WO2021256298A1 - Film de polyimide multicouche incolore, corps multicouche et procédé de fabrication de dispositif électronique flexible - Google Patents

Film de polyimide multicouche incolore, corps multicouche et procédé de fabrication de dispositif électronique flexible Download PDF

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Publication number
WO2021256298A1
WO2021256298A1 PCT/JP2021/021330 JP2021021330W WO2021256298A1 WO 2021256298 A1 WO2021256298 A1 WO 2021256298A1 JP 2021021330 W JP2021021330 W JP 2021021330W WO 2021256298 A1 WO2021256298 A1 WO 2021256298A1
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layer
film
polyimide
mass
solution
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PCT/JP2021/021330
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English (en)
Japanese (ja)
Inventor
伝一朗 水口
哲雄 奧山
洋行 涌井
誠 中村
直樹 渡辺
治美 米虫
郷司 前田
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東洋紡株式会社
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Priority to CN202180032888.5A priority Critical patent/CN115515790A/zh
Priority to JP2021559597A priority patent/JPWO2021256298A1/ja
Priority to KR1020227023194A priority patent/KR20230025652A/ko
Publication of WO2021256298A1 publication Critical patent/WO2021256298A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08—Dimensions, e.g. volume
    • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105—Thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
    • B32B2379/08—Polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment

Definitions

  • the present invention relates to a polyimide film that is colorless and has a low coefficient of linear expansion and good mechanical properties, a laminate of the polyimide film and an inorganic substrate, and a method for manufacturing a flexible electronic device via the laminate.
  • Polyimide film has excellent heat resistance and good mechanical properties, and is widely used in the electric and electronic fields as a flexible material.
  • a general polyimide film is colored yellowish brown, it cannot be applied to a part such as a display device that requires light transmission.
  • display devices are becoming thinner and lighter, and further flexibility is required. Therefore, attempts are being made to replace the substrate material from a glass substrate with a flexible polymer film substrate, but the colored polyimide film is a substrate material for a liquid crystal display that displays by turning on / off light transmission. It cannot be used as a peripheral circuit such as a TAB or COF on which a drive circuit of a display device is mounted, or can be applied only to a small part such as the back side of a reflective display system or a self-luminous display device.
  • Patent Document 4 a method of heat treatment while spraying a gas having an oxygen content has been proposed (Patent Document 4), but the manufacturing cost is high in an environment where the oxygen concentration is less than 18%, and industrial production is not possible. It's extremely difficult.
  • Patent Documents 5 and 6 Attempts have also been made to obtain a white heat-resistant film by blending a colorless filler (white pigment) with colorless transparent polyimide.
  • Semi-alicyclic or full-alicyclic polyimides can obtain colorless transparency by increasing the number of monomer components having an alicyclic structure, but become hard and brittle and the elongation at break decreases, making it difficult to produce as a film. Become.
  • an aromatic monomer or a monomer having an amide bond in the molecule is introduced, the toughness is increased, the mechanical properties of the film are improved, but the film is easily colored and the colorless transparency is lowered.
  • a filler inorganic component
  • heat resistance and colorless transparency are improved, the coefficient of linear expansion is further lowered, and processing suitability is improved, but the resin physical properties become hard and brittle.
  • a white heat-resistant film can be obtained by introducing a filler made of a substance having a large difference in refractive index from the polyimide resin, but it is also sufficient to obtain high whiteness and hiding power.
  • the amount is mixed, the film becomes brittle and it becomes difficult to produce it industrially. That is, there is a trade-off relationship between practical properties such as heat resistance and mechanical properties and colorlessness (transparency or whiteness), and it has been extremely difficult to produce a colorless transparent polyimide film that satisfies all of them.
  • the present inventors tried to realize a well-balanced polyimide film by combining a plurality of polyimide resins.
  • a combination of resins of a plurality of components is blended, blended, or copolymerized, it is not always possible to obtain a result in which only the good points of each component are combined, but rather the drawbacks are synergistically expressed. There are many cases of doing so.
  • the present inventors have found that the advantages of each component can be fully brought out by combining polyimide resins to form a film so as to form a specific structure.
  • a multilayer polyimide film having a thickness of 3 ⁇ m or more and 120 ⁇ m or less, a yellow index of 5 or less, and containing at least two layers, a layer (a) and a layer (b).
  • a layer A layer containing a polyimide composition having an inorganic filler content of 0.05% by mass or more and less than 2.5%.
  • B Layer: A layer containing a polyimide composition having an inorganic filler content of 1% by mass or more and 35% by mass or less. However, the content of the inorganic filler in the layer (b) is higher than the content of the inorganic filler in the layer (a).
  • the content of the inorganic filler in the layer (a) is higher than the content of the inorganic filler in the layer (c).
  • the multilayer polyimide film according to any one of [1] to [5] which has a total light transmittance of 80% or more.
  • a method for manufacturing a flexible electronic device which comprises forming an electronic device on a multilayer polyimide film surface of the laminate according to the above [7], and then peeling it from an inorganic substrate.
  • the present invention may further include the following configurations.
  • [9] 1 (a) A step of applying a polyimide solution for forming a layer or a polyimide precursor solution to a temporary support to obtain a coating film a1.
  • 2 A step of applying (b) a polyimide solution for forming a layer or a polyimide precursor solution to the coating film a1 within 100 seconds after the coating film a1 is produced to obtain the coating film a1b1.
  • 3 A step of heating all layers to obtain a laminate having a residual solvent amount of 0.5% by mass or less based on all layers.
  • [10] 1 (a) A step of applying a polyimide solution for forming a layer or a polyimide precursor solution to a temporary support to obtain a coating film a1.
  • 2 A step of applying (b) a polyimide solution for forming a layer or a polyimide precursor solution to the coating film a1 within 100 seconds after the coating film a1 is produced to obtain the coating film a1b1.
  • 3 A step of heating all layers to obtain a laminate having a residual solvent amount of 5% by mass or more and 40% by mass based on all layers, and then peeling from the temporary support to obtain a self-supporting film.
  • 2 A step of applying (b) a polyimide solution for forming a layer or a polyimide precursor solution to the coating film a1 within 100 seconds after the coating film a1 is produced to obtain the coating film a1b1.
  • [12] 1 (a) A step of applying a polyimide solution for forming a layer or a polyimide precursor solution to a temporary support to obtain a coating film a1.
  • 4 A step of heating all layers to obtain a laminate having a residual solvent amount of 8% by mass or more and 40% by mass based on all layers, and then peeling from the temporary support to obtain a self-supporting film.
  • the present invention may further include the following configurations.
  • [13] 1 (a) A step of applying a polyimide solution for forming a layer or a polyimide precursor solution to a temporary support to obtain a coating film a1.
  • 2 A step of drying the coating film a1 to obtain a coating film a2 having a residual solvent amount of 5 to 40% by mass.
  • 3 (b) A step of applying a polyimide solution for forming a layer or a polyimide precursor solution to the coating film a2 to obtain the coating film a2b1.
  • 4 A step of heating all layers to obtain a laminate having a residual solvent amount of 0.5% by mass or less based on all layers.
  • the method for producing a multilayer polyimide film according to any one of [1] to [6], which comprises at least.
  • [14] 1 (a) A step of applying a polyimide solution for forming a layer or a polyimide precursor solution to a temporary support to obtain a coating film a1.
  • 2 A step of drying the coating film a1 to obtain a coating film a2 having a residual solvent amount of 5 to 40% by mass.
  • 3 (b) A step of applying a polyimide solution for forming a layer or a polyimide precursor solution to the coating film a2 to obtain the coating film a2b1.
  • 2 A step of drying the coating film a1 to obtain a coating film a2 having a residual solvent amount of 5 to 40% by mass.
  • the present invention may further include the following configurations.
  • [17] 1 (a) A step of applying a polyimide solution for forming a layer or a polyimide precursor solution onto a temporary support to obtain a coating film a1.
  • 2 A step of applying (b) a polyimide solution for forming a layer or a polyimide precursor solution to the coating film a1 within 100 seconds after the coating film a1 is produced to obtain the coating film a1b1.
  • 3 A step of applying (c) a polyimide solution for forming a layer or a polyimide precursor solution to the coating film a1b1 within 100 seconds after producing the coating film a1b1 to obtain the coating film a1b1c1.
  • 2 A step of applying (b) a polyimide solution for forming a layer or a polyimide precursor solution to the coating film a1 within 100 seconds after the coating film a1 is produced to obtain the coating film a1b1.
  • 4 A step of heating all layers to obtain a laminate having a residual solvent amount of 8% by mass or more and 40% by mass based on all layers, and then peeling from the temporary support to obtain a self-supporting film.
  • 5 A step of grasping both ends of the self-supporting film and further heating to obtain a film having a residual solvent amount of 0.5% by mass or less based on all layers.
  • the method for producing a multilayer polyimide film according to any one of [1] and [3] to [6], which comprises at least.
  • [19] 1 (a) A step of applying a polyimide solution for forming a layer or a polyimide precursor solution onto a temporary support to obtain a coating film a1.
  • 2 A step of drying the coating film a1 to obtain a coating film a2 having a residual solvent amount of 5 to 40% by mass.
  • 3 (b) A step of applying a polyimide solution for forming a layer or a polyimide precursor solution to the coating film a2 to obtain the coating film a2b1.
  • [20] 1 (a) A step of applying a polyimide solution for forming a layer or a polyimide precursor solution onto a temporary support to obtain a coating film a1. 2: A step of drying the coating film a1 to obtain a coating film a2 having a residual solvent amount of 5 to 40% by mass. 3: (b) A step of applying a polyimide solution for forming a layer or a polyimide precursor solution to the coating film a2 to obtain the coating film a2b1. 4: A step of drying the coating film a2b1 to obtain a coating film a2b2 having a residual solvent amount of 5 to 40% by mass based on the total layer.
  • the present invention may further include the following configurations.
  • [21] 1 (a) A step of applying a polyimide solution for forming a layer or a polyimide precursor solution to a temporary support to obtain a coating film a1. 2: Within 100 seconds after the coating film a1 is produced, (b) a step of applying a polyimide solution for forming a layer or a polyimide precursor solution to the coating film a1 to obtain a coating film a1b1.
  • 3 A step of heating all layers to obtain a coating film (a1b1) 2 having a residual solvent amount of 5% by mass or more and 40% by mass based on all layers.
  • [24] 1 (a) A step of applying a polyimide solution for forming a layer or a polyimide precursor solution to a temporary support to obtain a coating film a1. 2: Within 100 seconds after the coating film a1 is produced, (b) a step of applying a polyimide solution for forming a layer or a polyimide precursor solution to the coating film a1 to obtain a coating film a1b1.
  • 3 A step of heating all layers to obtain a coating film (a1b1) 2 having a residual solvent amount of 5% by mass or more and 40% by mass based on all layers.
  • the present invention may further include the following configurations.
  • [25] 1 (a) A step of applying a polyimide solution for forming a layer or a polyimide precursor solution to a temporary support to obtain a coating film a1.
  • 2 A step of drying the coating film a1 to obtain a coating film a2 having a residual solvent amount of 5 to 40% by mass.
  • 3 (b) A step of applying a polyimide solution for forming a layer or a polyimide precursor solution to the coating film a2 to obtain the coating film a2b1.
  • the method for producing a multilayer polyimide film according to any one of [1] and [3] to [6], which comprises at least.
  • [28] 1 (a) A step of applying a polyimide solution for forming a layer or a polyimide precursor solution to a temporary support to obtain a coating film a1.
  • 2 A step of drying the coating film a1 to obtain a coating film a2 having a residual solvent amount of 5 to 40% by mass.
  • 3 (b) A step of applying a polyimide solution for forming a layer or a polyimide precursor solution to the coating film a2 to obtain the coating film a2b1.
  • a method for producing a multilayer polyimide film which comprises repeating 1 and 2 in the above [9] to [28] to form an odd-numbered layer of 5 or more layers.
  • the total thickness of the (a) layer is 1% or more, preferably 2% or more, more preferably 4% or more, preferably 25% or less, preferably the total thickness of the film.
  • (a) A polyimide solution or a polyimide precursor solution for forming a layer, and (b) a polyimide solution or a polyimide precursor solution for forming a layer are simultaneously applied onto a temporary support, and then the entire layer is heated.
  • the multilayer polyimide film according to any one of [1] to [6], [22], and [23], which comprises at least a step of obtaining a laminate having a residual solvent amount of 0.5% by mass or less based on the total layer.
  • Production method [33] (a) A polyimide solution or a polyimide precursor solution for forming a layer, and (b) a polyimide solution or a polyimide precursor solution for forming a layer are simultaneously applied onto a temporary support, and then the entire layer is heated. After obtaining a laminate having a residual solvent amount of 8% by mass or more and 40% by mass based on the total layer, the film is peeled off from the temporary support to form a self-supporting film, and then both ends of the self-supporting film.
  • the method for producing a multilayer polyimide film according to. [34] (a) Polyimide solution or polyimide precursor solution for layer formation, (b) Polyimide solution or polyimide precursor solution for layer formation, (c) Polyimide solution or polyimide precursor solution for layer formation. After simultaneous application on the temporary support, all layers are heated to obtain a laminate having a residual solvent amount of 0.5% by mass or less based on all layers [3] to [6], [30]. ], The method for producing a multilayer polyimide film according to any one of [31].
  • the polyimide composition of the layer (b) in the present invention has a low CTE by containing an inorganic filler. Further, when an inorganic filler having a large difference in refractive index from the resin is used, a highly concealed white film is obtained. However, the polyimide composition in which the inorganic filler is added to a level where the CTE is lowered by 5 ppm / ° C. or more as compared with the resin to which the inorganic filler is not added, and the polyimide composition in which the inorganic filler is added to a level having sufficient concealing property are brittle. It can be extremely difficult to produce as an industrial production level, that is, a long continuous film.
  • the polyimide composition of the (a) layer which has a low content of the inorganic filler, is more preferably combined with the polyimide composition of the (c) layer to form a multilayer, the outer layer has less inorganic filler, and the inner layer has more inorganic filler.
  • a transition layer having a slanted composition can be formed between the applied layers. ..
  • the transition layer is formed by repeating coating of each component and drying until it loses fluidity and becomes semi-solid, and after forming the necessary layer, it is dried by final heating. It can also be formed in the step of obtaining a solid film by performing a chemical reaction as needed. Since polyimide is chemically stable, for example, a second polyimide solution or a polyimide precursor solution having a different composition (or the same chemical composition may be used) is applied onto the first polyimide composition layer and dried by heating.
  • the multilayer polyimide film of the present invention has a thickness of 3 ⁇ m or more and 120 ⁇ m or less. It is preferably 4 ⁇ m or more, more preferably 5 ⁇ m or more, and further preferably 8 ⁇ m or more because the mechanical properties are good. Further, it is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, and further preferably 60 ⁇ m or less because the transparency becomes good.
  • the multilayer polyimide film of the present invention has a yellow index of 5 or less. It is preferably 4 or less, more preferably 3.5 or less, and further preferably 3 or less because the transparency is good. Since the lower the yellow index is, the lower limit is not particularly limited, but industrially, it may be 0.1 or more, and 0.2 or more may be used.
  • the multilayer polyimide film of the present invention preferably has a coefficient of linear expansion of 50 ppm / ° C. or less. It is more preferably 45 ppm / ° C. or lower, and even more preferably 40 ppm / ° C. or lower.
  • the lower limit is not particularly limited, but industrially, 1 ppm / ° C. or higher is sufficient, and 5 ppm / ° C. or higher may be used.
  • the multilayer polyimide film of the present invention preferably has a total light transmittance of 86% or more. It is preferably 87% or more, more preferably 88% or more, and further preferably 89% or more because the transparency becomes good.
  • the upper limit is not particularly limited, but industrially, it may be 99% or less, and may be 98% or less.
  • the polyimide composition contains at least a polyimide resin and an inorganic filler.
  • the polyimide solution or polyimide precursor solution in the present invention contains at least a polyimide resin or a polyimide precursor and a solvent. Further, when forming a layer to which the inorganic filler is added, a solution in which the inorganic filler is dispersed in advance is used.
  • the polyimide resin (hereinafter, also simply referred to as polyimide) is a polymer generally obtained by a polycondensation reaction between a tetracarboxylic acid anhydride and a diamine.
  • a polycondensation of a tetracarboxylic acid anhydride containing 70% by mass or more of an alicyclic tetracarboxylic acid anhydride and a diamine containing 70% by mass or more of a diamine having an amide bond in the molecule Shrinkage of a polyimide obtained by polymerization or a tetracarboxylic acid anhydride containing 70% by mass or more of an alicyclic tetracarboxylic acid anhydride and a diamine containing 70% by mass or more of a diamine having a trifluoromethyl group in the molecule.
  • the polyimide obtained by polymerization can be exemplified.
  • the polyimide preferably used in the present invention is obtained from a tetracarboxylic acid anhydride containing 70% by mass or more of aromatic tetracarboxylic acid anhydride and a diamine containing at least 70% by mass or more of a diamine having a sulfur atom in the molecule.
  • An example can be exemplified of the polyimide obtained by the condensation polymerization with the diamine.
  • Examples of the alicyclic tetracarboxylic acid anhydride in the present invention include 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid and 1,2,3,4-cyclohexane.
  • Tetracarboxylic acid 1,2,4,5-cyclohexanetetracarboxylic acid, 3,3', 4,4'-bicyclohexyltetracarboxylic acid, bicyclo [2,2,1] heptane-2,3,5,6 -Tetracarboxylic acid, bicyclo [2,2,2] octane-2,3,5,6-tetracarboxylic acid, bicyclo [2,2,2] octo-7-en-2,3,5,6-tetra Carboxylic acid, tetrahydroanthracene-2,3,6,7-tetracarboxylic acid, tetradecahydro-1,4: 5,8: 9,10-trimethanoanthracene-2,3,6,7-tetracarboxylic acid, Decahydronaphthalene-2,3,6,7-tetracarboxylic acid, decahydro-1,4: 5,8-dimethanonaphthalene-2,3,6,7-te
  • dianhydride having two acid anhydride structures is preferable, and in particular, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and 1,2,3,4-cyclohexanetetracarboxylic are preferable.
  • Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride is preferred, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride is more preferred, and 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride is even more preferred. These may be used alone or in combination of two or more.
  • aromatic tetracarboxylic acid anhydride in the present invention examples include 4,4'-(2,2-hexafluoroisopropyridene) diphthalic acid, 4,4'-oxydiphthalic acid, and bis (1,3-dioxo-1,3).
  • tricarboxylic acid and dicarboxylic acid may be used in addition to the tetracarboxylic dianhydride.
  • tricarboxylic acids include aromatic tricarboxylic acids such as trimellitic acid, 1,2,5-naphthalene tricarboxylic acid, diphenyl ether-3,3', 4'-tricarboxylic acid, and diphenylsulfone-3,3', 4'-tricarboxylic acid.
  • An acid or an alkylene such as a hydrogenated additive of the above aromatic tricarboxylic acid such as hexahydrotrimellitic acid, ethylene glycol bistrimerite, propylene glycol bistrimerite, 1,4-butanediol bistrimerite, polyethylene glycol bistrimerite.
  • Glycolbitrimeritate and these monoanhydrides and esterified products can be mentioned.
  • monoanhydride having one acid anhydride structure is preferable, and in particular, trimellitic acid anhydride and hexahydrotrimellitic acid anhydride are preferable. These may be used alone or in combination of two or more.
  • dicarboxylic acids examples include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, 4,4'-oxydibenzenecarboxylic acid, and the above aromatic dicarboxylic acid such as 1,6-cyclohexanedicarboxylic acid.
  • Hydrogen additives oxalic acid, succinic acid, glutaric acid, adipic acid, heptanedioic acid, octanedioic acid, azelaioic acid, sevacinic acid, undecadioic acid, dodecanedioic acid, 2-methylsuccinic acid, and acid acidates thereof.
  • an esterified product or the like can be mentioned.
  • aromatic dicarboxylic acids and hydrogen additives thereof are preferable, and terephthalic acid, 1,6-cyclohexanedicarboxylic acid, 4,4'-oxydibenzenecarboxylic acid are particularly preferable.
  • the dicarboxylic acids may be used alone or in combination of two or more.
  • aromatic diamines and alicyclic amines can be mainly used.
  • aromatic diamines include 2,2'-dimethyl-4,4'-diaminobiphenyl, 1,4-bis [2- (4-aminophenyl) -2-propyl] benzene, and 1,4-bis.
  • a part or all of the hydrogen atoms on the aromatic ring of the aromatic diamine may be substituted with a halogen atom, an alkyl group or an alkoxyl group having 1 to 3 carbon atoms, or a cyano group, and further, the carbon number 1 may be substituted.
  • a part or all of the hydrogen atom of the alkyl group or the alkoxyl group of ⁇ 3 may be substituted with a halogen atom.
  • alicyclic diamines examples include 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-2-ethylcyclohexane, and 1,4-diamino-2-n-propyl.
  • inorganic filler used in the polyimide composition in the present invention electrically insulating inorganic fine particles are preferable. Further, fine particles made of an inorganic substance having a coefficient of linear expansion of 0 to 15 ppm / ° C. are preferable. More preferably, the fine particles are made of an inorganic substance having a linear expansion coefficient of 1 to 14 ppm / ° C., and more preferably, the fine particles are made of an inorganic substance having a linear expansion coefficient of 2 to 13 ppm / ° C.
  • metal oxides such as aluminum oxide, silicon oxide, magnesium oxide, zinc oxide, zirconium oxide, tin oxide, titanium oxide and calcium oxide
  • metal fluorides such as calcium fluoride
  • metal sulfides such as zinc sulfide
  • Metallic sulfates such as calcium sulfate and barium sulfate
  • phosphates such as calcium phosphate
  • fine particles such as basic zinc molybdate, zinc basic calcium molybdate, molybdenum white, and nitrate.
  • aluminum oxide, silicon oxide, magnesium oxide, zinc oxide, zirconium oxide, tin oxide, rutile-type titanium oxide, calcium fluoride, barium sulfate or calcium phosphate are preferable.
  • an inorganic filler made of a substance having a high refractive index preferably an inorganic filler made of a substance having a refractive index of 1.98 or more at a wavelength of 550 nm at 25 ° C.
  • the refractive index is more preferably 1.99 or more, still more preferably 2.00 or more.
  • the lower limit of the refractive index of such an inorganic filler is not particularly limited, but is preferably 4 or less, and more preferably 3 or less.
  • the total light transmittance of the film is increased, preferably 80% or more, and further. It can be preferably increased to 85% or more, and a so-called colorless and transparent film can be obtained. Since the colorless transparency is further improved, the refractive index is more preferably 1.42 or more and 1.97 or less, and further preferably 1.44 or more and 1.96 or less.
  • the lower limit of the average diameter of the particles of the inorganic filler used in the present invention is preferably 10 nm, more preferably 20 nm, and even more preferably 50 nm.
  • the upper limit is preferably 5 ⁇ m, more preferably 1.5 ⁇ m, and even more preferably 0.3 ⁇ m.
  • the multilayer polyimide film of the present invention has a content of at least 0.05% by mass or more and less than 2.5%, preferably 0.08% by mass or more and 1.6% by mass or less, and more preferably 0.2% by mass or more.
  • (A) layer containing a polyimide composition of 1.2% by mass or less (B) Contains a polyimide composition having an inorganic filler content of 1% by mass or more and 35% by mass or less, preferably 3% by mass or more and 32% by mass or less, and more preferably 6% by mass or more and 28% by mass or less (b). It contains a layer, and the content of the inorganic filler in the layer (a) ⁇ the content of the inorganic filler in the layer (b).
  • the structure is such that the layer (b), which has a high content of inorganic filler and a low coefficient of linear expansion but tends to be brittle, is reinforced with a layer (a) having a high content of inorganic filler and high toughness.
  • the polyimide composition contained in the layer (a) is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 100% by mass. Is.
  • the polyimide composition contained in the layer (b) is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 100. It is mass%.
  • the content of the inorganic filler in the layer (b) is higher than the content of the inorganic filler in the layer (a). That is, the ratio ((b) / (a)) of the inorganic filler content of the layer (a) to the inorganic filler content of the layer (b) is preferably more than 1, more preferably 2 or more. It is more preferably 3 or more, and particularly preferably 5 or more. Further, it is preferably 700 or less, more preferably 100 or less, still more preferably 50 or less, and particularly preferably 30 or less.
  • the layer (a) has a three-layer structure ((a) / (b) / (a)) existing on both one surface side and the other surface side of the layer (b). Is preferable. Warpage of the film can be suppressed by making it symmetrical in the thickness direction as a three-layer structure.
  • the structure of the multilayer polyimide film is further configured such that the layer (a) is present on one surface side of the layer (b) and the layer (c) is present on the other surface side of the layer (b). It can have a layered structure ((a) / (b) / (c)).
  • the relationship between the layers is that the content of the inorganic filler in the layer (b) is higher than the content of the inorganic filler in the layer (a), and the content of the inorganic filler in the layer (a) is higher than the content of the inorganic filler in the layer (c). It is preferable that there are many. That is, it is preferable that the content of the inorganic filler in the layer (c) ⁇ the content of the inorganic filler in the layer (a) ⁇ the content of the inorganic filler in the layer (b).
  • This configuration is basically a structure in which a layer (b) having a high content of an inorganic filler is sandwiched between a layer (a) and a layer (c) having a low content of an inorganic filler, but the inorganic filler of the layer (c) is sandwiched.
  • the content is preferably 0.3% by mass or less, more preferably 0.1% by mass or less, still more preferably substantially 0% by mass, so that the surface of one side of the outer layer of the multilayer film is highly smooth. Surface can be realized.
  • the ratio of the inorganic filler content of the (a) to the inorganic filler content of the layer (b) ((b) / (a)) is As described above.
  • the ratio of the inorganic filler content of the (a) to the inorganic filler content of the layer (c) ((c) / (a)) is 1. It is preferably less than, more preferably 0.5 or less, still more preferably 0.2 or less, still more preferably 0.1 or less, and particularly preferably 0.
  • the inorganic filler added to the layer (a), the layer (b), and the layer (c) may be the same inorganic filler or different inorganic fillers.
  • an inorganic filler having a uniform particle size for the outer layer (a) to (c) and using a highly transparent inorganic filler for the inner layer (b) protrusions on the film surface are used. It is possible to realize a film having a uniform color and high colorless transparency as a whole film. It was
  • the polyimide resin used for the layer (a), the layer (b), and the layer (c) may all be a polyimide resin having the same chemical composition, or may be a different polyimide resin.
  • the inner layer (b) is made of a polyimide resin having a high CTE control effect by adding an inorganic filler
  • the outer layers (a) and (c) are made of a highly tough polyimide resin. A well-balanced film can be obtained.
  • the number of layers may be increased so as to have four or more layers, preferably an odd number of layers.
  • the total thickness of the layer (a) and the layer (c) is preferably 34% or less, and further 26% or less of the total thickness of the film. It is preferable that the composition is 13% or less, more preferably 7% or less.
  • the total thickness of the layer (a) and the layer (c) is preferably 1% or more, more preferably 2% or more, and further. It is preferably 4% or more.
  • a transition layer whose composition continuously changes from the polyimide of the (a) layer to the polyimide of the (b) layer exists between the (a) layer and the (b) layer.
  • the upper limit of the thickness of the transition layer is preferably 8% or less, or 3 ⁇ m or less, more preferably 3% or less, or 1 ⁇ m or less of the total thickness of the film.
  • the thickness of the transition layer is the thickness of the region where the polyimide of the (a) layer and the polyimide of the (b) layer are mixed and the composition is inclined from one to the other, and the thickness of the (a) layer of the mixed layer.
  • the polyimide composition ratio (mass ratio) of the polyimide / (b) layer is in the range of 5/95 to 95/5.
  • the thickness of the transition layer can be measured by cutting the film diagonally in the thickness direction and observing the composition distribution of the polyimide. The same applies to the transition layer between the layer (b) and the layer (c).
  • the multilayer polyimide film of the present invention can be laminated with an inorganic substrate to form a laminated body.
  • the inorganic substrate may be a plate-shaped substrate that can be used as a substrate made of an inorganic substance.
  • a glass plate, a ceramic plate, a semiconductor wafer, a metal or the like, and these glass plates and ceramic plates are used.
  • the semiconductor wafer and the composite of the metal include those in which these are laminated, those in which they are dispersed, and those in which these fibers are contained.
  • a flexible electronic device can be manufactured by forming an electronic device on the surface of the multilayer polyimide film of the laminate of the present invention and then peeling it from the inorganic substrate.
  • the manufacturing method for obtaining the multilayer polyimide film of the present invention will be described below.
  • the two-layer polyimide film is placed on a long and flexible temporary support.
  • 3' Heating is performed over a period of 5 minutes or more and 45 minutes or less until the residual solvent amount of all layers becomes 8% by mass or more and 40% by mass or less.
  • the step may be a step of grasping both ends of the self-supporting film and further heating until the residual solvent amount of all layers becomes 0.5% by mass or less.
  • the polyimide solution or the polyimide precursor solution for (a) layer formation or (c) layer formation may be applied once again after the above 1 and 2, and the process is repeated. By repeating the coating, a more multi-layered film can be obtained.
  • 1 (a) Step of applying polyimide solution or polyimide precursor solution for layer formation, 2: A step of drying the layer (a) so that the amount of residual solvent is 5 to 40% by mass. 3: A step of applying (b) a polyimide solution for forming a layer or a polyimide precursor solution onto the (a) layer. 4: Next, a step of heating over a time of preferably 5 minutes or more and 60 minutes or less until the average residual solvent amount of all layers becomes 0.5% by mass or less. Can be produced via.
  • process of 4 is divided into two stages, 4': After heating for 5 minutes or more and 45 minutes or less until the residual solvent amount of all layers becomes 8% by mass or more and 40% by mass or less, the film is peeled off from the temporary support to obtain a self-supporting film.
  • Process, 5 A step of grasping both ends of the self-supporting film and further heating until the residual solvent amount of all layers becomes 0.5% by mass or less. May be.
  • the polyimide solution or the polyimide precursor solution for (a) layer formation or (c) layer formation may be applied once again after the above 1 and 2, and the application may be repeated. By doing so, a multi-layered film can be obtained.
  • the temperature of the polyimide solution or the polyimide precursor solution is 10 ° C. or higher and 40 ° C. or lower, preferably 15 ° C. or higher and 35 ° C. or lower, and the humidity is 10% RH or higher and 55% RH or lower, preferably 20% RH or higher. It is preferably performed on a long and flexible polyimide in the atmosphere or an inert gas at 50% RH.
  • the first layer to be applied can be applied using a comma coater, a bar coater, a slit coater, or the like, and the second and subsequent layers can be applied by a die coater, a curtain coater, a spray coater, or the like. .. It is also possible to apply these plurality of layers substantially at the same time by using a multilayer die.
  • the environment for applying the solution is preferably in the atmosphere or in an inert gas.
  • the inert gas may be interpreted as a gas having a substantially low oxygen concentration, and nitrogen or carbon dioxide may be used from an economical point of view.
  • the temperature in the coating environment affects the viscosity of the coating liquids, and when the two types of coating liquids are overlapped, the two types of coating liquids are mixed with each other at the interface to form a transition layer. Affects.
  • the viscosity of the polyimide solution or the polyimide precursor solution of the present invention is preferably adjusted to an appropriate viscosity range especially in the non-contact coating method after the second layer, and such a temperature range is in the mixture of the two-layer interface. Also contributes to properly maintaining the fluidity in the viscosity range.
  • the viscosity (viscosity 1) of the solution 1 is applied.
  • the ratio of the viscosity represented by the viscosity 2 / viscosity 1 is preferably 1.5 or less, more preferably 1.0 or less, and further preferably 0.8 or less. .. Further, it is preferably 0.1 or more, and more preferably 0.2 or more.
  • the viscosity 1 measured at 25 ° C. using an E-type viscometer is preferably 20 Pa ⁇ s or more, and more preferably 50 Pa ⁇ s or more. ..
  • the viscosity (viscosity 1, viscosity 2) of the polyimide solution or the polyimide precursor solution is preferably 300 Pa ⁇ s or less, and more preferably 200 Pa ⁇ s or less, from the viewpoint of handleability.
  • the solvents used in polyimide solutions or polyimide precursor solutions are hygroscopic, and when the solvent absorbs moisture and the water content of the solvent increases, the solubility of the resin component decreases, and the dissolved component precipitates in the solution, resulting in a solution. May cause a sharp increase in viscosity. If such a situation occurs after coating, the internal structure of the film may become inhomogeneous, resulting in void-like defects and impairing mechanical properties.
  • the temporary support used in the present invention glass, a metal plate, a metal belt, a metal drum, a polymer film, a metal foil, or the like can be used.
  • a film such as polyethylene terephthalate, polyethylene naphthalate, or polyimide can be used as the temporary support. It is one of the preferable embodiments to perform a mold release treatment on the surface of the temporary support.
  • the polyimide solution or the polyimide precursor solution it is preferable to apply the polyimide solution or the polyimide precursor solution to the temporary support, dry the coating film until the residual solvent amount is 5 to 40% by mass, and then apply the next layer. Drying to a residual solvent amount of 40% by mass is a sufficiently dry state in which the applied coating liquid loses its fluidity and reaches a semi-solid. When the amount of residual solvent in the coating film reaches 5% by mass or less, when the next solution is applied, the re-swelling of the previously dried coating film becomes inhomogeneous, and the boundary between two adjacent layers may be disturbed. There is.
  • the solvent of the coating liquid can be uniformly diffused and transferred at the boundary surface, and a transition layer having an appropriate thickness is formed by microscopic flow mixing.
  • heat treatment is performed to accelerate drying and, if necessary, a chemical reaction.
  • a polyimide solution it may be simply dried in the sense of removing the solvent, but when a polyimide precursor solution is used, both drying and a chemical reaction are required.
  • the polyimide precursor is preferably in the form of polyamic acid or polyisoimide. A dehydration condensation reaction is required to convert polyamic acid to polyimide.
  • the dehydration condensation reaction can be carried out only by heating, but an imidization catalyst can also be allowed to act if necessary. Even in the case of polyisoimide, the conversion from isoimide bond to imide bond can be performed by heating. It is also possible to use an appropriate catalyst in combination.
  • the amount of residual solvent in the final multilayer polyimide film is preferably 0.5% by mass or less, more preferably 0.2% by mass or less, still more preferably 0.08% by mass as an average value of all layers of the film. It is as follows.
  • the heating time is preferably 5 minutes or more and 60 minutes or less, more preferably 6 minutes or more and 50 minutes or less, and further preferably 7 minutes or more and 30 minutes or less.
  • the solvent can be removed, the necessary chemical reaction can be completed, the transition layer can be controlled to an appropriate thickness, and the colorless transparency, mechanical properties, especially the elongation at break can be achieved. Can be kept high. If the heating time is short, the formation of the transition layer is delayed, and if the heating time is longer than necessary, the film coloring may become stronger and the breaking elongation of the film may decrease.
  • the applied solution dries or undergoes a chemical reaction by heating and is self-supporting and can be peeled off from the temporary support, it may be peeled off from the temporary support during the heating step. More specifically, until the residual solvent amount of the entire film layer reaches the range of 5% by mass or more and 40% by mass, preferably 5 minutes or more and 45 minutes or less, more preferably 6 minutes or more and 30 minutes or less, still more preferably 7. After heating for a time of 1 minute or more and 20 minutes or less, the self-supporting film is peeled off from the temporary support, and both ends of the self-supporting film are sandwiched between clips or pierced into a pin to grip the film.
  • the residual solvent amount of all layers is preferably 0.5% by mass or less, more preferably 0.2% by mass or less, still more preferably 0.08% by mass or less. Therefore, a step of obtaining a multilayer polyimide film can be adopted.
  • a step of obtaining a multilayer polyimide film can be adopted.
  • the self-supporting film may be stretched.
  • the stretching may be in either the longitudinal direction of the film (MD direction) or the width direction (TD) of the film, or both.
  • Stretching in the longitudinal direction of the film can be performed by using the speed difference of the transport roll or the difference in speed between the transport roll and the speed after gripping both ends.
  • Stretching in the film width direction can be performed by widening the gripped clip or pin. Stretching and heating may be performed at the same time.
  • the draw ratio can be arbitrarily selected from 1.00 times to 2.5 times.
  • a polyimide that is difficult to stretch by itself and a polyimide that can be stretched can be combined to enable the polyimide to be stretched to a composition that is difficult to stretch, that is, easily broken by stretching.
  • Mechanical properties can be improved. Since the volume of polyimide becomes smaller during film formation due to drying or dehydration condensation, the stretching effect is exhibited even when both ends are gripped at equal intervals (stretching ratio is 1.00 times).
  • ⁇ Measurement of thickness of multilayer polyimide film> The thicknesses of the multilayer polyimide films A to F were measured using a micrometer (Millitron 1245D manufactured by Fine Wolf Co., Ltd.).
  • the multilayer polyimide film was cut into strips of 100 mm ⁇ 10 mm in the flow direction (MD direction) and the width direction (TD direction) at the time of coating, and used as test pieces.
  • Tensile tester manufactured by Shimadzu, Autograph (R) model name AG-5000A
  • the tensile elastic modulus and tensile strength are obtained in each of the MD and TD directions under the conditions of a tensile speed of 50 mm / min and a chuck distance of 40 mm.
  • the elongation at break were obtained, and the average value of the measured values in the MD direction and the TD direction was obtained.
  • CTE Coefficient of linear expansion
  • ⁇ Transition layer thickness> The diagonally cut surface of the film is prepared by SAICAS DN-20S type (Daipla Wintes), and then the obliquely cut surface is microscopically ATR using germanium crystal (incident angle 30 °) by microscopic IR Cary 620 FTIR (Agilent).
  • the spectrum was obtained by the method, and the increase / decrease of the characteristic peaks of each of the (a) layer and (b) layer and the slope of the composition were obtained in terms of mass ratio from the calibration line obtained in advance, and (a) layer composition / ( b)
  • the thickness in the range of 5/95 mass ratio to 95/5 mass ratio of the layer composition was determined as the transition layer thickness.
  • ⁇ Haze> The haze of the film was measured using HAZEMETER (NDH5000, manufactured by Nippon Denshoku Co., Ltd.). A D65 lamp was used as the light source. The same measurement was performed three times, and the arithmetic mean value was adopted.
  • Total light transmittance The total light transmittance (TT) of the film was measured using HAZEMETER (NDH5000, manufactured by Nippon Denshoku Co., Ltd.). A D65 lamp was used as the light source. The same measurement was performed three times, and the arithmetic mean value was adopted.
  • ⁇ Film warp> A film cut into a square having a size of 100 mm ⁇ 100 mm is used as a test piece, and the test piece is allowed to stand on a flat surface at room temperature so as to be concave, and the distances from the flat surface at the four corners (h1rt, h2rt, h3rt, h4rt: unit mm). ) was measured, and the average value was taken as the amount of warpage (mm).
  • a polyamic acid solution Caa having a solid content of 25% by mass and a reduction viscosity of 1.10 dl / g was obtained.
  • 204 parts by mass of DMAc was added to the obtained polyamic acid solution Caa to dilute the polyamic acid concentration to 15% by mass, and then 1.3 parts by mass of isoquinoline was added as an imidization accelerator.
  • 12.25 parts by mass of acetic anhydride was slowly added dropwise as an imidizing agent.
  • stirring was continued for 24 hours and a chemical imidization reaction was carried out to obtain a polyimide solution Cpi.
  • the polyimide solution and the polyamic acid solution (polyimide precursor solution) obtained in the production example were formed into a film by the following method, and the optical properties and mechanical properties were measured.
  • the results are shown in Table 1.
  • a polyimide solution or a polyamic acid solution was applied to the center of a glass plate having a side of 30 cm, approximately 20 cm square, using a bar coater so that the final thickness was 25 ⁇ 2 ⁇ m, and dry nitrogen was gently poured. After heating in an inert oven at 100 ° C. for 30 minutes and confirming that the amount of residual solution in the coating film was 40% by mass or less, the mixture was heated in a muffle furnace substituted with dry nitrogen at 300 ° C. for 20 minutes. Then, it is taken out from the muffle furnace, the end of the dry coating film (film) is raised with a utility knife, and it is carefully peeled from the glass to obtain a film.
  • Example 1 Inorganic filler No. 2 shown in Table 2 was added to the polyamic acid solution A obtained in Production Example 1. 2: A dispersion obtained by dispersing colloidal silica in dimethylacetamide (“Snowtex (registered trademark) DMAC-ST-ZL” manufactured by Nissan Chemical Industries, Ltd.) is prepared by silica (lubricant) with respect to the total amount of polymer solids in the polyamic acid solution. The mixture was added so as to be 0.8% by mass and uniformly dispersed. Inorganic filler No. 2 shown in Table 2 was added to the polyimide solution C obtained in Production Example 3. 1: Calcium fluoride particles with an average particle diameter of 0.2 ⁇ m manufactured by Stella Chemifa Co., Ltd.
  • a polyamic acid solution in which 2 is dispersed is placed on a non-slip material surface of a polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd., hereinafter abbreviated as PET film) which is a temporary support, and a comma coater is applied so that the final film thickness is 1 ⁇ m. It was applied using and made the first layer. Subsequently, after 10 seconds, the inorganic filler No. The polyimide solution in which 1 was dispersed was applied on the first layer previously applied with a die coater so that the final film thickness was 23 ⁇ m to form the second layer.
  • the self-supporting film is peeled off from the A4100 film that has been used as a support, passed through a pin tenter having a pin sheet on which pins are arranged, and the film end is gripped by inserting the pin into the pin so that the film does not break and is unnecessary.
  • the pin sheet spacing was adjusted so that sagging did not occur, and the film was conveyed, and heated at 200 ° C. for 3 minutes, 250 ° C. for 3 minutes, and 300 ° C. for 6 minutes to proceed with the imidization reaction.
  • the film was cooled to room temperature in 2 minutes, and the portions of the film having poor flatness were cut off with a slitter and wound into a roll to obtain a roll of a film (actual 1) having a width of 580 mm and a length of 100 m.
  • Table 3 shows the evaluation results of the obtained film (actual 1).
  • Example 2 to 21 Comparative Examples 1 to 9
  • a film was produced and evaluated in the same manner as in Example 1 by combining the polyamic acid solution or polyimide solution shown in Table 1 with the inorganic filler shown in Table 1. The results are shown in Tables 3-7.
  • a die coat was used in the case of a single layer in the comparative example.
  • Comparative Example 1 a film formation was attempted using only the polyimide resin C, but the film was not slippery and it was difficult to wind it up without wrinkles.
  • Comparative Example 2 lacks the inorganic filler of the layer (b) from the configuration of Example 3. It can be seen that the CTE is higher than that of Example 3. Moreover, this CTE is equivalent to Comparative Example 1.
  • Example 3 only the layer (b) in Example 3 was extracted and prepared so that the film thickness was the same.
  • the CTE is controlled to be relatively low, which is about the same as in Example 3, but as can be understood from the extremely low breaking elongation, the film is extremely brittle and the film breaks frequently during the production.
  • Examples 1 to 7 and 12 to 15 relatively high light transmittance is obtained, and the haze indicating turbidity of the film is also low, however, in Examples 8 to 11 using an inorganic filler having a high refractive index. Has increased haze and decreased light transmittance. However, the yellow index is kept low, indicating that these films have a high degree of whiteness. That is, these are also not transparent, but are highly colorless films.
  • Examples 16 to 21 are cases where the same polyimide resin component is used for the (a) layer, the (b) layer, and the (c) layer, and the inorganic filler content of each layer is changed.
  • Comparative Examples 4 to 9 are films produced so that only the layer (b) has the same film thickness, corresponding to Examples 16 to 21.
  • the CET was lower than that of the films of the same resin composition produced on the laboratory scale without the addition of the inorganic filler shown in Table 1, indicating the effect of the addition of the inorganic filler. ing.
  • the film was broken when the self-supporting film was peeled from the temporary support base material, so that the film could be gripped by a pin. I could't do it, and I could't get a film that was good enough for evaluation.
  • the transition layer thickness could not be measured because the resin composition of each layer was the same.
  • Inorganic filler No. 2 shown in Table 2 was added to the polyamic acid solution A obtained in Production Example 1.
  • a dispersion obtained by dispersing colloidal silica in dimethylacetamide (“Snowtex (registered trademark) DMAC-ST-ZL” manufactured by Nissan Chemical Industries, Ltd.) is prepared by silica (lubricant) with respect to the total amount of polymer solids in the polyamic acid solution. It was added to 1.5% by mass and evenly dispersed.
  • Inorganic filler No. 2 shown in Table 2 was added to the polyimide solution C obtained in Production Example 3.
  • Silica particle Seahoster (registered trademark) S150 having an average particle diameter of 1.5 ⁇ m manufactured by Nippon Catalyst Co., Ltd. is first dispersed in DMAC with an attritor, and then 25% by mass with respect to the total amount of polymer solids in the polyimide solution. The mixture was uniformly mixed and stirred to disperse.
  • the inorganic filler No. A polyamic acid solution in which 2 was dispersed was applied onto a non-slip material surface of a polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd., hereinafter abbreviated as PET film) as a temporary support so that the final film thickness was 3 ⁇ m. Then, it was heated at 110 ° C. for 5 minutes as primary heating by a continuous dryer to form a semi-dry film having a residual solvent amount of 18% by mass, and the temporary support was wound into a roll. This semi-dry film is called GF (green film).
  • the obtained roll was set again in the above-mentioned apparatus, the semi-dried film was unwound together with the temporary support, and the inorganic filler No. 1 was placed on the semi-dried film.
  • the polyimide solution C in which 3 was dispersed was applied with a die coater so that the final film thickness was 19 ⁇ m, and then dried at 110 ° C. for 10 minutes. After drying, the amount of residual solvent is 23% by mass, and the self-supporting film is peeled off from the PET film that has been used as a support, passed through a pin tenter having a pin sheet on which pins are arranged, and gripped by inserting the film end into the pin.
  • the film is conveyed by adjusting the pin sheet spacing so that the film does not break and unnecessary slack does not occur, and the final heating is 200 ° C for 3 minutes, 250 ° C for 3 minutes, and 300 ° C for 6 minutes.
  • the film was heated under the above conditions, and the required imidization reaction was allowed to proceed with drying. Then, the film was cooled to room temperature in 2 minutes, and the portions of the film having poor flatness were cut off with a slitter and wound into a roll to obtain a roll of a film (actual 22) having a width of 510 mm and a length of 100 m.
  • Table 8 shows the evaluation results of the obtained film (actual 22). This coating method is called "wet / GF method".
  • Example 22 shows a large warp, which is due to the film being asymmetric in the thickness direction.
  • Inorganic filler No. 2 shown in Table 2 was added to the polyamic acid solution B obtained in Production Example 2.
  • a dispersion obtained by dispersing colloidal silica in dimethylacetamide (Nissan Chemical Industries, Ltd. "Snowtex (registered trademark) DMAC-ST-ZL") is prepared by silica (lubricant) with respect to the total amount of polymer solids in the polyamic acid solution. It was added to 1.5% by mass and evenly dispersed.
  • Inorganic filler No. 2 shown in Table 2 was added to the polyimide solution F obtained in Production Example 6.
  • Silica particle Seahoster (registered trademark) S150 having an average particle diameter of 1.5 ⁇ m manufactured by Nippon Catalyst Co., Ltd. is first dispersed in DMAC with an attritor, and then 25% by mass with respect to the total amount of polymer solids in the polyimide solution. The mixture was uniformly mixed and stirred to disperse. Under the combinations and conditions shown in Table 8, the mirror-finished stainless steel belt was coated with a three-layer co-extruded T-shaped die. That is, the order is the inorganic filler-containing polyamic acid solution B, the inorganic filler-containing polyamic acid solution F, and the inorganic filler-free polyamic acid solution B.
  • Example 1 First, the multilayer polyimide film (actual 25) obtained in Example 25 was cut into a rectangle having a size of 360 mm ⁇ 460 mm. Next, a UV / O 3 irradiator (SKR1102N-03 manufactured by LAN Technical) was used as the film surface treatment, and the layer (a) was irradiated with UV / O 3 for 3 minutes. In this case the distance between the UV / O 3 lamps and the film was 30 mm.
  • a UV / O 3 irradiator SSR1102N-03 manufactured by LAN Technical
  • the glass substrate coated with the silane coupling agent is set on a roll laminator equipped with a silicone rubber roller, and first, 500 ml of pure water is dropped on the surface coated with the silane coupling agent with a dropper so as to spread over the entire substrate.
  • the surface-treated surface of the surface-treated multilayer polyimide film (actual 25) is laminated so as to face the silane coupling agent-coated surface of the glass substrate, that is, the surface wetted with pure water, and from one side of the glass substrate.
  • a temporary laminate was obtained by laminating the glass substrate and the polyimide film under pressure while sequentially extruding pure water between the polyimide film and the glass substrate with a rotating roll.
  • the laminator used was a laminator with an effective roll width of 650 mm manufactured by MCK, and the bonding conditions were air source pressure: 0.5 MPa, laminating speed: 50 mm / sec, roll temperature: 22 ° C, environmental temperature 22 ° C, humidity. It was 55% RH.
  • the obtained temporary laminate was heat-treated in a clean oven at 200 ° C. for 10 minutes to obtain a laminate composed of a multilayer polyimide film and a glass substrate.
  • a tungsten film (thickness 75 nm) was formed on the polyimide film surface of the obtained laminate by the following steps, and a silicon oxide film (thickness 150 nm) was laminated and formed as an insulating film without being exposed to the atmosphere.
  • a silicon oxide nitride film (thickness 100 nm) to be a base insulating film was formed by a plasma CVD method, and an amorphous silicon film (thickness 54 nm) was laminated and formed without being exposed to the atmosphere.
  • a TFT element was manufactured using the obtained amorphous silicon film.
  • the amorphous silicon thin film is patterned to form a silicon region having a predetermined shape, and a gate insulating film is formed, a gate electrode is formed, a source region or a drain region is formed by doping the active region, and an interlayer insulating film is formed.
  • the source electrode and the drain electrode were formed, and the activation treatment was performed to prepare an array of P-channel TFTs.
  • the polyimide film part is burnt off with a UV-YAG laser along the inside of the TFT array about 0.5 mm, and peeled off from the end of the cut by using a thin razor-shaped blade to scoop up the flexible A3 size TFT. Obtained an array.
  • the peeling was possible with a very small force, and it was possible to peel without damaging the TFT.
  • the obtained flexible TFT array did not show any deterioration in performance even when wound around a round bar having a diameter of 5 mm, and maintained good
  • Example 28 to 30 (Comparative Examples 10 to 12) A film was produced and evaluated in the same manner as in Example 1 by combining the polyamic acid solution or polyimide solution shown in Table 1 with the inorganic filler shown in Table 2. The results are shown in Table 9. In the case of a single layer in the comparative example, a die coat was used.
  • Inorganic filler No. 2 shown in Table 2 was added to the polyamic acid solution A obtained in Production Example 1.
  • 2 A dispersion obtained by dispersing colloidal silica in dimethylacetamide (Nissan Chemical Industries, Ltd. "Snowtex (registered trademark) DMAC-ST-ZL") is prepared by silica (lubricant) with respect to the total amount of polymer solids in the polyamic acid solution. The mixture was added so as to be 0.8% by mass and uniformly dispersed.
  • Inorganic filler No. 2 shown in Table 2 was added to the polyimide solution C obtained in Production Example 3.
  • 1 Calcium fluoride particles with an average particle diameter of 0.2 ⁇ m manufactured by Stella Chemifa Co., Ltd.
  • a polyamic acid solution A in which 2 is dispersed is placed on a non-slip material surface of a polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd., hereinafter abbreviated as PET film) as a temporary support so that the final film thickness is 1 ⁇ m.
  • PET film polyethylene terephthalate film
  • the inorganic filler No was applied to make the first layer.
  • the polyimide solution C in which 1 was dispersed was applied on the first layer previously applied by a die coater so that the final film thickness was 23 ⁇ m to form the second layer. Then, it was heated at 110 ° C.
  • the third layer After applying the third layer, it was dried in a continuous drying oven at 110 ° C. for 10 minutes to obtain a self-supporting film having a residual solvent amount of 18% by mass.
  • the self-supporting film is peeled off from the A4100 film that has been used as a support, passed through a pin tenter having a pin sheet on which pins are arranged, and the film end is gripped by inserting the pin into the pin so that the film does not break and is unnecessary.
  • the pin sheet spacing was adjusted so as not to cause sagging, and the film was conveyed, and heated at 200 ° C. for 3 minutes, 250 ° C. for 3 minutes, and 300 ° C. for 6 minutes to proceed the imidization reaction.
  • Example 32 Similarly, a film was produced and evaluated in the same manner as in Example 31 by combining the polyamic acid solution or polyimide solution shown in Table 1 with the inorganic filler shown in Table 2.
  • Inorganic filler No. 2 shown in Table 2 was added to the polyamic acid solution A obtained in Production Example 1.
  • a dispersion obtained by dispersing colloidal silica in dimethylacetamide (“Snowtex (registered trademark) DMAC-ST-ZL” manufactured by Nissan Chemical Industries, Ltd.) is prepared by silica (lubricant) with respect to the total amount of polymer solids in the polyamic acid solution. The mixture was added so as to be 0.5% by mass and uniformly dispersed.
  • Inorganic filler No. 2 shown in Table 2 was added to the polyimide solution C obtained in Production Example 3.
  • the inorganic filler No In the atmosphere air-conditioned to 25 ° C. and 45% RH, the inorganic filler No.
  • the polyamic acid solution A in which 2 was dispersed was applied onto a non-slip material surface of a polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd., hereinafter abbreviated as PET film) as a temporary support so that the final film thickness was 1 ⁇ m. .. Then, it was heated at 110 ° C. for 5 minutes as primary heating by a continuous dryer to form a semi-dry film having a residual solvent amount of 18% by mass, and the temporary support was wound into a roll.
  • This semi-dry film is called GF (green film).
  • the obtained roll was set again in the above-mentioned apparatus, the semi-dried film was unwound together with the temporary support, and the inorganic filler No. 1 was placed on the semi-dried film.
  • the polyimide solution C in which 1 was dispersed was applied with a die coater so that the final film thickness was 23 ⁇ m. 10 seconds after the second layer was applied by the die coater, the same inorganic filler No. as the first layer was applied.
  • the polyamic acid solution A in which 2 was dispersed was applied so that the final film thickness was 1 ⁇ m, and the third layer was formed.
  • this coating method is referred to as "wet / wet / GF method”. After applying the third layer, it was dried at 110 ° C.
  • the self-supporting film is peeled off from the PET film that has been used as a support, passed through a pin tenter having a pin sheet on which pins are arranged, and gripped by inserting the film end into the pin.
  • the film is conveyed by adjusting the pin sheet spacing so that the film does not break and unnecessary slack does not occur, and the final heating is 200 ° C for 3 minutes, 250 ° C for 3 minutes, and 300 ° C for 6 minutes.
  • the film was heated under the above conditions, and the required imidization reaction was allowed to proceed with drying.
  • films (actual 35) and (actual 36) were obtained by setting the conditions shown in Table 10.
  • the results of the same evaluation are shown in Table 10. All of them showed relatively low CTE and high transparency, and there was no particular problem in terms of mechanical strength from the viewpoint of handleability.
  • the characteristic values measured by forming this polyamic acid solution into a film were film thickness 25 ⁇ m, haze 0.42%, total light transmittance 87.6%, yellow index 3.9, and breaking strength 165 MPa.
  • the elongation at break was 8.9%, the elastic modulus was 4.3 GPa, the CTE was 28 ppm / K, and the warp was 0.1 mm or less.
  • the silica sol component was added so as to have a total polymer solid content of 12.5% by mass in the polyamic acid solution) and completely dissolved, and then 9.81 parts by mass of 1,2,3,4-cyclobutanetetracarboxylic acid. 11.34 parts by mass of 3,3', 4,4'-biphenyltetracarboxylic acid, 4.85 parts by mass of 4,4'-oxydiphthalic acid unihydrate (ODPA) After each solid was added separately, the mixture was stirred at room temperature for 24 hours.
  • ODPA 4,4'-oxydiphthalic acid unihydrate
  • the characteristic values measured by forming this polyamic acid solution into a film are film thickness 25 ⁇ m, haze 0.76%, total light transmittance 85.6%, yellow index 3.5, breaking strength 121 MPa.
  • the elongation at break was 5.4%
  • the elastic modulus was 5.3 GPa
  • the CTE was 21 ppm / K
  • the warp was 0.2 mm.
  • Example 37 In the air air-conditioned to 25 ° C. and 45% RH, the polyamic acid solution J obtained in Production Example 9 was subjected to a temporary support using a device equipped with a roll-to-roll type comma coater and a continuous type drying furnace. A PET film was applied onto the non-slip material surface so that the final film thickness was 5 ⁇ m. Then, 10 seconds later, using a die coater, the filler-containing polyamic acid solution K obtained in Production Example 10 was applied onto the film of the polyamic acid solution K so that the final film thickness was 20 ⁇ m, and another 20 seconds later.
  • a polyamic acid solution J was applied with a die coater so that the final film thickness was 5 ⁇ m, and the film was dried at 110 ° C. for 15 minutes in a continuous transport type drying furnace to obtain self-supporting film after drying. It is peeled off from the PET film that has been used as a support, passed through a pin tenter having a pin sheet on which pins are arranged, and gripped by inserting the end of the film into the pins so that the film does not break and unnecessary slack does not occur. The pin sheet spacing was adjusted and conveyed, and the final heating was carried out under the conditions of 200 ° C. for 3 minutes, 250 ° C. for 3 minutes, 300 ° C. for 3 minutes, and 400 ° C.
  • the film was cooled to room temperature in 2 minutes, and the portions of the film having poor flatness were cut off with a slitter and wound into a roll to obtain a roll of a film (actual 37) having a width of 530 mm and a length of 80 m.
  • the obtained film (actual 37) has a total film thickness of 30 ⁇ m, a haze of 0.57%, a total light transmittance of 86.5%, a yellow index of 4.5, a breaking strength of 180 MPa, a breaking elongation of 12.5%, and an elastic modulus.
  • the film characteristics were 4.6 GPa, CTE 22 ppm / K, and warp 0.1 mm, and the film characteristics were improved by the multi-layered structure.
  • the multilayer polyimide film of the present invention has better optical properties and mechanical properties as compared with the case where polyimides having different compositions are individually filmed. Further, according to the production method of the present invention, it is possible to form a transition layer having a specific thickness and a composition gradient between layers having different compositions divided into multiple layers and sharing functions, thereby forming a well-balanced film. Is possible.
  • the multilayer polyimide film of the present invention has excellent optical properties, colorless transparency, excellent mechanical properties, and exhibits a relatively low CTE. Therefore, the film is attached to a rigid inorganic substrate such as glass on a flat surface.
  • a flexible electronic device can be produced by processing various electronic devices on the film after combining them and finally peeling them from the inorganic substrate.

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Abstract

La présente invention concerne un film de polyimide incolore qui présente une résistance de traction à la rupture élevée et un module d'élasticité de traction élevé, tout en ayant un allongement à la rupture élevé et un faible coefficient de dilatation linéaire.　Selon la présente invention, un film multicouche utilise un polyimide, auquel 0,05 à 2,5 % en masse d'une charge inorganique sont ajoutés, pour une couche externe (a), tout en utilisant un polyimide, auquel 1 à 35 % en masse d'une charge inorganique sont ajoutés, pour une couche interne (b). Selon la présente invention, un film de polyimide multicouche est obtenu par : application d'une solution de polyimide ou d'une solution de précurseur de polyimide pour former une couche (a) sur un support temporaire ; séchage de la solution jusqu'à ce que la teneur en solvant atteigne 5 à 40 % en masse ; ensuite, application d'une solution de polyimide ou d'une solution de précurseur de polyimide pour former une couche (b) sur le support temporaire ; répétition de l'application de la même manière, si nécessaire ; et enfin, conduite d'un traitement thermique. Par conséquent, un film blanc est obtenu si une charge inorganique ayant un indice de réfraction élevé est utilisée pour la couche interne, tandis qu'un film transparent incolore est obtenu si une charge inorganique ayant un indice de réfraction qui est proche de l'indice de réfraction d'une résine de polyimide est utilisée.
PCT/JP2021/021330 2020-06-16 2021-06-04 Film de polyimide multicouche incolore, corps multicouche et procédé de fabrication de dispositif électronique flexible WO2021256298A1 (fr)

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CN202180032888.5A CN115515790A (zh) 2020-06-16 2021-06-04 无色多层聚酰亚胺膜、层叠体、柔性电子设备的制造方法
JP2021559597A JPWO2021256298A1 (fr) 2020-06-16 2021-06-04
KR1020227023194A KR20230025652A (ko) 2020-06-16 2021-06-04 무색 다층 폴리이미드 필름, 적층체, 플렉시블 전자 디바이스의 제조 방법

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JPH03114830A (ja) * 1989-09-29 1991-05-16 Toray Ind Inc 積層フィルム
JP2007106839A (ja) * 2005-10-12 2007-04-26 Toyobo Co Ltd ポリイミドフィルムおよびプリント配線基板用ベース基板
JP2010076438A (ja) * 2008-08-27 2010-04-08 Toyobo Co Ltd 易滑性多層ポリイミドフィルム
JP2012519960A (ja) * 2009-03-06 2012-08-30 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 電子回路用途の多層フィルムおよびそれに関連する方法
WO2016117636A1 (fr) * 2015-01-22 2016-07-28 ユニチカ株式会社 Stratifié, son procédé de fabrication, son procédé d'utilisation et solution de précurseur de polyimide pour couche stratifiée de substrat en verre

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JP3425854B2 (ja) 1997-10-02 2003-07-14 日本電信電話株式会社 低屈折率透明ポリイミド共重合体、及びそれらの前駆体溶液、及びそれらの製造方法
JP2002146021A (ja) 2000-11-10 2002-05-22 Ube Ind Ltd 可溶性、透明なポリイミドおよびその製造法
JP2002348374A (ja) 2001-05-25 2002-12-04 Hitachi Cable Ltd ポリアミック酸又はポリイミド及び液晶配向剤
JP2008169237A (ja) 2007-01-09 2008-07-24 Toyobo Co Ltd 白色ポリイミドフィルム
CN101674923B (zh) 2007-05-24 2013-01-09 三菱瓦斯化学株式会社 无色透明树脂薄膜的制备方法及制备装置
JP5383343B2 (ja) 2008-06-26 2014-01-08 新日鉄住金化学株式会社 白色ポリイミドフィルム

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JPH0321447A (ja) * 1989-06-20 1991-01-30 Ube Ind Ltd 記録媒体用ポリイミドフィルム及びその製造法
JPH03114830A (ja) * 1989-09-29 1991-05-16 Toray Ind Inc 積層フィルム
JP2007106839A (ja) * 2005-10-12 2007-04-26 Toyobo Co Ltd ポリイミドフィルムおよびプリント配線基板用ベース基板
JP2010076438A (ja) * 2008-08-27 2010-04-08 Toyobo Co Ltd 易滑性多層ポリイミドフィルム
JP2012519960A (ja) * 2009-03-06 2012-08-30 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 電子回路用途の多層フィルムおよびそれに関連する方法
WO2016117636A1 (fr) * 2015-01-22 2016-07-28 ユニチカ株式会社 Stratifié, son procédé de fabrication, son procédé d'utilisation et solution de précurseur de polyimide pour couche stratifiée de substrat en verre

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