# US 11,898,009 B2 · Polyimide, laminate, and electronic device including same

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- Number: US 11,898,009 B2
- Document ID: US11898009B2
- Status: Granted
- Kind: B2
- Application number: 17/048,431
- Filed: 2019-04-19
- Published: 2021-06-10
- Granted: 2024-02-13
- Earliest claimed: 2018-04-20
- Assignees: Ube Corporation
- Applicants: Ube Industries, Ltd.
- Inventors: Norio Miura; Kazutaka Narita
- Web page: https://patentgrep.com/patent/US11898009B2

## CPC

- C08G 73/1067: {Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound}
- C08G 73/1014: {in the form of (mono)anhydrid}
- C08G 73/1017: {in the form of (mono)amine}
- C08G 73/1039: {comprising halogen-containing substituents}
- C08G 73/1042: {Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds}
- C08G 73/1071: {Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain}
- C08G 73/126: {the unsaturated precursors being wholly aromatic}
- C09D 179/085: {Unsaturated polyimide precursors}
- H05B 33/02: Details
- H10D 86/411: {characterised by materials, geometry or structure of the substrates}
- H10D 86/60: wherein the TFTs are in active matrices
- G02F 1/133305: {Flexible substrates, e.g. plastics, organic film}
- H10D 86/0214: {using temporary substrates}
- H10K 77/111: {Flexible substrates}
- Y02E 10/549: Organic PV cells
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- H05B: ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- G02F: OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A flexible electronic device containing a polyimide film exhibiting excellent C-V characteristics. The polyimide film is a film that shows a maximum gradient of 0.005/V or more in a capacitance-voltage measurement of a laminate in which a polyimide film having a film thickness of 0.75 μm is formed on a silicon wafer having a resistance value of 4 Ωcm; the maximum gradient meaning a maximum value of an absolute value of a gradient in a normalized capacity-voltage curve during a third scan of forward direction scans; a capacity-voltage curve being measured by applying a direct current voltage is to the polyimide film with respect to the silicon wafer between a lowest voltage V1 and a highest voltage V2, and measuring capacitance while the direct current voltage is scanned in a forward direction and scanned in a negative direction; the normalized capacity-voltage curve being normalized so that the capacity at the lowest voltage V1 is 1.

## Claims

### Claim 1

A polyimide film-based flexible electronic device substrate formed from a polyimide that does not comprise a compound including a Si-containing group, wherein the polyimide has a maximum gradient of 0.005/V or more in a capacitance-voltage measurement of a laminate in which a polyimide film having a film thickness of 0.75 μm is formed on a silicon wafer having a resistance value of 4 Ωcm; wherein the maximum gradient is a maximum value of an absolute value of a gradient in a normalized capacity-voltage curve during a third scan of forward direction scans; wherein a capacity-voltage curve is measured by applying a direct current voltage to the polyimide film with respect to the silicon wafer between a lowest voltage V1 and a highest voltage V2, and measuring capacitance while the direct current voltage is scanned in a forward direction from the lowest voltage V1 to the highest voltage V2 and scanned in a negative direction from the highest voltage V2 to the lowest voltage V1; where the lowest voltage V1 is a voltage at which the capacity of only the polyimide film is observed, and the normalized capacity-voltage curve is normalized so that the capacity at the lowest voltage V1 is 1.

### Claim 2 (depends on 1)

The polyimide film-based flexible electronic device substrate according to claim 1, wherein a weight ratio of an imide group (—CONCO—) in a repeating unit of the polyimide is less than 38.3 wt %.

### Claim 3 (depends on 1)

The polyimide film-based flexible electronic device substrate according to claim 1, wherein the concentration of amine end groups calculated from a feed ratio in the entire polyimide is 29 μmol/g or less.

### Claim 4

A polyimide precursor comprising a repeating unit which is obtainable by reacting:
a tetracarboxylic acid component (A) comprising at least 3,3′, 4,4′-biphenyltetracarboxylic dianhydride, and
a diamine component (B) comprising:
(B-1) at least one diamine selected from the group consisting of 1,4-diaminobenzene, [1.1′: 4′,1″-terphenyl]-4,4″-diamine, and 1,4-bis [2-(4-aminophenyl)-2-propyl]benzene, and
(B-2) at least one diamine selected from the group consisting of 9,9-bis (4-aminophenyl) fluorene, 4,4′-(49H-fluorene-9,9-diyl)bis([1,1′-biphenyl]-5,2-diyl))bis(oxy))diamine, and 4,4′-([1,1′-binaphthalene]-2,2′-diylbis(oxy))diamine,
with the proviso that when the diamine component (B) comprises 1,4-diaminobenzene and 9,9-bis(4-aminophenyl)fluorene), the amount of diamine compound(s) other than the diamine of (B-1) and the diamine (B-2) is 20 mol % or less, with the proviso that the repeating unit does not include a Si-containing group.

### Claim 5 (depends on 4)

The polyimide precursor according to claim 4, wherein the diamine component (B) comprises the diamine of (B-1) and the diamine of (B-2) in an amount of 40 mol % or more in total.

### Claim 6 (depends on 4)

The polyimide precursor according to claim 4, wherein a sum of ratios of the repeating units derived from 3,3′, 4,4′-biphenyltetracarboxylic dianhydride and the diamine (B-1) and the repeating units derived from 3,3′, 4,4′-biphenyltetracarboxylic dianhydride and the diamine (B-2) is 40 mol % or more.

### Claim 7 (depends on 4)

A polyimide obtained by imidizing the polyimide precursor according to claim 4.

### Claim 8 (depends on 7)

A polyimide film comprising the polyimide according to claim 7.

### Claim 9 (depends on 1)

A flexible electronic device comprising the polyimide film according to claim 1.

### Claim 10 (depends on 8, 9)

The flexible electronic device according to claim 9, wherein the substrate is formed from the polyimide film according to claim 8.

### Claim 11 (depends on 9)

A method for manufacturing a flexible electronic device according to claim 9, comprising:
applying a polyimide precursor solution or a polyimide precursor solution composition onto a carrier substrate, and performing imidization to form a laminate having a carrier substrate and a polyimide film that becomes the substrate.