the flexibility tends to decrease.
  • the polyimide insulating layer 20 satisfies the following conditions (a) to (f).
  • the thickness must be within the range of 3 ⁇ m or more and 25 ⁇ m or less. If the thickness of the polyimide insulating layer 20 is less than 3 ⁇ m, it becomes difficult to secure the insulating property.
  • the thickness of the polyimide insulating layer 20 is preferably 5 ⁇ m or more. On the other hand, if the thickness of the polyimide insulating layer 20 exceeds 25 ⁇ m, warpage tends to occur and the flexibility tends to decrease.
  • the thickness of the polyimide insulating layer 20 is preferably 15 ⁇ m or less, more preferably 12 ⁇ m or less, still more preferably 10 ⁇ m or less.
  • the thickness of the polyimide insulating layer 20 as a whole may be within the above range.
  • the thickness T1 of the thermoplastic polyimide layer 21 is, for example, within the range of 3 ⁇ m or less.
  • the thickness T2 of the non-thermoplastic polyimide layer 23 is preferably in the range of, for example, 2 ⁇ m or more and 25 ⁇ m or less.
  • the ratio (T2 / T3) of the thickness T2 of the non-thermoplastic polyimide layer 23 to the total thickness T3 of the polyimide insulating layer 20 is set.
  • it is preferably 50% or more, and more preferably 80% or more.
  • the thickness ratio to the metal layer 10 is in the range of 0.1 or more and 0.5 or less.
  • the thickness ratio to the metal layer 10 thickness of the polyimide insulating layer 20 / thickness of the metal layer 10.
  • the thickness ratio to the metal layer 10 is less than 0.1, the surface roughness of the exposed surface of the polyimide insulating layer 20 that is not in contact with the metal layer 10 is large. Also, the mechanical strength is reduced.
  • the thickness ratio to the metal layer 10 exceeds 0.5, warpage is likely to occur, flexibility as a device substrate is lowered, and productivity tends to be deteriorated.
  • the coefficient of thermal expansion is 25 ppm / K or less. If the coefficient of thermal expansion exceeds 25 ppm / K, the metal-clad laminate 30 for flexible electronic devices tends to warp. Even when the polyimide insulating layer 20 is composed of a plurality of layers, the coefficient of thermal expansion of the polyimide insulating layer 20 as a whole may be within the above range. Further, the polyimide layer having an exposed surface that is not in contact with the metal layer 10 (hereinafter, may be referred to as “the outermost polyimide layer”) also has a low expansion coefficient of 25 ppm / K or less. A polyimide layer is preferable.
  • the low-expansion polyimide layer constitutes a non-thermoplastic polyimide layer
  • the high-expansion polyimide layer constitutes a thermoplastic polyimide layer.
  • the low-expansion polyimide layer refers to a polyimide layer having a coefficient of thermal expansion of 25 ppm / K or less, preferably 20 ppm / K or less, more preferably 15 ppm / K or less, and further preferably 12 ppm / K or less.
  • the highly thermally expandable polyimide layer refers to a polyimide layer having a coefficient of thermal expansion preferably in the range of 35 ppm / K or more, more preferably 35 ppm / K or more and 80 ppm / K or less.
  • the polyimide insulating layer 20 is the outermost polyimide layer
  • the non-thermoplastic polyimide layer 23 is the outermost polyimide layer.
  • the material is composed of non-thermoplastic polyimide, and as a forming means, a casting method in which a solution of the polyimide precursor is applied onto the metal layer 10 is adopted, and coating, drying, and imide are adopted.
  • thermoplastic polyimide layer 23 between the metal layer 10 and the outermost surface polyimide layer (non-thermoplastic polyimide layer 23). This is because the coefficient of thermal expansion of the thermoplastic polyimide layer 21 has a small effect on the warp even when the 21 is interposed. That is, the relationship between the coefficient of thermal expansion of the metal layer 10 and the outermost polyimide layer is a dominant factor in the generation and suppression of warpage.
  • the coefficient of thermal expansion CTE M of the metal layer 10 and the coefficient of thermal expansion CTE P of the outermost polyimide layer satisfy the following relationship.
  • Humidity expansion coefficient is 30ppm /% RH or less.
  • polyimide contains many polar groups in its molecule and has high hygroscopicity. Therefore, when the polyimide insulating layer 20 expands and contracts due to fluctuations in environmental humidity, it causes warpage. Therefore, in the present embodiment, a polyimide having a humidity expansion coefficient of 30 ppm /% RH or less, preferably 15 ppm /% RH or less is used.
  • the humidity expansion coefficient of the polyimide insulating layer 20 as a whole may be 30 ppm /% RH or less.
  • the specific configuration of the polyimide for suppressing the humidity expansion coefficient of the polyimide insulating layer 20 to 30 ppm /% RH or less will be described later.
  • the coefficient of thermal expansion can be measured by the method and conditions shown in the examples below.
  • the arithmetic mean roughness (Ra) of the exposed surface that is not in contact with the metal layer 10 is 1.0 nm or less.
  • the exposed surface that is not in contact with the metal layer 10 is a surface (device forming surface S) that forms a device such as an organic EL element, and therefore, smoothness equivalent to that of a glass substrate is required. Therefore, the arithmetic mean roughness (Ra) of the exposed surface that is not in contact with the metal layer 10 needs to be 1.0 nm or less, preferably 0.6 nm or less, and more preferably 0.4 nm or less. In FIG.
  • the surface of the polyimide insulating layer 20 is the device forming surface S
  • the surface of the non-thermoplastic polyimide layer 23 is the device forming surface S.
  • the arithmetic mean roughness (Ra) of the device forming surface S is such that the polyimide layer (outermost surface polyimide layer) having an exposed surface that is not in contact with the metal layer 10 is made of a non-thermoplastic polyimide, and the forming means thereof. This can be controlled by adopting a casting method in which a solution of the polyimide precursor is applied onto the metal layer 10 and controlling various conditions of application, drying, and imidization.
  • the polyimide constituting the polyimide layer having an exposed surface that is not in contact with the metal layer 10 is non-thermoplastic. Since the polyimide layer (outermost surface polyimide layer) having an exposed surface that is not in contact with the metal layer 10 is made of non-thermoplastic polyimide, the coefficient of thermal expansion can be easily controlled and warpage is suppressed. Further, by forming the outermost surface polyimide layer with non-thermoplastic polyimide, it is possible to reduce the arithmetic mean roughness (Ra) of the device forming surface S, which is an exposed surface that is not in contact with the metal layer 10, and is smooth. Sex is ensured.
  • Ra arithmetic mean roughness
  • the tensile elastic modulus of the polyimide insulating layer 20 is preferably in the range of 3 GPa or more and 15 GPa or less, and more preferably in the range of 5 GPa or more and 12 GPa or less, from the viewpoint of balancing the strength and flexibility required for the insulating resin layer. If the tensile elastic modulus of the polyimide insulating layer 20 is less than 3 GPa, the mechanical strength becomes insufficient. On the other hand, when the tensile elastic modulus of the polyimide insulating layer 20 exceeds 15 GPa, the insulating resin layer becomes brittle and the flexibility tends to decrease.
  • the ratio of the tensile elastic modulus of the polyimide insulating layer 20 to the tensile elastic modulus of the metal layer 10 is in the range of 1/70 or more and 1/10 or less. Is preferable. Within such a range, warpage can be suppressed and flexibility can be ensured, which is suitable as an electronic device substrate.
  • non-thermoplastic polyimide is a polyimide that generally does not soften or show adhesiveness even when heated, but in the present invention, it was measured using a dynamic viscoelasticity measuring device (DMA).
  • DMA dynamic viscoelasticity measuring device
  • 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.
  • Tg glass transition temperature
  • the storage elastic modulus at 30 ° C. measured using DMA is 1.0.
  • Non-thermoplastic polyimide The non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer 23 contains a tetracarboxylic acid residue and a diamine residue.
  • the tetracarboxylic acid 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 non-thermoplastic polyimide preferably contains an aromatic tetracarboxylic acid residue derived from an aromatic tetracarboxylic dianhydride and an aromatic diamine residue derived from an aromatic diamine.
  • Non-plastic polyimide contains 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 1,4-phenylenebis (trimellitic acid monoester) dianhydride as tetracarboxylic acid residues. From at least one tetracarboxylic dian residue derived from (TAHQ) and at least one pyromellitic dianhydride (PMDA) and 2,3,6,7-naphthalenetetracarboxylic dianhydride (NTCDA). It preferably contains an induced tetracarboxylic dian residue.
  • TAHQ tetracarboxylic dian residue
  • PMDA pyromellitic dianhydride
  • NTCDA 2,3,6,7-naphthalenetetracarboxylic dianhydride
  • BPDA residue BPDA residue
  • TAHQ residue tetracarboxylic acid residue derived from TAHQ
  • a tetracarboxylic acid residue derived from pyromellitic dianhydride (hereinafter, also referred to as “PMDA residue”) and a tetra derived from 2,3,6,7-naphthalenetetracarboxylic dianhydride.
  • PMDA residue pyromellitic dianhydride
  • NTCDA residue carboxylic acid residue
  • the PMDA residue since the PMDA residue has a small molecular weight, if the amount is too large, the imide group concentration of the polymer increases, the polar group increases, and the hygroscopicity increases. In addition, the NTCDA residue tends to make the film brittle due to the highly rigid naphthalene skeleton, and tends to increase the elastic modulus.
  • the total of at least one of BPDA residue and TAHQ residue and at least one of PMDA residue and NTCDA residue is total tetracarboxylic. It is preferably 80 mol parts or more, preferably 90 mol parts or more, with respect to 100 mol parts of the acid residue.
  • the total amount of PMDA and NTCDA charged is preferably 40 mol parts or more with respect to 100 mol parts of the total acid anhydride component of the raw material. If the total amount of PMDA and NTCDA charged is less than 40 mol parts with respect to 100 mol parts of the total acid anhydride component of the raw material, the in-plane orientation of the molecule is lowered, it becomes difficult to reduce the CTE, and Tg. The heat resistance and dimensional stability of the film during heating are reduced due to the decrease in temperature.
  • BPDA and TAHQ are effective in suppressing molecular motion and lowering the hygroscopicity by lowering the concentration of imide groups, but increase CTE as a polyimide film after imidization.
  • the total amount of BPDA and TAHQ charged is preferably not more than 60 mol parts with respect to 100 mol parts of the total acid anhydride component of the raw material, and is in the range of 20 to 50 mol parts. Is more preferable.
  • Examples of the tetracarboxylic acid residue other than the BPDA residue, TAHQ residue, PMDA residue, and NTCDA residue contained in the non-thermal polyimide constituting the non-thermal polyimide layer 23 include 3,3',. 4,4'-Diphenylsulfone tetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid anhydride, 2,3', 3,4'-biphenyltetracarboxylic acid dianhydride, 2,2', 3,3 '-, 2,3,3', 4'-or 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 2,3', 3,4'-diphenyl ether tetracarboxylic dianhydride, Bis (2,3-dicarboxyphenyl) ether dianhydride, 3,3'', 4,4''-, 2,3,3'', 4'-or 2,2'', 3,3 '' -
  • Diamine residue As the diamine residue contained in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer 23, a diamine residue derived from the diamine compound represented by the general formula (1) is preferable.
  • the linking group Z represents a single bond, -COO- or -NHCO-
  • Y is a monovalent hydrocarbon having 1 to 3 carbon atoms which may be independently substituted with a halogen atom or a phenyl group.
  • n represents an integer of 0 to 2
  • p and q independently represent an integer of 0 to 4.
  • "independently” means that, in the above formula (1), a plurality of substituents Y and further integers p and q may be the same or different.
  • the hydrogen atom in the two terminal amino groups may be substituted, for example, -NR 2 R 3 (where R 2 and R 3 are independently alkyl groups and the like. It may mean any substituent).
  • the diamine compound represented by the general formula (1) (hereinafter, may be referred to as "diamine (1)”) is an aromatic diamine having 1 to 3 benzene rings. Since the diamine (1) has a rigid structure, it has an action of imparting an ordered structure to the entire polymer. Therefore, a polyimide having low gas permeability and low hygroscopicity can be obtained, and the water content inside the molecular chain can be reduced.
  • the linking group Z a single bond is preferable.
  • diamine (1) examples include 1,4-diaminobenzene (p-PDA; paraphenylenediamine), 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB), 2,2'-. Diethyl-4,4'-diaminobiphenyl (m-EB), 2,2'-diethoxy-4,4'-diaminobiphenyl (m-EOB), 2,2'-dipropoxy-4,4'-diaminobiphenyl ( m-POB), 2,2'-n-propyl-4,4'-diaminobiphenyl (m-NPB), 2,2'-divinyl-4,4'-diaminobiphenyl (VAB), 4,4'- Diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl (TFMB), 4-aminophenyl-4'-aminobenzoate (APAB), 4,4'-
  • the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer 23 contains the diamine residue derived from the diamine (1) in an amount of preferably 20 mol parts or more, more preferably 20 mol parts or more, based on 100 mol parts of the total diamine residues. It is preferable to contain 50 mol parts or more.
  • the diamine (1) in an amount within the above range, the rigid structure derived from the monomer facilitates the formation of an ordered structure in the entire polymer, resulting in a non-thermoplastic polyimide having low gas permeability and low hygroscopicity. Easy to obtain.
  • Examples of other amine residues contained in the non-thermal polyimide constituting the non-thermal polyimide layer 23 include 2,2-bis- [4- (3-aminophenoxy) phenyl] propane and bis [4- ( 3-Aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) biphenyl, bis [1- (3-aminophenoxy)] biphenyl, bis [4- (3-aminophenoxy) phenyl] methane, bis [ 4- (3-Aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy)] benzophenone, 9,9-bis [4- (3-aminophenoxy) phenyl] fluorene, 2,2-bis- [ 4- (4-Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis- [4- (3-aminophenoxy) phenyl] hexafluoropropane,
  • non-thermoplastic polyimide thermal expansion is performed by selecting the types of the above tetracarboxylic acid residue and diamine residue and the molar ratio of each when two or more types of tetracarboxylic acid residue or diamine residue are applied.
  • the coefficient, storage elastic modulus, tensile elastic modulus, etc. can be controlled.
  • when a plurality of structural units of polyimide are present it may exist as a block or randomly, but it is preferable that it exists randomly.
  • both the tetracarboxylic acid residue and the diamine residue contained in the non-thermoplastic polyimide are aromatic groups because the dimensional accuracy of the polyimide film in a high temperature environment can be improved.
  • the imide group concentration of the non-thermoplastic polyimide is preferably 33% or less, more preferably 32% or less.
  • the "imide group concentration” means a value obtained by dividing the molecular weight of the imide base portion (-(CO) 2 -N-) in the polyimide by the molecular weight of the entire structure of the polyimide.
  • the imide group concentration exceeds 33%, the molecular weight of the resin itself decreases, and the hygroscopicity increases due to the increase in polar groups.
  • the orientation of the molecules in the non-thermoplastic polyimide is controlled, thereby suppressing the increase in CTE due to the decrease in the imide group concentration and ensuring low hygroscopicity. ing.
  • the weight average molecular weight of the non-thermoplastic polyimide is preferably in the range of, for example, 10,000 to 400,000, and more preferably in the range of 50,000 to 350,000. 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 film thickness unevenness and streaks tend to occur during the coating operation.
  • the non-thermoplastic polyimide layer 23 preferably has a glass transition temperature (Tg) of 280 ° C. or higher from the viewpoint of heat resistance.
  • non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer 23 includes, as optional components, other curing resin components such as a plasticizer and an epoxy resin, a curing agent, a curing accelerator, a coupling agent, a filler, and the like.
  • other curing resin components such as a plasticizer and an epoxy resin, a curing agent, a curing accelerator, a coupling agent, a filler, and the like.
  • a solvent, a flame retardant, etc. can be appropriately blended.
  • thermoplastic polyimide layer 21 Since the thermoplastic polyimide layer 21 is interposed between the metal layer 10 and the non-thermoplastic polyimide layer 23 and functions as an adhesive layer, it is preferable that the thermoplastic polyimide layer 21 has excellent adhesiveness.
  • the thermoplastic polyimide constituting the thermoplastic polyimide layer 21 contains a tetracarboxylic acid residue and a diamine residue, and the aromatic tetracarboxylic acid residue and the aromatic are derived from the aromatic tetracarboxylic acid dianhydride. It preferably contains an aromatic diamine residue derived from diamine.
  • thermoplastic polyimide constituting the thermoplastic polyimide layer 21
  • tetracarboxylic acid residue As the tetracarboxylic dian residue used for the thermoplastic polyimide constituting the thermoplastic polyimide layer 21, the same one as exemplified as the tetracarboxylic dian residue in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer 23 is used. Can be used.
  • diamine residue As the diamine residue contained in the thermoplastic polyimide constituting the thermoplastic polyimide layer 21, diamine residues derived from the diamine compounds represented by the general formulas (B1) to (B7) are preferable.
  • R 1 independently represents a monovalent hydrocarbon group or an alkoxy group having 1 to 6 carbon atoms
  • the linking group A independently represents -O-, -S-, and -CO-.
  • -SO-, -SO 2- , -COO-, -CH 2- , -C (CH 3 ) 2- , -NH- or -CONH- indicates a divalent group
  • n 1 is independent. Indicates an integer from 0 to 4. However, the formula (B3) that overlaps with the formula (B2) is excluded, and the formula (B5) that overlaps with the formula (B4) is excluded.
  • the diamine represented by the formula (B1) (hereinafter, may be referred to as "diamine (B1)") is an aromatic diamine having two benzene rings.
  • This diamine (B1) has a high degree of flexibility due to an increase in the degree of freedom of the polyimide molecular chain by having an amino group directly linked to at least one benzene ring and a divalent linking group A at the meta position. It is considered that this contributes to the improvement of the flexibility of the polyimide molecular chain. Therefore, the use of diamine (B1) enhances the thermoplasticity of the polyimide.
  • the linking group A -O-, -CH 2- , -C (CH 3 ) 2- , -CO-, -SO 2- , -S- are preferable.
  • Examples of the diamine (B1) include 3,3'-diaminodiphenylmethane, 3,3'-diaminodiphenylpropane, 3,3'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone, and 3,3'-diamino.
  • Diphenyl ether, 3,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylpropane, 3,4'-diaminodiphenylsulfide, 3,3'-diaminobenzophenone, (3,3'- Bisamino) diphenylamine and the like can be mentioned.
  • the diamine represented by the formula (B2) (hereinafter, may be referred to as "diamine (B2)") is an aromatic diamine having three benzene rings.
  • This diamine (B2) has a high degree of flexibility due to an increase in the degree of freedom of the polyimide molecular chain by having an amino group directly linked to at least one benzene ring and a divalent linking group A at the meta position. It is considered that this contributes to the improvement of the flexibility of the polyimide molecular chain. Therefore, the use of diamine (B2) enhances the thermoplasticity of the polyimide.
  • the linking group A —O— is preferable.
  • diamine (B2) examples include 1,4-bis (3-aminophenoxy) benzene, 3- [4- (4-aminophenoxy) phenoxy] benzeneamine, and 3- [3- (4-aminophenoxy) phenoxy].
  • Benzene amine and the like can be mentioned.
  • the diamine represented by the formula (B3) (hereinafter, may be referred to as "diamine (B3)”) is an aromatic diamine having three benzene rings.
  • This diamine (B3) has two divalent linking groups A directly linked to one benzene ring at the meta position of each other, so that the degree of freedom of the polyimide molecular chain is increased and the diamine has high flexibility. Therefore, it is considered that it contributes to the improvement of the flexibility of the polyimide molecular chain. Therefore, the use of diamine (B3) enhances the thermoplasticity of the polyimide.
  • the linking group A —O— is preferable.
  • diamine (B3) examples include 1,3-bis (4-aminophenyloxy) benzene (TPE-R), 1,3-bis (3-aminophenoxy) benzene (APB), and 4,4'-[2-].
  • TPE-R 1,3-bis (4-aminophenyloxy) benzene
  • APIB 1,3-bis (3-aminophenoxy) benzene
  • B3 4,4'-[2-].
  • Methyl- (1,3-phenylene) bisoxy] bisaniline, 4,4'-[4-methyl- (1,3-phenylene) bisoxy] bisaniline, 4,4'-[5-methyl- (1,3-phenylene) ) Benzene] Bisaniline and the like can be mentioned.
  • the diamine represented by the formula (B4) (hereinafter, may be referred to as "diamine (B4)”) is an aromatic diamine having four benzene rings.
  • This diamine (B4) has high flexibility because the amino group directly linked to at least one benzene ring and the divalent linking group A are in the meta position, which improves the flexibility of the polyimide molecular chain. It is thought to contribute. Therefore, the use of diamine (B4) enhances the thermoplasticity of the polyimide.
  • the linking group A -O-, -CH 2- , -C (CH 3 ) 2- , -SO 2- , -CO-, and -CONH- are preferable.
  • Diamines (B4) include bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) phenyl] ether, and bis. Examples thereof include [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy)] benzophenone, and bis [4,4'-(3-aminophenoxy)] benzanilide.
  • the diamine represented by the formula (B5) (hereinafter, may be referred to as "diamine (B5)”) is an aromatic diamine having four benzene rings.
  • This diamine (B5) has two divalent linking groups A directly linked to at least one benzene ring at the meta position of each other, so that the degree of freedom of the polyimide molecular chain is increased and the diamine has high flexibility. It is considered that this contributes to the improvement of the flexibility of the polyimide molecular chain. Therefore, the use of diamine (B5) enhances the thermoplasticity of the polyimide.
  • the linking group A —O— is preferable.
  • Examples of the diamine (B5) include 4- [3- [4- (4-aminophenoxy) phenoxy] phenoxy] aniline and 4,4'-[oxybis (3,1-phenyleneoxy)] bisaniline. ..
  • diamine (B6) The diamine represented by the formula (B6) (hereinafter, may be referred to as "diamine (B6)”) is an aromatic diamine having four benzene rings.
  • This diamine (B6) has high flexibility by having at least two ether bonds, and is considered to contribute to the improvement of the flexibility of the polyimide molecular chain. Therefore, the use of diamine (B6) enhances the thermoplasticity of the polyimide.
  • the linking group A -C (CH 3 ) 2- , -O-, -SO 2- , and -CO- are preferable.
  • diamine (B6) examples include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), bis [4- (4-aminophenoxy) phenyl] ether (BAPE), and bis [4).
  • BAPP 2,2-bis [4- (4-aminophenoxy) phenyl] propane
  • BAPE bis [4- (4-aminophenoxy) phenyl] ether
  • BAPS bis [4- (4-aminophenoxy) phenyl] ketone
  • BAPK bis [4- (4-aminophenoxy) phenyl] ketone
  • diamine (B7) The diamine represented by the formula (B7) (hereinafter, may be referred to as "diamine (B7)”) is an aromatic diamine having four benzene rings. Since this diamine (B7) has highly flexible divalent linking groups A on both sides of the diphenyl skeleton, it is considered to contribute to the improvement of the flexibility of the polyimide molecular chain. Therefore, the use of diamine (B7) enhances the thermoplasticity of the polyimide.
  • the linking group A —O— is preferable.
  • Examples of the diamine (B7) include bis [4- (3-aminophenoxy)] biphenyl and bis [4- (4-aminophenoxy)] biphenyl.
  • the thermoplastic polyimide constituting the thermoplastic polyimide layer 21 contains a diamine residue derived from at least one diamine compound selected from diamine (B1) to diamine (B7) with respect to 100 mol parts of all diamine residues. It may be contained in an amount of 60 mol parts or more, preferably 60 mol parts or more and 100 mol parts or less, and more preferably 70 mol parts or more and 100 mol parts or less. Since diamines (B1) to diamines (B7) have a flexible molecular structure, the flexibility of the polyimide molecular chain is improved by using at least one diamine compound selected from these in an amount within the above range. And can impart thermoplasticity. If the total amount of diamine (B1) to diamine (B7) in the raw material is less than 60 mol parts with respect to 100 mol parts of the total diamine component, sufficient thermoplasticity cannot be obtained due to insufficient flexibility of the polyimide resin.
  • a diamine residue derived from the diamine compound represented by the general formula (1) is also preferable.
  • the diamine compound [diamine (1)] represented by the formula (1) is as described in the description of the non-thermoplastic polyimide. Since the diamine (1) has a rigid structure and has an action of imparting an ordered structure to the entire polymer, the hygroscopicity can be lowered by suppressing the movement of molecules. Further, by using it as a raw material for thermoplastic polyimide, a polyimide having low gas permeability and excellent long-term heat-resistant adhesiveness can be obtained.
  • the thermoplastic polyimide constituting the thermoplastic polyimide layer 21 contains the diamine residue derived from the diamine (1) in a range of preferably 1 mol part or more and 40 mol parts or less, more preferably 5 mol parts or more and 30 mol parts or more. It may be contained within the following range.
  • the diamine (1) in an amount within the above range, an ordered structure is formed in the entire polymer due to the rigid structure derived from the monomer. A polyimide having excellent heat-resistant adhesiveness can be obtained.
  • thermoplastic polyimide constituting the thermoplastic polyimide layer 21 can contain diamine residues derived from diamine compounds other than diamines (1) and (B1) to (B7) as long as the effects of the invention are not impaired. ..
  • the coefficient of thermal expansion is selected by selecting the types of the tetracarboxylic acid residue and the diamine residue and the molar ratio of each when two or more types of the tetracarboxylic acid residue or the diamine residue are applied. , Tylic elastic modulus, glass transition temperature, etc. can be controlled. Further, in the thermoplastic polyimide, when a plurality of structural units of polyimide are present, it may exist as a block or randomly, but it is preferable that it exists randomly.
  • thermoplastic polyimide By using both the tetracarboxylic acid residue and the diamine residue contained in the thermoplastic polyimide as an aromatic group, the dimensional accuracy of the polyimide film in a high temperature environment can be improved.
  • the imide group concentration of the thermoplastic polyimide is preferably 33% or less, more preferably 32% or less.
  • the "imide group concentration” means a value obtained by dividing the molecular weight of the imide base portion (-(CO) 2 -N-) in the polyimide by the molecular weight of the entire structure of the polyimide.
  • the imide group concentration exceeds 33%, the molecular weight of the resin itself decreases, and the hygroscopicity increases due to the increase in polar groups.
  • the weight average molecular weight of the thermoplastic polyimide is preferably in the range of 10,000 to 400,000, more preferably in the range of 50,000 to 350,000, for example. 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 film thickness unevenness and streaks tend to occur during the coating operation.
  • thermoplastic polyimide constituting the thermoplastic polyimide layer 21 is interposed between the metal layer 10 and the non-thermoplastic polyimide layer 23 and functions as an adhesive layer, it prevents the diffusion of metal elements into the polyimide insulating layer 20. Therefore, a completely imidized structure is most preferable. However, a part of the polyimide may be amic acid.
  • the resin used for the thermoplastic polyimide layer 21 includes, as optional components, other curing resin components such as a plasticizer and an epoxy resin, a curing agent, a curing accelerator, an inorganic filler, and a coupling agent.
  • other curing resin components such as a plasticizer and an epoxy resin, a curing agent, a curing accelerator, an inorganic filler, and a coupling agent.
  • a filler, a solvent, a flame retardant and the like can be appropriately blended.
  • the polyimide constituting the polyimide insulating layer 20 can be produced by reacting the above acid anhydride and diamine in a solvent to produce a precursor resin and then heating and ring-closing the polyimide.
  • it is a precursor of polyimide by dissolving an acid anhydride component and a diamine component in an organic solvent in approximately equimolar amounts, stirring at a temperature in the range of 0 to 100 ° C. for 30 minutes to 24 hours, and carrying out a polymerization reaction. Polyamic acid is obtained.
  • the reaction components are dissolved in an organic solvent so that the precursor produced is in the range of 5 to 30% by weight, preferably in the range of 10 to 20% by weight.
  • 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, dioxane, and the like. Examples thereof include tetrahydrofuran, jiglime, triglime and the like. Two or more of these solvents can be used in combination, and aromatic hydrocarbons such as xylene and toluene can be used in combination.
  • the amount of such an organic solvent used is not particularly limited, but the amount used is such that the concentration of the polyamic acid solution (polyimide precursor solution) obtained by the polymerization reaction is about 5 to 30% by weight. It is preferable to adjust to.
  • the acid anhydride and the diamine may be used alone or in combination of two or more.
  • the coefficient of thermal expansion, adhesiveness, glass transition temperature, etc. can be controlled by selecting the types of acid anhydride and diamine, and the molar ratio of each when two or more types of acid anhydride or diamine are used. ..
  • the synthesized precursor is usually advantageous to be used as a reaction solvent solution, but can be concentrated, diluted or replaced with another organic solvent if necessary.
  • precursors are generally excellent in solvent solubility and are therefore used advantageously.
  • the method for imidizing the precursor is not particularly limited, and for example, a heat treatment such as heating in the solvent under a temperature condition in the range of 80 to 400 ° C. for 1 to 24 hours is preferably adopted.
  • the metal-clad laminate 30 for a flexible electronic device of the present embodiment having the above configuration has a 50 mm square convex surface on a flat surface after 24 hours of humidity control in an atmosphere of 23 ° C. and 50% humidity.
  • the amount of warpage is 10 mm or less when the maximum value of the amount of lift of the four corners is taken as the amount of warpage. If the amount of warpage exceeds 10 mm, the handleability is deteriorated, and it becomes difficult to form the organic EL layer on the device forming surface S (exposed surface not in contact with the metal layer 10) of the polyimide insulating layer 20.
  • the metal-clad laminate 30 for a flexible electronic device of the present embodiment preferably has a water vapor transmittance of 10 to 6 g / (m 2 ⁇ day) or less from the viewpoint of ensuring gas barrier properties.
  • the casting method is a method in which a resin solution of polyamic acid, which is a precursor of polyimide, is applied onto a metal foil, which is a raw material of the metal layer 10, to form a coating film, and then dried and cured by heat treatment.
  • a resin solution of polyamic acid which is a precursor of polyimide
  • the coating film can be formed by applying a resin solution of polyamic acid on a metal foil to be a metal layer 10 and then drying it.
  • another polyamic acid solution having different constituent components may be sequentially applied onto the polyamic acid solution to form the polyamic acid solution, or the polyamic acid solution having the same composition may be applied twice or more. ..
  • a plurality of coating films may be laminated and formed at the same time by multi-layer extrusion. It is also possible to imidize the coating film of polyamic acid once to form a single-layer or a plurality of polyimide layers, and then further coat a resin solution of polyamic acid on the imidized film to imidize the polyimide insulating layer 20.
  • the method of application 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.
  • the stainless steel foil may have a shape such as a cut sheet, a roll, or an endless belt. In order to obtain productivity, it is efficient to use a roll-shaped or endless belt-shaped form so that continuous production is possible.
  • the imidization method is not particularly limited, and for example, a heat treatment such as heating for a time in the range of 1 to 60 minutes under a temperature condition in the range of 80 to 400 ° C. is preferably adopted.
  • heat treatment is preferably performed in a low oxygen atmosphere, specifically, in an inert gas atmosphere such as nitrogen or a rare gas, in a reducing gas atmosphere such as hydrogen, or in a vacuum. Is preferable.
  • the polyamic acid in the coating film is imidized to form a polyimide.
  • the metal-clad laminate 30 for flexible electronic devices of the present embodiment a case where the metal-clad laminate 30 for flexible electronic devices in which the metal layer 10 is a stainless steel layer is manufactured by a casting method is taken as an example. This will be described in detail.
  • the first coating film is a non-thermoplastic polyimide precursor resin layer in the embodiment shown in FIG. 1, and is a thermoplastic polyimide precursor resin layer in the embodiment shown in FIG. 2.
  • a resin solution of polyamic acid is further applied on the first layer coating film and dried to form the second layer coating film.
  • the second coating film is a precursor resin layer of non-thermoplastic polyimide. If necessary, the third and subsequent coating films may be sequentially formed while selecting the type of polyamic acid.
  • a metal-clad laminate 30 for a flexible electronic device in which layers 20 are laminated can be produced.
  • the flexible electronic device includes the metal-clad laminate 30 for the flexible electronic device.
  • the flexible electronic device is an organic EL device, although not shown, the device formation of the metal-clad laminate 30 for the flexible electronic device and the polyimide insulating layer 20 in the metal-clad laminate 30 for the flexible electronic device 30 is omitted.
  • a layer (organic EL layer) including an organic EL element laminated on a surface S (exposed surface that is not in contact with the metal layer 10) is provided.
  • the organic EL layer and other configurations are the same as those of a general flexible organic EL device.
  • CTE coefficient of thermal expansion
  • Metal leaf CTE A metal foil with a size of 3 mm x 15 mm is subjected to a constant temperature rise rate (10 ° C./min) and temperature drop rate (10 ° C.) while applying a load of 5.0 g using a thermomechanical analysis (TMA: device name TMA / SS6100) device.
  • TMA thermomechanical analysis
  • a tensile test was performed by raising and lowering the temperature in the temperature range of room temperature ° C to 300 ° C at (/ min), and the coefficient of thermal expansion in the plane direction (ppm / min) was determined from the change in the amount of elongation with respect to the temperature change from 100 ° C to 30 ° C during the temperature drop. K) was measured.
  • thermogravimetric temperature (Td5) 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 5% was defined as the thermogravimetric temperature (Td5).
  • TG thermogravimetric analysis
  • the surface roughness is AFM (Bruker AXS Co., Ltd., trade name: Measurement Icon type SPM), probe (Bruker AXS Co., Ltd., trade name: TESSA (NCHV), tip curvature radius 10 nm, spring constant 42N. Using / m), measurements were made in the range of 1 ⁇ m ⁇ 1 ⁇ m in the tapping mode, and the arithmetic mean roughness (Ra) and the maximum head (Rz) were determined.
  • Tensile test is performed using a Tencilon universal testing machine (manufactured by Orientec Co., Ltd., trade name; RTA-250) at a tensile speed of 10 mm / min in an environment of a temperature of 23 ° C. and a relative humidity of 50% RH to determine the tensile elastic modulus. It was measured.
  • PMDA pyromellitic dianhydride
  • BPDA 3,3', 4,4'-biphenyltetracarboxylic dianhydride
  • m-TB 2,2'-dimethyl-4,4'-diaminobiphenyl
  • BAPP 2,2-bis (4-aminophenoxyphenyl) propane
  • MABA 4,4'-diamino-2'-methoxybenzanilide
  • DAPE 4,4'-diaminodiphenyl ether
  • TPE-R 1,3-bis (4) -Aminophenoxy) Benzene
  • DMAc N, N-dimethylacetamide
  • Example 1 The polyamic acid solution A is cured on a stainless steel foil 1 (SUS304, thickness; 30 ⁇ m, coefficient of thermal expansion; 17 ppm / K, Ra; 5.12 nm, Rz; 43.3 nm) so that the thickness after curing is 4.9 ⁇ m. After uniformly applying the mixture, the mixture was dried by heating at 120 ° C. to remove the solvent. Next, a stepwise heat treatment was performed from 130 ° C. to 360 ° C. to complete imidization, and a metal-clad laminate 1a was prepared.
  • SUS304 thickness; 30 ⁇ m, coefficient of thermal expansion; 17 ppm / K, Ra; 5.12 nm, Rz; 43.3 nm
  • the adhesiveness and warpage of the metal-clad laminate 1a were good, and Ra and Rz of the exposed surface of the polyimide insulating layer not in contact with the stainless steel foil 1 were 0.37 nm and 4.4 nm, respectively. These results are shown in Table 2. Further, the stainless steel foil 1 on the metal-clad laminate 1a was removed by etching using an aqueous ferric chloride solution to prepare a polyimide film 1a. The CTE of the polyimide film 1a was 5 ppm / K, Td5 was 517 ° C, Tg was 365 ° C, CHE was 9 ppm /% RH, and the hygroscopicity was 0.91 wt%. These results are shown in Table 3.
  • a thin film transistor is formed on the surface of the polyimide insulating layer in the metal-clad laminate 1a prepared in Example 1, an electrode, an organic EL layer and an electrode are sequentially formed on the thin film transistor, and these are hermetically sealed with a glass substrate to be flexible.
  • Electronic device 1 was prepared. The flexible electronic device 1 was allowed to stand in a constant temperature and humidity chamber at 40 ° C./90% RH for 1000 hours, and it was confirmed that the change in the brightness of the flexible electronic device 1 was within 10%.
  • the metal-clad laminate 1a prepared in Example 1 was heated from room temperature to 400 ° C. in a nitrogen atmosphere, held at 400 ° C. for 30 minutes, and then cooled to room temperature.
  • the oxygen concentration when maintained at 400 ° C. was 50 ppm or less.
  • the adhesiveness of the metal-clad laminate 1a after heating and cooling was good, and the warp of the sample obtained by cutting the metal-clad laminate 1a into a size of 5 cm ⁇ 5 cm was 0.5 mm, which was good.
  • Example 2 A metal-clad laminate 2b and a polyimide film 2b were prepared in the same manner as in Example 1 except that the polyamic acid solution B was used and applied so that the thickness after curing was 5 ⁇ m. The adhesiveness and warpage of the metal-clad laminate 2b were good, and Ra and Rz of the exposed surface of the polyimide insulating layer not in contact with the stainless steel foil 1 were 0.34 nm and 3.2 nm, respectively. These results are shown in Table 2.
  • the CTE of the polyimide film 2b was 11.3 ppm / K, Td5 was 510 ° C., Tg was 390 ° C., CHE was 14 ppm /% RH, and the hygroscopicity was 1.2 wt%.
  • Example 3 A metal-clad laminate 3c and a polyimide film 3c were prepared in the same manner as in Example 1 except that the polyamic acid solution C was used and applied so that the thickness after curing was 5 ⁇ m. The adhesiveness and warpage of the metal-clad laminate 3c were good, and Ra and Rz of the exposed surface of the polyimide insulating layer not in contact with the stainless steel foil 1 were 0.39 nm and 4.5 nm, respectively. These results are shown in Table 2.
  • the CTE of the polyimide film 3c was 3 ppm / K, Td5 was 510 ° C., Tg was 310 ° C., CHE was 15 ppm /% RH, and the hygroscopicity was 1.3 wt%.
  • Example 4 A metal-clad laminate 4d and a polyimide film 4d were prepared in the same manner as in Example 1 except that the polyamic acid solution D was used and applied so that the thickness after curing was 4.9 ⁇ m.
  • the adhesiveness and warpage of the metal-clad laminate 4d were good, and Ra and Rz of the exposed surface of the polyimide insulating layer not in contact with the stainless steel foil 1 were 0.32 nm and 3.1 nm, respectively.
  • the CTE of the polyimide film 4d was 11.9 ppm / K, Td5 was 492 ° C, Tg was 372 ° C, CHE was 26 ppm /% RH, and the hygroscopicity was 1.6 wt%.
  • Example 5 A metal-clad laminate 5e and a polyimide film 5e were prepared in the same manner as in Example 1 except that the polyamic acid solution E was applied so that the thickness after curing was 3.2 ⁇ m. The adhesiveness and warpage of the metal-clad laminate 5e were good, and Ra and Rz of the exposed surface of the polyimide insulating layer not in contact with the stainless steel foil 1 were 0.5 nm and 5.2 nm, respectively. These results are shown in Table 2.
  • the CTE of the polyimide film 5e was 2 ppm / K, Td5 was 517 ° C, Tg was 365 ° C, CHE was 9 ppm /% RH, and the hygroscopicity was 0.9 wt%.
  • Example 6 Stainless steel foil 2 (SUS304, thickness; 50 ⁇ m, coefficient of thermal expansion; 17 ppm / K, Ra; 9.8 nm, Rz; 72.2 nm) was used instead of the stainless steel foil 1, and the polyamide was used instead of the polyamic acid solution A.
  • a metal-clad laminate 6b and a polyimide film 6b were prepared in the same manner as in Example 1 except that the acid solution B was used and applied so that the thickness after curing was 6.3 ⁇ m. The adhesiveness and warpage of the metal-clad laminate 6b were good, and Ra and Rz of the exposed surface of the polyimide insulating layer not in contact with the stainless steel foil 2 were 0.34 nm and 4.2 nm, respectively.
  • Comparative Example 1 A metal-clad laminate f and a polyimide film f were prepared in the same manner as in Example 1 except that the polyamic acid solution F was used and applied so that the thickness after curing was 5.5 ⁇ m. The adhesiveness of the metal-clad laminate f was good, but the warp was poor. The Ra and Rz of the exposed surface of the polyimide insulating layer not in contact with the stainless steel foil 1 were 0.5 nm and 4.6 nm, respectively. These results are shown in Table 2.
  • the CTE of the polyimide film f was 56 ppm / K
  • Td5 was 511 ° C
  • Tg was 310 ° C
  • CHE was 7 ppm /% RH
  • the hygroscopicity was 0.2 wt%.
  • Comparative Example 2 A metal-clad laminate g and a polyimide film g were prepared in the same manner as in Example 1 except that the polyamic acid solution G was used and applied so that the thickness after curing was 4.7 ⁇ m. The adhesiveness of the metal-clad laminate g was good, but the warp was poor. The Ra and Rz of the exposed surface of the polyimide insulating layer not in contact with the stainless steel foil 1 were 0.68 nm and 7.8 nm, respectively. These results are shown in Table 2.
  • the CTE of the polyimide film g was 51 ppm / K, Td5 was 511 ° C, Tg was 215 ° C, CHE was 8 ppm /% RH, and the hygroscopicity was 0.3 wt%.
  • Example 7 The polyamic acid solution F was uniformly applied onto the stainless steel foil 1 so as to have a thickness of 1.5 ⁇ m after curing, and then heated and dried at 120 ° C. to remove the solvent. Next, the polyamic acid solution A was uniformly applied so that the thickness after curing was 3.2 ⁇ m, and then a stepwise heat treatment was performed from 130 ° C. to 360 ° C. to complete imidization, and the metal-clad laminate 7 Was prepared. The adhesiveness and warpage of the metal-clad laminate 7 were good, and Ra and Rz of the exposed surface of the polyimide insulating layer not in contact with the stainless steel foil 1 were 0.38 nm and 3.2 nm, respectively. Further, the polyimide film 7 was prepared by etching and removing in the same manner as in Example 1. The CTE of the polyimide film 7 was 20 ppm / K, and the CHE was 8 ppm /% RH.
  • Example 8 The polyamic acid solution B was uniformly applied onto the stainless steel foil 1 so as to have a thickness of 2.2 ⁇ m after curing, and then heat-dried at 120 ° C. to remove the solvent. Next, the polyamic acid solution A was uniformly applied so that the thickness after curing was 3.2 ⁇ m, and then a stepwise heat treatment was performed from 130 ° C. to 360 ° C. to complete imidization, and the metal-clad laminate 8 Was prepared. The adhesiveness and warpage of the metal-clad laminate 8 were good, and Ra and Rz of the exposed surface of the polyimide insulating layer not in contact with the stainless steel foil 1 were 0.39 nm and 3.8 nm, respectively. Further, the polyimide film 8 was prepared by etching and removing in the same manner as in Example 1. The CTE of the polyimide film 8 was 7 ppm / K, and the CHE was 11 ppm /% RH.
  • Example 9 instead of the stainless foil 1, the stainless foil 3 (SUS444, thickness; 25 ⁇ m, coefficient of thermal expansion; 11 ppm / K, tensile modulus; 215 GPa, Ra; 5.58 nm, Rz; 36.4 nm) is used and a polyamic acid solution is used.
  • a metal-clad laminate 9a and a polyimide film 9a were prepared in the same manner as in Example 1 except that A was applied so as to have a thickness of 6.0 ⁇ m after curing.
  • the adhesiveness and warpage of the metal-clad laminate 9a were good, and Ra and Rz of the exposed surface of the polyimide insulating layer not in contact with the stainless steel foil 3 were 0.31 nm and 3.2 nm, respectively.
  • Table 4 The CTE of the polyimide film 9a was ⁇ 1.6 ppm / K, Td5 was 517 ° C, Tg was 365 ° C, CHE was 9 ppm /% RH, the hygroscopicity was 0.91 wt%, and the tensile elastic modulus was 10.5 GPa. .. These results are shown in Table 5.
  • Example 10 Example 1 except that the stainless foil 3 was used instead of the stainless foil 1, the polyamic acid solution B was used instead of the polyamic acid solution A, and the film was applied so that the thickness after curing was 6.0 ⁇ m.
  • a metal-clad laminate 10b and a polyimide film 10b were prepared.
  • the adhesiveness and warpage of the metal-clad laminate 10b were good, and Ra and Rz of the exposed surface of the polyimide insulating layer not in contact with the stainless steel foil 3 were 0.25 nm and 2.1 nm, respectively.
  • the CTE of the polyimide film 10b was 6.4 ppm / K
  • Td5 was 510 ° C.
  • Tg was 390 ° C.
  • CHE was 14 ppm /% RH
  • the hygroscopicity was 1.2 wt%
  • the tensile elastic modulus was 8.5 GPa.
  • Example 11 instead of the stainless steel foil 1, a titanium foil 1 (TR270C, thickness; 50 ⁇ m, coefficient of thermal expansion; 11 ppm / K, tensile modulus; 113 GPa, Ra; 9.71 nm, Rz; 97.5 nm) was used, and a polyamic acid solution was used.
  • a metal-clad laminate 11a and a polyimide film 11a were prepared in the same manner as in Example 1 except that A was applied so that the thickness after curing was 6.0 ⁇ m. The adhesiveness and warpage of the metal-clad laminate 11a were good, and Ra and Rz of the exposed surface of the polyimide insulating layer not in contact with the titanium foil 1 were 0.24 nm and 2.5 nm, respectively.
  • Example 12 Example 1 except that titanium foil 1 was used instead of stainless steel foil 1, polyamic acid solution B was used instead of polyamic acid solution A, and the film was applied so that the thickness after curing was 6.0 ⁇ m.
  • a metal-clad laminate 12b and a polyimide film 12b were prepared. The adhesiveness and warpage of the metal-clad laminate 12b were good, and Ra and Rz of the exposed surface of the polyimide insulating layer not in contact with the titanium foil 1 were 0.28 nm and 3.7 nm, respectively.
  • the CTE of the polyimide film 12b was 6.4 ppm / K
  • Td5 was 510 ° C.
  • Tg was 390 ° C.
  • CHE was 14 ppm /% RH
  • the hygroscopicity was 1.2 wt%
  • the tensile elastic modulus was 8.5 GPa.
  • Example 13 A metal-clad laminate 13a and a polyimide film 13a were prepared in the same manner as in Example 1 except that the polyamic acid solution A was applied so as to have a thickness of 12.2 ⁇ m after curing.
  • the adhesiveness and warpage of the metal-clad laminate 13a were good, and Ra and Rz of the exposed surface of the polyimide insulating layer not in contact with the stainless steel foil 1 were 0.57 nm and 9.4 nm, respectively.
  • the CTE of the polyimide film 13a was 22 ppm / K
  • Td5 was 517 ° C
  • Tg was 365 ° C
  • CHE was 9 ppm /% RH
  • the hygroscopicity was 0.91 wt%.
  • Example 14 instead of the stainless steel foil 1, the stainless steel foil 2 was used and applied so that the thickness of the polyamic acid solution A after curing was 5.0 ⁇ m.
  • the metal-clad laminate 14a and the metal-clad laminate 14a and the same as in Example 1 were applied.
  • a polyimide film 14a was prepared.
  • the water vapor transmittance was measured over 4 days by touching water vapor from the polyimide insulating layer side under the conditions of 40 ° C. and 90% RH, but the lower limit of measurement (1.0 ⁇ 10) was measured. -7 g / (m 2 ⁇ day )) were below.

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