WO2024024901A1 - ポリイミド前駆体組成物、ポリイミドフィルムおよびポリイミドフィルム／基材積層体 - Google Patents

ポリイミド前駆体組成物、ポリイミドフィルムおよびポリイミドフィルム／基材積層体 Download PDF

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WO2024024901A1
WO2024024901A1 PCT/JP2023/027627 JP2023027627W WO2024024901A1 WO 2024024901 A1 WO2024024901 A1 WO 2024024901A1 JP 2023027627 W JP2023027627 W JP 2023027627W WO 2024024901 A1 WO2024024901 A1 WO 2024024901A1
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Prior art keywords
polyimide
polyimide precursor
mol
formula
polyimide film
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English (en)
French (fr)
Japanese (ja)
Inventor
卓也 岡
雄基 根本
幸徳 小濱
太一 伊藤
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Ube Corp
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Ube Corp
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Priority to KR1020247026332A priority Critical patent/KR102841382B1/ko
Priority to CN202380014149.2A priority patent/CN118139913B/zh
Priority to JP2024537232A priority patent/JPWO2024024901A1/ja
Priority to KR1020247012185A priority patent/KR102693676B1/ko
Priority to CN202510438782.5A priority patent/CN120059184A/zh
Publication of WO2024024901A1 publication Critical patent/WO2024024901A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • 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
    • 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
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a polyimide precursor composition, a polyimide film, and a polyimide film/substrate laminate that are suitably used for electronic device applications such as flexible device substrates.
  • Polyimide film has been widely used in fields such as electrical and electronic devices and semiconductors because it has excellent heat resistance, chemical resistance, mechanical strength, electrical properties, and dimensional stability.
  • optical materials such as optical fibers and optical waveguides in the field of optical communications, liquid crystal alignment films and protective films for color filters in the field of display devices has progressed.
  • lightweight and flexible plastic substrates are being actively investigated as an alternative to glass substrates, and displays that can be bent or rolled are being actively developed.
  • TFTs thin film transistors
  • the substrate is required to have heat resistance and dimensional stability.
  • Polyimide films are promising as substrates for display applications because they have excellent heat resistance, chemical resistance, mechanical strength, electrical properties, and dimensional stability.
  • Patent Document 1 describes the process of forming a solid polyimide resin film by coating a specific precursor resin composition on a carrier substrate, and forming a circuit on the resin film.
  • a method for manufacturing a flexible device which is a display device or a light receiving device, including the steps of forming a solid resin film on the surface of which the circuit is formed, and peeling off the solid resin film on the surface of which the circuit is formed from the carrier substrate.
  • Patent Document 2 describes a method for manufacturing a flexible device in which elements and circuits necessary for the device are formed on a polyimide film/glass substrate laminate obtained by forming a polyimide film on a glass substrate.
  • a method is disclosed that includes irradiating laser from the glass substrate side to peel off the glass substrate.
  • Polyimide is generally colored yellow-brown, which has limited its use in transmissive devices such as backlit liquid crystal displays, but in recent years polyimide has improved in addition to its mechanical and thermal properties.
  • Polyimide films with excellent light transmittance have been developed and are expected to be used as substrates for display applications.
  • Patent Document 3 describes a semi-alicyclic polyimide that has excellent mechanical properties, heat resistance, etc. in addition to optical transparency.
  • Patent Documents 4 and 5 aromatic polyimides for use in flexible electronic device substrates
  • diamines containing fluorine-containing aromatic diamines such as 2,2'-bis(trifluoromethyl)benzidine (TFMB)
  • TFMB 2,2'-bis(trifluoromethyl)benzidine
  • Patent Documents 6 and 8 disclose examples in which a diamine component containing an aromatic diamine compound containing an ester bond is used.
  • Polyimides containing aromatic diamine compounds containing ester bonds are also known for use in copper-clad laminates (for example, Patent Document 9) and for forming release layers (Patent Document 10).
  • Patent Documents 11 to 15 also disclose examples in which a diamine component containing an aromatic diamine compound containing an ester bond is used.
  • Aromatic polyimides have problems with coloration, but they generally have excellent heat resistance, so if coloration is reduced as much as possible, they may be used as substrates for display applications.
  • Patent Documents 4 and 5 disclose examples of the use of 2,2'-bis(trifluoromethyl)benzidine (TFMB), but as the present inventor continued to study, it was found that TFMB was used as a monomer component.
  • TFMB 2,2'-bis(trifluoromethyl)benzidine
  • the adhesion is weak, it is necessary to increase the laser intensity, which may cause discoloration of the polyimide after processing or a decrease in mechanical properties. Therefore, the adhesion between the polyimide film and the glass substrate, ie, the peel strength, is required to be extremely high.
  • Patent Documents 6 and 7 describe examples of using a diamine component containing 4-aminophenyl-4-aminobenzoate (APAB; abbreviated as 4-BAAB in this application), but these are insufficient in terms of coloring properties of the film. It is.
  • Patent Document 8 requires a diamine compound with a specific structure, and is insufficient in terms of film colorability and film elastic modulus.
  • the polyimide precursor compositions described in Patent Documents 11, 14, and 15 also require a diamine compound with a specific structure, and are not satisfactory in terms of use in flexible display substrates such as haze.
  • polyimide films obtained from polyimide precursor compositions for other uses described in Patent Documents 9, 10, 12, and 13 do not satisfy the performance required for display uses, including adhesion.
  • the present invention utilizes the advantages of aromatic polyimide films such as heat resistance and coefficient of linear thermal expansion, while improving light transmittance and adhesion in polyimide film/substrate laminates for use in flexible electronic devices, particularly flexible displays.
  • An object of the present invention is to provide a polyimide precursor composition for producing a polyimide film for substrate use.
  • a further object of the present invention is to provide a polyimide film and a polyimide film/substrate laminate obtained from this polyimide precursor.
  • inventions related to terms A1 to A14 are referred to as invention A series, and inventions related to terms B1 to B12 are referred to as invention B series.
  • a polyimide precursor whose repeating units are represented by the following general formula (I), and at least one kind of imidazole compound as an optional component, in an amount of less than 1 mole per mole of repeating units of the polyimide precursor, polyimide precursor composition;
  • X 1 is a tetravalent aliphatic group or aromatic group
  • Y 1 is a divalent aliphatic group or aromatic group
  • R 1 and R 2 are independently hydrogen an alkyl group having 1 to 6 carbon atoms or an alkylsilyl group having 3 to 9 carbon atoms, where: X 1 satisfies either (i) or (ii), (i) Contains 50 mol% or more of the structure represented by formula (1-1), and a total of 70 mol of the structure represented by formula (1-1) and the structure represented by formula (1-2) Contains more than % (ii) containing 70 mol% or more of the structure represented by formula (1-1) and
  • At least one imidazole compound may be contained as an essential component in an amount of 0.01 mol or more and less than 1 mol per mol of repeating unit of the polyimide precursor. subject to the following conditions.
  • polyimide precursor composition according to any one of the preceding items, wherein 80 mol% or more of Y1 has a structure represented by formula (B).
  • polyimide precursor according to any one of the preceding items, further comprising at least one imidazole compound in an amount of 0.01 mol or more and less than 1 mol based on 1 mol of repeating units of the polyimide precursor. body composition.
  • the imidazole compound is at least one selected from the group consisting of 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 1-phenylimidazole, imidazole, and benzimidazole.
  • At least one silane compound having a Si-OR a structure (where R a is a hydrogen atom or a hydrocarbon group) is added to a mixture of a tetracarboxylic dianhydride and a diamine compound when producing a polyimide precursor composition.
  • the polyimide precursor composition according to any one of the preceding items, which is contained in an amount of more than 0 parts by mass and 60 parts by mass or less based on a total of 100 parts by mass.
  • the silane compound has the following formula: (R a O) n Si(R b ) 4-n (In the formula, n is an integer of 1 to 4, R a is a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, and R b is an alkyl group or aryl group having 10 or less carbon atoms)
  • a polyimide film obtained from the polyimide precursor composition according to any one of the preceding items A polyimide film/base material laminate comprising a base material.
  • A12 (a) applying the polyimide precursor composition according to any one of the preceding items onto a substrate; and (b) heat-treating the polyimide precursor on the substrate;
  • step (b) The method for producing a laminate according to item A12 above, further comprising the step of forming an inorganic thin film layer on the polyimide film of the laminate.
  • A14 (d) forming at least one layer selected from a conductor layer and a semiconductor layer on the inorganic thin film layer of the laminate produced in the above item A13; and (e) forming the base material and the polyimide film.
  • a method for manufacturing a flexible electronic device including a step of peeling.
  • A15 A flexible electronic device comprising the polyimide film according to item A8 above.
  • A16 A flexible electronic device substrate comprising the polyimide film according to item A8 above.
  • a polyimide precursor whose repeating unit is represented by the following general formula (I), and containing at least one imidazole compound in an amount of 0.01 mol or more and less than 1 mol per mol of the repeating unit of the polyimide precursor.
  • a polyimide precursor composition A polyimide precursor composition.
  • X 1 is a tetravalent aliphatic group or aromatic group
  • Y 1 is a divalent aliphatic group or aromatic group
  • R 1 and R 2 are independently hydrogen an alkyl group having 1 to 6 carbon atoms or an alkylsilyl group having 3 to 9 carbon atoms, where: X 1 contains 70 mol% or more of the structure represented by formula (1-1) and/or the structure represented by formula (1-2), Y 1 contains 50 mol% or more of the structure represented by formula (B).
  • X 1 contains a total of 60 mol% or more of a structure represented by formula (1-1) and a structure represented by formula (1-2). body composition.
  • the imidazole compound is at least one selected from the group consisting of 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 1-phenylimidazole, imidazole, and benzimidazole.
  • the polyimide precursor composition according to any one of the above items.
  • a polyimide film obtained from the polyimide precursor composition according to any one of the preceding items A polyimide film/base material laminate comprising a base material.
  • step (b) The method for producing a laminate according to item B10 above, further comprising the step of forming an inorganic thin film layer on the polyimide film of the laminate.
  • a method for manufacturing a flexible electronic device including a step of peeling.
  • a polyimide precursor composition can be provided. That is, the polyimide precursor composition of the present invention is optimal for producing a polyimide film used as a flexible display substrate. Furthermore, the present invention can provide a polyimide film and a polyimide film/substrate laminate obtained from this polyimide precursor.
  • a polyimide precursor composition with more stable viscosity can be provided.
  • a polyimide film and a polyimide film/substrate laminate obtained using the polyimide precursor composition Furthermore, according to another aspect of the present invention, it is possible to provide a method for manufacturing a flexible electronic device using the polyimide precursor composition, and a flexible electronic device.
  • the term “flexible (electronic) device” means that the device itself is flexible, and the device is usually completed by forming a semiconductor layer (elements such as transistors and diodes) on a substrate.
  • a “flexible (electronic) device” is distinguished from a device such as a COF (chip on film) in which a "hard” semiconductor element such as an IC chip is mounted on a conventional FPC (flexible printed wiring board).
  • “hard” semiconductor elements such as IC chips may be mounted on a flexible substrate or electrically connected and used in combination. There is no problem in doing so.
  • Flexible (electronic) devices that are preferably used include flexible displays such as liquid crystal displays and organic EL displays, display devices such as electronic paper, solar cells, and light receiving devices such as CMOS. More specifically, the term “flexible (electronic) device board” does not include flexible wiring boards (also referred to as flexible substrates, flexible printed wiring boards, etc.).
  • the polyimide film itself is the main component of the substrate (or the substrate itself) present in the final product. refers to films and layers that are not present in the final product, and does not refer to additional layers laminated to the substrate.
  • the release layer is not the substrate.
  • polyimide precursor compositions that directly produce polyimide films for the above substrates, and specifically By applying the polyimide precursor composition onto a base material and imidizing it, a polyimide film for "flexible (electronic) device substrates (including flexible display substrates; the same shall apply hereinafter)" is obtained. Therefore, for example, when two or more polyimide precursor compositions (intermediate compositions) are mixed and used for producing a polyimide film, the individual polyimide precursor compositions are It is not for the board.
  • the structure of the resulting polyimide film depends on the structure of the polyimide precursor composition from which the polyimide film is directly produced.
  • copper (or metal) clad laminates are used to manufacture flexible wiring boards (flexible circuit boards, flexible printed wiring boards), but since they are not used to manufacture flexible (electronic) devices, copper clad laminates
  • the polyimide precursor composition for manufacturing is not a "flexible (electronic) device substrate" polyimide precursor composition. Note that the definitions of the above terms may be explained in more detail in this specification.
  • the polyimide precursor composition of the present invention will be explained, and then the method for manufacturing a flexible electronic device will be explained.
  • the invention A series will be mainly explained, and the invention B series containing an imidazole compound as an essential component will be explained in the section of the imidazole compound.
  • the description of the A series of inventions also applies to the inventions of the B series.
  • a polyimide precursor composition for forming a polyimide film contains a polyimide precursor.
  • the polyimide precursor composition further contains a solvent, and the polyimide precursor is dissolved in the solvent.
  • the polyimide precursor has the following general formula (I):
  • X 1 is a tetravalent aliphatic group or aromatic group
  • Y 1 is a divalent aliphatic group or aromatic group
  • R 1 and R 2 are independently hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.
  • R 1 and R 2 are independently hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.
  • R 1 and R 2 are independently hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.
  • R 1 and R 2 are independently hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.
  • R 1 and R 2 are independently hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having
  • X 1 contains 50 mol% or more of the structure represented by formula (1-1), and the structure represented by formula (1-1) and formula (1-2) Contains a total of 70 mol% or more of the structure represented by.
  • formula (1-1) and formula (1-2) are oxydiphthalic dianhydride (abbreviated as ODPA) and 3,3',4,4'-biphenyltetracarboxylic dianhydride (abbreviated as s- The structure is derived from BPDA).
  • Y 1 is a structure represented by formula (B), that is, a structure derived from 4-aminophenyl-4-aminobenzoate (abbreviated as 4-BAAB).
  • polyimide film that has high light transmittance and high elastic modulus, as well as improved adhesion in a polyimide film/substrate laminate.
  • the obtained polyimide film also has excellent properties such as heat resistance and low coefficient of linear thermal expansion, which are advantages of wholly aromatic polyimide films.
  • the polyimide precursor will be explained using monomers (tetracarboxylic acid component, diamine component, and other components) that provide X 1 and Y 1 in general formula (I), and then the manufacturing method will be explained.
  • the tetracarboxylic acid component refers to tetracarboxylic acid, tetracarboxylic dianhydride, other tetracarboxylic acid silyl esters, tetracarboxylic acid esters, tetracarboxylic acid chlorides, etc. used as raw materials for producing polyimide.
  • tetracarboxylic dianhydride it is convenient to use tetracarboxylic dianhydride for production purposes, and in the following description, an example will be described in which tetracarboxylic dianhydride is used as the tetracarboxylic acid component.
  • the diamine component is a diamine compound having two amino groups (-NH 2 ), which is used as a raw material for producing polyimide.
  • the polyimide film refers to both a film formed on a (carrier) base material and present in a laminate, and a film after the base material is peeled off.
  • a material constituting a polyimide film that is, a material obtained by heat-treating (imidizing) a polyimide precursor composition is sometimes referred to as a "polyimide material.”
  • X 1 and tetracarboxylic acid component > As mentioned above, (i) or (ii) is satisfied.
  • (i) Of all the repeating units of the polyimide precursor preferably 50 mol% or more of X 1 has a structure (derived from ODPA) represented by the following formula (1-1), preferably formula (1-1) The total amount of the structure represented by (derived from ODPA) and the structure represented by formula (1-2) (derived from s-BPDA) is 70 mol% or more of X 1 .
  • X 1 may consist only of the structure of formula (1-1) and the structure of formula (1-2) (that is, the structure of formula (1-1) The total of the structure and formula (1-2) is 100 mol%).
  • X 1 has the structure of formula (1-1), which is advantageous when high light transmittance is desired. Even more preferably, 70 mol% or more of X 1 has the structure of formula (1-1), even more preferably 80 mol% or more, and even more preferably 90 mol% or more of X 1 has the structure of formula (1-1). ) structure.
  • the total proportion of the structures of formula (1-1) and formula (1-2) is more preferably 75 mol% or more, more preferably 80 mol% or more, and 90 mol% or more, and further It is also preferable that it is 100 mol%. Therefore, the proportion of the structure of formula (1-2) is 50 mol% or less, and may be 0%.
  • the coefficient of linear thermal expansion and mechanical properties can be improved. For example, by containing the structure of 10 mol% to 40 mol%, these properties can be improved. and light transmittance can be improved in a well-balanced manner.
  • X 1 a tetravalent aliphatic group or aromatic group other than the structures represented by formula (1-1) and formula (1-2) (abbreviated as “other X 1 ”) is used.
  • the aliphatic group is preferably a tetravalent group having an alicyclic structure. Therefore, the tetracarboxylic acid component contains "other tetracarboxylic acid derivatives" other than ODPA and s-BPDA at 30 mol% or less, more preferably at 20 mol% or less, based on 100 mol% of the tetracarboxylic acid component. More preferably, it may be contained in an amount of 10 mol% or less. It is also a preferred embodiment that the amount of "other tetracarboxylic acid derivatives" is 0 mol%.
  • “other X 1 ” may be more than 0 mol%, e.g. It is also preferable to contain it in a proportion of 10 mol% or more and 30 mol% or less, for example, 20 mol% or less.
  • particularly preferable other A tetravalent group derived from dianhydride and a tetravalent group derived from 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA) are preferred.
  • a-BPDA 2,3,3',4'-biphenyltetracarboxylic dianhydride
  • “Other X 1 ” is preferably a tetravalent group having an aromatic ring, and preferably a tetravalent group having an aromatic ring having 6 to 40 carbon atoms.
  • Examples of the tetravalent group having an aromatic ring include the following. However, groups corresponding to formulas (1-1) and (1-2) are excluded.
  • Z 1 is a direct bond or the following divalent group:
  • Z 2 in the formula is a divalent organic group
  • Z 3 and Z 4 are each independently an amide bond, an ester bond, and a carbonyl bond
  • Z 5 is an organic group containing an aromatic ring.
  • Z 2 include aliphatic hydrocarbon groups having 2 to 24 carbon atoms and aromatic hydrocarbon groups having 6 to 24 carbon atoms.
  • Z 5 include aromatic hydrocarbon groups having 6 to 24 carbon atoms.
  • the tetravalent group having an aromatic ring the following are particularly preferable because they can achieve both high heat resistance and high light transmittance of the resulting polyimide film.
  • Z 1 is a direct bond or a hexafluoroisopropylidene bond.
  • Z1 be a direct bond, since the resulting polyimide film can achieve both high heat resistance, high light transmittance, and a low coefficient of linear thermal expansion.
  • Z 1 is the following formula (3A):
  • Z 11 and Z 12 are each independently, preferably the same, a single bond or a divalent organic group.
  • Z 11 and Z 12 are preferably organic groups containing an aromatic ring, for example, formula (3A1):
  • Z 13 and Z 14 are each independently a single bond, -COO-, -OCO- or -O-, where Z 14 is bonded to a fluorenyl group, Z 13 is -COO-, -OCO- or -O- with a structure in which Z 14 is a single bond;
  • R 91 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, preferably methyl, and n is an integer of 0 to 4, preferably 1.
  • a structure represented by is preferable.
  • tetracarboxylic acid component that provides the repeating unit of general formula (I) in which X 1 is a tetravalent group having an aromatic ring
  • X 1 is a tetravalent group having an aromatic ring
  • pyromellitic acid 2,3,3',4'-biphenyltetracarboxylic acid, etc.
  • Examples include derivatives such as anhydrides, tetracarboxylic acid silyl esters, tetracarboxylic acid esters, and tetracarboxylic acid chlorides.
  • Examples of the tetracarboxylic acid component providing the repeating unit of general formula (I) in which X 1 is a tetravalent group having an aromatic ring containing a fluorine atom include 2,2-bis(3,4-dicarboxylic acid). (phenyl)hexafluoropropane, and its derivatives such as tetracarboxylic dianhydride, tetracarboxylic acid silyl ester, tetracarboxylic acid ester, and tetracarboxylic acid chloride.
  • the tetracarboxylic acid component may be used alone or in combination.
  • Examples of the tetracarboxylic acid component providing the repeating unit of formula (I) in which X 1 is a tetravalent group having an alicyclic structure include 1,2,3,4-cyclobutanetetracarboxylic acid, isopropylidene diphenoxybis Phthalic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, [1,1'-bi(cyclohexane)]-3,3',4,4'-tetracarboxylic acid, [1,1'-bi(cyclohexane)]-3,3',4,4'-tetracarboxylic acid, (cyclohexane)]-2,3,3',4'-tetracarboxylic acid, [1,1'-bi(cyclohexane)]-2,2',3,3'-tetracarboxylic acid, 4,4'- Methylenebis(cyclohexane-1,2-dicarboxylic acid), 4,
  • Y1 has the structure of formula (B), and further, in order, 80 mol% or more and 90 mol% or more have the structure of formula (B). More preferably, the structure is 100 mol%.
  • Y 1 a divalent aliphatic group or aromatic group other than the structure represented by formula (B) (abbreviated as “other Y 1 ”) may be used within the range that does not impair the effects of the present invention. It can be contained in any amount. That is, in addition to 4-aminophenyl-4-aminobenzoate (4-BAAB), the diamine component contains "other diamine compounds" in an amount of 30 mol% or less, more preferably 20 mol%, based on 100 mol% of the diamine component. % or less, even more preferably in an amount of 10 mol % or less. In one preferred embodiment, the amount of "other diamine compounds" is 0 mol%.
  • “other Y 1 " may be more than 0 mol%, for example 10 mol%. % or more and 20 mol % or less, for example, 15 mol % or less.
  • particularly preferable “other Y 1 " is 4,4-oxydianiline (4,4-ODA), 4,4'-bis(4-aminophenoxy)biphenyl (BAPB), etc.
  • a diamine compound having an ether bond is preferred. Note that “other Y 1 " is not limited to this case, and will be explained below.
  • Y 1 is a divalent group having an aromatic ring, it is preferably a divalent group having an aromatic ring having 6 to 40 carbon atoms, more preferably 6 to 20 carbon atoms.
  • Examples of the divalent group having an aromatic ring include the following.
  • W 1 is a direct bond or a divalent organic group
  • n 11 to n 13 each independently represents an integer of 0 to 4
  • R 51 , R 52 , and R 53 each independently is an alkyl group having 1 to 6 carbon atoms, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group.
  • W 1 examples include a direct bond, a divalent group represented by the following formula (5), and a divalent group represented by the following formula (6). However, groups corresponding to formula (B) are excluded.
  • R 61 to R 68 in formula (6) each independently represent either a direct bond or a divalent group represented by formula (5) above.
  • W 1 is a direct bond or a formula: -NHCO-, -CONH-, -COO-, -OCO-, since the resulting polyimide can achieve both high heat resistance, high light transmittance, and low coefficient of linear thermal expansion. Particularly preferred is one selected from the group consisting of the groups represented by the following. Further, W 1 is one type selected from the group consisting of a direct bond or a group represented by the formula: -NHCO-, -CONH-, -COO- , -OCO-; Particularly preferred is any of the divalent groups represented by formula (6).
  • W 1 is the following formula (3B):
  • Z 11 and Z 12 are each independently, preferably the same, a single bond or a divalent organic group.
  • Z 11 and Z 12 are preferably organic groups containing an aromatic ring, for example, formula (3B1):
  • Z 13 and Z 14 are each independently a single bond, -COO-, -OCO- or -O-, where Z 14 is bonded to a fluorenyl group, Z 13 is -COO-, -OCO- or a structure in which Z 14 is a single bond in -O-;
  • R 91 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, preferably phenyl, and n is an integer of 0 to 4, preferably 1.
  • a structure represented by is preferable.
  • Another preferable group includes a compound in which W 1 is a phenylene group in the above formula (4), that is, a terphenyldiamine compound, and a compound in which all of the groups are para bonds is particularly preferable.
  • Another preferred group includes a compound in which, in the above formula (4), W 1 is the first phenyl ring of formula (6), and R 61 and R 62 are 2,2-propylidene groups.
  • W 1 is the following formula (3B2):
  • Examples include compounds represented by:
  • Examples of the diamine component that provides Y 1 which is a divalent group having an aromatic ring, include p-phenylenediamine, m-phenylenediamine, benzidine, 3,3'-diamino-biphenyl, 3,3'-bis( trifluoromethyl)benzidine, m-tolidine, 3,4'-diaminobenzanilide, N,N'-bis(4-aminophenyl)terephthalamide, N,N'-p-phenylenebis(p-aminobenzamide), 4-aminophenoxy-4-diaminobenzoate, bis(4-aminophenyl) terephthalate, biphenyl-4,4'-dicarboxylic acid bis(4-aminophenyl) ester, p-phenylene bis(p-aminobenzoate), bis( 4-aminophenyl)-[1,1'-biphenyl]-4,4'-dicarboxy
  • Examples of the diamine component providing the repeating unit of general formula (I) in which Y 1 is a divalent group having an aromatic ring containing a fluorine atom include 2,2'-bis(trifluoromethyl)benzidine, 3 , 3'-bis(trifluoromethyl)benzidine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2 '-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.
  • preferred diamine compounds include 9,9-bis(4-aminophenyl)fluorene, 4,4'-(((9H-fluorene-9,9-diyl)bis([1,1'-biphenyl]-5 ,2-diyl))bis(oxy))diamine, [1,1':4',1"-terphenyl]-4,4"-diamine, 4,4'-([1,1'-binaphthalene] -2,2'-diylbis(oxy))diamine is mentioned.
  • the diamine component may be used alone or in combination.
  • Y 1 is a divalent group having an alicyclic structure, it is preferably a divalent group having an alicyclic structure having 4 to 40 carbon atoms, at least one aliphatic 4 to 12-membered ring, More preferably, it has an aliphatic 6-membered ring.
  • divalent group having an alicyclic structure examples include the following.
  • V 1 and V 2 are each independently a direct bond or a divalent organic group
  • n 21 to n 26 each independently represent an integer of 0 to 4
  • R 81 to R 86 are each independently an alkyl group having 1 to 6 carbon atoms, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group
  • V 1 and V 2 include a direct bond and a divalent group represented by the above formula (5).
  • Examples of the diamine component that provides Y 1 which is a divalent group having an alicyclic structure, include 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, and 1,4-diamino-2- Ethylcyclohexane, 1,4-diamino-2-n-propylcyclohexane, 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1,4-diamino-2-isobutylcyclohexane , 1,4-diamino-2-sec-butylcyclohexane, 1,4-diamino-2-tert-butylcyclohexane, 1,2-diaminocyclohexane, 1,3-diaminocyclobutane, 1,4-bis(amino a
  • any of aliphatic tetracarboxylic acids (especially dianhydrides) other than alicyclic type and/or aliphatic diamines are used.
  • the content thereof is preferably less than 30 mol%, more preferably less than 20 mol%, even more preferably less than 10 mol% ( (including 0%) is preferable.
  • Y 1 the structure represented by formula (3B)
  • specific compounds include diamine compounds such as 9,9-bis(4-aminophenyl)fluorene, which can improve Tg and It may be possible to reduce the phase difference (retardation) in the film thickness direction.
  • the polyimide precursor composition for producing a polyimide film does not contain a specific tetracarboxylic acid compound and/or a specific diamine compound, or a specific compound.
  • a specific tetracarboxylic acid compound and/or a specific diamine compound, or a specific compound There are cases.
  • a surfactant and an alkoxysilane compound may be added, but it is also preferable that no surfactant is contained, and it is also preferable that the alkoxysilane compound does not contain any compounds other than the compounds that are preferred in the present invention.
  • it does not contain any of a diamine compound having a —SO 2 — group, a diamine compound having a fluorene structure, and a fluorine-containing diamine compound.
  • a diamine compound containing a benzamide structure, such as 3,5-diaminobenzamide, is preferably not contained in the diamine component in an amount of 5 mol % or more, and more preferably not contained at all.
  • the diamine component contains neither 2,2'-bistrifluoromethylbenzidine nor 1,4-diaminocyclohexane.
  • the diamine component does not contain a diamine monomer containing a nitrogen heterocyclic structure in an amount of 3 to 8 mol %, and it is also preferable that it does not contain it at all.
  • the polyimide precursor can be produced from the above tetracarboxylic acid component and diamine component.
  • the polyimide precursor (polyimide precursor containing at least one type of repeating unit represented by the above formula (I)) used in the present invention has the following chemical structure, depending on the chemical structure taken by R 1 and R 2 : 1) polyamic acid (R 1 and R 2 are hydrogen), 2) polyamic acid ester (at least a portion of R 1 and R 2 is an alkyl group), 3) 4) Polyamic acid silyl ester (at least a portion of R 1 and R 2 is an alkylsilyl group), It can be classified into The polyimide precursor can be easily manufactured by the following manufacturing method for each category. However, the method for producing the polyimide precursor used in the present invention is not limited to the following production method.
  • the polyimide precursor contains approximately equal moles of tetracarboxylic dianhydride as a tetracarboxylic acid component and a diamine component in a solvent, preferably at a molar ratio of the diamine component to the tetracarboxylic acid component [mole of the diamine component]. number/number of moles of tetracarboxylic acid component] is preferably 0.90 to 1.10, more preferably 0.95 to 1.05, and imidization is suppressed at a relatively low temperature of, for example, 120 ° C. or less.
  • a polyimide precursor solution can be suitably obtained by reacting the polyimide precursor solution.
  • diamine is dissolved in an organic solvent or water, and tetracarboxylic dianhydride is gradually added to this solution while stirring, and the temperature is 0 to 120°C, preferably 5°C.
  • a polyimide precursor can be obtained by stirring at a temperature of ⁇ 80°C for 1 to 72 hours.
  • the reaction is carried out at 80° C. or higher, the molecular weight varies depending on the temperature history during polymerization, and imidization progresses due to heat, so there is a possibility that the polyimide precursor cannot be stably produced.
  • the order of addition of diamine and tetracarboxylic dianhydride in the above production method is preferable because the molecular weight of the polyimide precursor tends to increase.
  • the amount of imidazole such as 1,2-dimethylimidazole or a base such as triethylamine is preferably 0.8 times equivalent to the carboxyl group of the polyamic acid (polyimide precursor) to be produced. It is preferable to add the above amount.
  • a polyimide precursor is obtained by stirring this diesterdicarboxylic acid chloride and diamine at a temperature of -20 to 120°C, preferably -5 to 80°C for 1 to 72 hours.
  • the reaction is carried out at 80° C. or higher, the molecular weight varies depending on the temperature history during polymerization, and imidization progresses due to heat, so there is a possibility that the polyimide precursor cannot be stably produced.
  • a polyimide precursor can be easily obtained by dehydrating and condensing a diester dicarboxylic acid and a diamine using a phosphorus condensing agent, a carbodiimide condensing agent, or the like.
  • the polyimide precursor obtained by this method is stable, it can also be purified by reprecipitation by adding a solvent such as water or alcohol.
  • a polyimide precursor is obtained by mixing the polyamic acid solution obtained by method 1) with a silylating agent and stirring at a temperature of 0 to 120°C, preferably 5 to 80°C for 1 to 72 hours.
  • a silylating agent preferably 5 to 80°C for 1 to 72 hours.
  • the reaction is carried out at 80° C. or higher, the molecular weight varies depending on the temperature history during polymerization, and imidization progresses due to heat, so there is a possibility that the polyimide precursor cannot be stably produced.
  • silylating agent that does not contain chlorine as the silylating agent used in the methods 3) and 4) eliminates the need to purify the silylated polyamic acid or the obtained polyimide.
  • the silylating agent that does not contain a chlorine atom include N,O-bis(trimethylsilyl)trifluoroacetamide, N,O-bis(trimethylsilyl)acetamide, and hexamethyldisilazane. N,O-bis(trimethylsilyl)acetamide and hexamethyldisilazane are particularly preferred because they do not contain fluorine atoms and are low cost.
  • an amine catalyst such as pyridine, piperidine, or triethylamine can be used to promote the reaction.
  • This catalyst can be used as it is as a polymerization catalyst for polyimide precursors.
  • Solvents used in preparing the polyimide precursor include water, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3 -Aprotic solvents such as dimethyl-2-imidazolidinone and dimethyl sulfoxide are preferred; any type of solvent can be used without any problem as long as it dissolves the raw material monomer component and the polyimide precursor to be produced; It is not limited to that structure.
  • an amide solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone.
  • cyclic ester solvents such as ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -methyl- ⁇ -butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, m-cresol, p-cresol, 3 Phenolic solvents such as -chlorophenol and 4-chlorophenol, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, and dimethyl sulfoxide are preferably employed.
  • the reaction is carried out by charging monomers and a solvent at a concentration such that the solid content concentration (polyimide equivalent mass concentration) of the polyimide precursor is, for example, 5 to 45% by mass, although it is not particularly limited.
  • the logarithmic viscosity of the polyimide precursor is not particularly limited, but the logarithmic viscosity in an N-methyl-2-pyrrolidone solution with a concentration of 0.5 g/dL at 30°C is 0.2 dL/g or more, more preferably 0.3 dL/ It is preferably at least 0.4 dL/g, particularly preferably at least 0.4 dL/g.
  • the logarithmic viscosity is 0.2 dL/g or more, the molecular weight of the polyimide precursor is high, and the resulting polyimide has excellent mechanical strength and heat resistance.
  • the polyimide precursor composition can contain at least one imidazole compound.
  • the imidazole compound is not particularly limited as long as it has an imidazole skeleton, such as 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 1-phenylimidazole, imidazole, and benzimidazole. can be mentioned.
  • a plurality of imidazole compounds may be used in combination.
  • the imidazole compound is preferably selected from imidazole compounds other than 1,2-dimethylimidazole, preferably dimethyl-substituted imidazole compounds other than 1,2-substituted, monomethyl-substituted imidazole compounds, aromatic-substituted imidazole compounds, Particularly preferred are 2-phenylimidazole, 1-phenylimidazole, imidazole and benzimidazole.
  • the content of the imidazole compound in the polyimide precursor composition can be appropriately selected in consideration of the balance between the effect of addition and the stability of the polyimide precursor composition.
  • the amount (total content) is more than 0 mol per 1 mol of repeating units of the polyimide precursor, and is 0.01 mol or more to exhibit a certain addition effect,
  • the amount is preferably 0.02 mol or more, and on the other hand, from the viewpoint of viscosity stability of the polyimide precursor composition, it is preferably less than 1 mol, more preferably less than 0.8 mol.
  • Addition of an imidazole compound is effective in improving light transmittance and adhesion under long-term high temperature environments such as annealing treatment.
  • the proportion of the structure of formula (1-1) (derived from ODPA) in X 1 is less than 90 mol%, especially less than 80 mol%, it is preferable to add an imidazole compound.
  • Imidazole compounds can be used when the proportion of the structure of formula (1-1) (derived from ODPA) in X 1 is small, or when the structure of formula (1-1) (derived from ODPA) and the structure of formula (1-2) (s - BPDA origin) can solve the problem when the total proportion is small.
  • the proportion of the structure of formula (1-1) (derived from ODPA) in X 1 can be 0 mol % or more. In other words, as long as the total proportion of the structure of formula (1-1) and the structure of formula (1-2) in X 1 is 70 mol% or more, only one of the structures may be included; The proportion of structure 1) may be zero.
  • this application is 1. of invention A series. As defined in the above, an embodiment in which the imidazole compound is not essential (in the case of condition (i)) and an embodiment in which the imidazole compound is essential (in the case of condition (ii)) are disclosed.
  • elements and matters other than those specified above comply with the description of the invention A series in the main text of the present application.
  • Silane compound a silane compound having a Si-OR a structure (R a is a hydrogen atom or a hydrocarbon group) as an additive to the polyimide precursor composition. Addition of a silane compound is effective in improving light transmittance.
  • R a is preferably a hydrocarbon group having 10 or less carbon atoms, preferably an alkyl group or an aryl group, particularly a straight chain or branched alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. , especially methyl group or ethyl group.
  • R a O n Si(R b ) 4-n (n is an integer from 1 to 4)
  • R a is as described above, and n is preferably 1 to 3, more preferably 2 or 3.
  • R b is a hydrocarbon group having 10 or less carbon atoms, preferably an alkyl group or an aryl group, more preferably an aryl group, and particularly preferably a phenyl group.
  • the amount of the silane compound added can be appropriately selected in consideration of the effect of the addition.
  • the amount (total content) is more than 0 parts by mass based on the total of 100 parts by mass of the tetracarboxylic acid component and the diamine component, and 0.05 parts by mass is required to exhibit a certain degree of addition effect.
  • the amount is at least 0.1 part by mass, preferably at least 0.3 part by mass, even more preferably at least 0.5 part by mass, and even more preferably at least 1 part by mass.
  • the polyimide precursor composition used in the present invention includes at least one polyimide precursor described above and preferably a solvent. Furthermore, as mentioned above, it is also preferable to contain at least one kind of imidazole compound.
  • the solvent those described above as solvents used when preparing the polyimide precursor can be used.
  • the solvent used when preparing the polyimide precursor can be used as it is, that is, as the polyimide precursor solution, but it may be diluted or concentrated if necessary.
  • the imidazole compound (if added) is present dissolved in the polyimide precursor composition.
  • the concentration of the polyimide precursor is not particularly limited, but is usually 5 to 45% by mass in polyimide equivalent mass concentration (solid content concentration).
  • the polyimide equivalent mass is the mass when all of the repeating units are completely imidized.
  • the viscosity (rotational viscosity) of the polyimide precursor composition of the present invention is not particularly limited; ⁇ sec is preferable, and 0.1 to 100 Pa ⁇ sec is more preferable. Additionally, thixotropy can be imparted if necessary. When the viscosity is in the above range, it is easy to handle when coating or forming a film, and since repelling is suppressed and the leveling property is excellent, a good film can be obtained.
  • the polyimide precursor composition of the present invention may contain chemical imidizing agents (acid anhydrides such as acetic anhydride, amine compounds such as pyridine and isoquinoline), antioxidants, ultraviolet absorbers, fillers (silica, etc.), as necessary. (inorganic particles, etc.), dyes, pigments, coupling agents such as silane coupling agents, primers, flame retardants, antifoaming agents, leveling agents, rheology control agents (flow aids), etc.
  • chemical imidizing agents as acid anhydrides such as acetic anhydride, amine compounds such as pyridine and isoquinoline
  • antioxidants ultraviolet absorbers
  • fillers silicon, etc.
  • fillers silicon, etc.
  • dyes, pigments, coupling agents such as silane coupling agents, primers, flame retardants, antifoaming agents, leveling agents, rheology control agents (flow aids), etc.
  • thermal imidization is suitable, and in that case, it is prefer
  • the polyimide precursor composition can be prepared by adding and mixing an imidazole compound or a solution of an imidazole compound to the polyimide precursor solution obtained by the method described above.
  • the tetracarboxylic acid component and the diamine component may be reacted in the presence of an imidazole compound.
  • the polyimide precursor composition of the present invention can be used as "a flexible electronic device substrate (particularly preferably a flexible display substrate; the same applies hereinafter)".
  • the polyimide precursor composition "for flexible electronic device substrates” refers to one that is directly applied onto a substrate, as explained below.
  • a polyimide film/substrate laminate can be manufactured using the polyimide precursor composition of the present invention (ie, polyimide precursor composition for flexible electronic device substrates).
  • the polyimide film/substrate laminate includes (a) applying a polyimide precursor composition onto a substrate, (b) heat-treating the polyimide precursor on the substrate, and applying polyimide onto the substrate. It can be manufactured by a process of manufacturing a laminate (polyimide film/base material laminate) in which films are laminated.
  • the method for producing a flexible electronic device of the present invention uses the polyimide film/substrate laminate produced in the steps (a) and (b) (preferably further step (b2)), and further steps ( c) forming at least one layer selected from a conductor layer and a semiconductor layer on the polyimide film of the laminate; and (d) peeling off the base material and the polyimide film.
  • step (a) a polyimide precursor composition is cast onto a base material, imidized and solvent removed by heat treatment to form a polyimide film, and a laminate of the base material and polyimide film (polyimide A film/substrate laminate) is obtained.
  • heat-resistant materials are used, such as ceramic materials (glass, alumina, etc.), metal materials (iron, stainless steel, copper, aluminum, etc.), semiconductor materials (silicon, compound semiconductors, etc.), etc.
  • a sheet-like base material or a film or sheet-like base material such as a heat-resistant plastic material (polyimide, etc.) is used.
  • glass substrates such as soda lime glass, borosilicate glass, alkali-free glass, and sapphire glass
  • semiconductor (including compound semiconductor) substrates such as silicon, GaAs, InP, and GaN
  • Metal substrates such as iron, stainless steel, copper, and aluminum are used.
  • a glass substrate is particularly preferred as the base material. Glass substrates that are flat, smooth, and have a large area have been developed and are easily available.
  • the thickness of the plate-like substrate such as a glass substrate is not limited, but from the viewpoint of ease of handling, it is, for example, 20 ⁇ m to 4 mm, preferably 100 ⁇ m to 2 mm.
  • the size of the plate-shaped base material is not particularly limited, but one side (the long side in the case of a rectangle) is, for example, about 100 mm to about 4000 mm, preferably about 200 mm to about 3000 mm, more preferably about 300 mm to 2500 mm. It is.
  • These base materials such as glass substrates may have an inorganic thin film (for example, a silicon oxide film) or a resin thin film formed on the surface.
  • an inorganic thin film for example, a silicon oxide film
  • a resin thin film formed on the surface.
  • the method for casting the polyimide precursor composition onto the base material is not particularly limited, but includes, for example, slit coating, die coating, blade coating, spray coating, inkjet coating, nozzle coating, spin coating, and screen printing. Conventionally known methods such as a method, a bar coater method, and an electrodeposition method can be used.
  • step (b) the polyimide precursor composition is heat-treated on the substrate to convert it into a polyimide film, and a polyimide film/substrate laminate is obtained.
  • the heat treatment conditions are not particularly limited, but for example, after drying at a temperature range of 50°C to 150°C, the maximum heating temperature is, for example, 150°C to 600°C, preferably 200°C to 550°C, more preferably 250°C.
  • the treatment is carried out at a temperature of ⁇ 500°C.
  • the thickness of the polyimide film is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and still more preferably 5 ⁇ m or more. When the thickness is less than 1 ⁇ m, the polyimide film cannot maintain sufficient mechanical strength, and when used, for example, as a flexible electronic device substrate, may not be able to withstand stress and may be destroyed. Moreover, the thickness of the polyimide film is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and still more preferably 20 ⁇ m or less. When the thickness of the polyimide film becomes thick, it may become difficult to make the flexible device thinner. In order to make the polyimide film thinner while maintaining sufficient durability as a flexible device, the thickness of the polyimide film is preferably 2 to 50 ⁇ m.
  • the polyimide film/substrate laminate has small warpage.
  • the properties of a polyimide film can be evaluated based on the residual stress between the polyimide film and the silicon substrate in a polyimide film/silicon substrate (wafer) laminate. The residual stress that can be achieved by the present invention will be described later.
  • the polyimide film in the polyimide film/substrate laminate may have a second layer such as an inorganic thin film on the surface. It is preferable to include a step of forming a thin film.
  • the inorganic thin film is preferably one that functions as a barrier layer against water vapor, oxygen (air), and the like.
  • the water vapor barrier layer include silicon nitride (SiN x ), silicon oxide (SiO x ), silicon oxynitride (SiO x N y ), aluminum oxide (Al 2 O 3 ), titanium oxide (TiO 2 ), and zirconium oxide.
  • Examples include inorganic thin films containing an inorganic substance selected from the group consisting of metal oxides, metal nitrides, and metal oxynitrides such as (ZrO 2 ).
  • methods for forming these thin films include physical vapor deposition methods such as vacuum evaporation, sputtering, and ion plating, and chemical vapor deposition such as plasma CVD and catalytic chemical vapor deposition (Cat-CVD). (CVD: chemical vapor deposition method) and the like are known.
  • CVD chemical vapor deposition method
  • the film is densified by performing high temperature annealing at, for example, 350° C. to 450° C. after film forming.
  • inorganic thin film refers to both before and after annealing. If only one or the other is meant, it will be explicitly indicated or clear from the context. Similarly, “polyimide film/substrate laminate” means both those with and without “inorganic thin films”.
  • This second layer can also be made into multiple layers.
  • different types of inorganic thin films may be formed, or a resin film and an inorganic thin film may be combined.
  • An example of the latter is, for example, an example in which a three-layer structure of barrier layer/polyimide layer/barrier layer is formed on a polyimide film in a polyimide film/substrate laminate.
  • step (c) the polyimide/substrate laminate obtained in step (b) is used to coat a polyimide film (including one in which a second layer such as an inorganic thin film is laminated on the surface of the polyimide film). At least one layer selected from a conductor layer and a semiconductor layer is formed. These layers may be formed directly on the polyimide film (including a second layer laminated) or indirectly, on top of other layers necessary for the device. good.
  • step (c) of the present invention when forming at least one of the conductor layer and the semiconductor layer, it is also preferable to form at least one of the conductor layer and the semiconductor layer on a polyimide film on which an inorganic film is formed.
  • the conductive layer and the semiconductor layer include both those formed on the entire surface of the polyimide film and those formed on a portion of the polyimide film.
  • the present invention may proceed to step (d) immediately after step (c), or after forming at least one layer selected from a conductor layer and a semiconductor layer in step (c), the device structure may be further formed. After the formation, the process may proceed to step (d).
  • TFT liquid crystal display device When manufacturing a TFT liquid crystal display device as a flexible device, for example, metal wiring, TFTs made of amorphous silicon or polysilicon, and transparent pixel electrodes are formed on a polyimide film on which an inorganic film is formed on the entire surface if necessary.
  • a TFT includes, for example, a gate metal layer, a semiconductor layer such as an amorphous silicon film, a gate insulating layer, a wiring connected to a pixel electrode, and the like.
  • structures necessary for a liquid crystal display can also be formed by known methods.
  • a transparent electrode and a color filter may be formed on the polyimide film.
  • a TFT is formed as necessary on a polyimide film on which an inorganic film is formed on the entire surface, if necessary. can do.
  • the polyimide film preferred in the present invention has excellent properties such as heat resistance and toughness, there are no particular restrictions on the method of forming circuits, elements, and other structures necessary for devices.
  • the peeling method may be a mechanical peeling method in which physical peeling is performed by applying an external force, but since the polyimide film/substrate laminate of the present invention has excellent adhesion, it can be peeled by irradiating laser light from the substrate surface. It is particularly preferable to perform the peeling by a so-called laser peeling method.
  • a flexible electronic device including a polyimide film is completed, and in the flexible electronic device, the polyimide film functions as a flexible electronic device substrate.
  • the polyimide film is peeled off, and a conductive layer is formed on the polyimide film as in the above step (c). It is also possible to manufacture a (semi-)product using a polyimide film as a substrate by forming at least one layer selected from semiconductor layers and a necessary structure.
  • polyimide film/base material laminate As described above is produced from the polyimide precursor composition of the present invention, it is particularly preferably used for this purpose because it has excellent adhesion between the polyimide film and the base material.
  • the polyimide film produced from the polyimide precursor composition of the present invention has excellent light transmittance, thermal properties, and heat resistance, as well as excellent adhesion to substrates such as glass substrates.
  • Adhesion can be evaluated by peel strength.
  • the peel strength between the polyimide film and the base material in the polyimide film/base material laminate is preferably 50 gf/cm when measured in accordance with JIS K6854-1, for example, in a 90° peel test at a tensile rate of 2 mm/min. (0.49 N/cm) or more (first range), further 100 gf/cm (0.98 N/cm) or more (second range), and 150 gf/cm (1.47 N/cm) or more (third range).
  • the upper limit is usually 5 kgf/cm (49.0 N/cm) or less, preferably 3 kgf/cm (29.4 N/cm) or less. Peel strength is usually measured in air or atmosphere.
  • the polyimide film/base material laminate has small warpage, and the properties of the polyimide film can be evaluated by the residual stress between the polyimide film and the silicon substrate in the polyimide film/silicon substrate (wafer) laminate. can. Details of the measurement are described in Japanese Patent No. 6798633. However, it is assumed that the polyimide film is placed in a dry state at 23°C.
  • the residual stress evaluated by this is preferably 20 MPa or less (first range), and more preferably 15 MPa or less (second range), 12 MPa or less (third range), and 10 MPa or less (fourth range) in that order.
  • the 450 nm light transmittance of the polyimide film is preferably 73% or more (first range), and further 74% or more (second range), when measured with a 10 ⁇ m thick film.
  • the order of 75% or more (third range) is more preferable.
  • the yellowness index (YI) of the polyimide film is preferably 13 or less (first range), further 12 or less (second range), and 11 or less (third range). , 10 or less (fourth range), and 9 or less (fifth range). Further, the yellowness index (YI) is preferably 0 or more.
  • the haze value of the polyimide film is preferably less than 1.0% (first range), further 0.9% or less (second range), and 0.8%. It is more preferable in this order: below (third range), below 0.7% (fourth range), and below 0.6% (fifth range).
  • the polyimide film of the present invention has an extremely low coefficient of linear thermal expansion (CTE).
  • CTE linear thermal expansion
  • the linear thermal expansion coefficient of the polyimide film from 150° C. to 250° C. is preferably 27 ppm/K or less (first range), and further 25 ppm/K or less, when measured with a film having a thickness of 10 ⁇ m.
  • the more preferable order is: /K or less (second range), 20 ppm or less (third range), 15 ppm/K or less (fourth range), and 13 ppm/K or less (fifth range).
  • the polyimide film of the present invention (or the polyimide constituting the same) has excellent heat resistance, and the 1% weight loss temperature is preferably 512°C or higher (first range), and further 515°C or higher (second range). , 520°C or higher (third range), and 522°C or higher (fourth range).
  • the glass transition temperature (Tg) of the polyimide film is preferably 350°C or higher, more preferably 370°C or higher, even more preferably 390°C or higher, and The temperature is more preferably 400°C or higher, even more preferably 410°C or higher, even more preferably 420°C or higher, even more preferably 430°C or higher, even more preferably 435°C or higher, and most preferably 440°C or higher.
  • the polyimide film of the present invention exhibits a very high elastic modulus.
  • the elastic modulus of the polyimide film is preferably 6.5 GPa or more (first range), further 6.9 GPa or more (second range), 7.3 GPa or more (third range), More preferred is the order of 7.5 GPa or more (fourth range), 7.6 GPa or more (fifth range), 8.0 GPa or more (sixth range), and 8.3 GPa or more (seventh range).
  • a value obtained from a film having a thickness of about 8 to 12 ⁇ m, for example, can be used.
  • the elongation at break of the polyimide film is preferably 10% or more (first range), and further 20% or more (second range) when measured with a film having a thickness of 10 ⁇ m. , 25% or more (third range), and 30% or more (fourth range).
  • the breaking strength of the polyimide film is preferably 200 MPa or more (first range), further 250 MPa or more (second range), 270 MPa or more (third range), and 300 MPa or more. (Fourth range) is preferred.
  • a value obtained from a film having a thickness of about 5 to 100 ⁇ m, for example, can be used.
  • the adhesion, light transmittance, and elastic modulus satisfy the "preferred range” at the same time, and it is especially preferable that the linear thermal expansion coefficient and 1% weight loss temperature also satisfy the "preferred range” at the same time. preferable.
  • Polyimide films having such properties are novel in themselves and independently patentable. Particularly preferred embodiments are as follows. (1) The 450 nm light transmittance of the polyimide film is 74% or more (second range), and the elastic modulus is 6.9 GPa or more (second range), preferably 7.3 GPa or more (third range), The linear thermal expansion coefficient and elongation at break satisfy the above-mentioned first range.
  • the polyimide film has a 450 nm light transmittance of 75% or more (third range), preferably 76% (fourth range), an elastic modulus of 7.3 GPa or more (third range), and The expansion coefficient and elongation at break satisfy the above-mentioned first range.
  • the 450 nm light transmittance of the polyimide film is 74% or more (second range), preferably 75% or more (third range), and the distance between the polyimide film and the base material in the polyimide film/base material laminate is The peel strength satisfies 200 gf/cm or more (fourth range), preferably 300 gf/cm or more (fifth range).
  • polyimide and single polyimide films can also be produced using the polyimide precursor composition of the present invention.
  • the manufacturing method is not particularly limited, and any known imidization method can be suitably applied.
  • Preferred forms of the polyimide obtained include films, coatings, powders, beads, molded bodies, and foamed bodies.
  • a single polyimide film can be manufactured by a known method.
  • a typical method is to cast a polyimide precursor composition onto a substrate, heat imidize it on the substrate, and then peel off the polyimide film.
  • the self-supporting film is peeled off from the base material and, for example, the film is held with a tenter and both sides of the film are exposed.
  • a polyimide film can also be obtained by thermal imidization in a degassable state.
  • the thickness of a single polyimide film depends on the application, but is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, even more preferably 5 ⁇ m or more, and, for example, 250 ⁇ m or less, preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less, and More preferably, it is 50 ⁇ m or less.
  • the light source was D65, and the viewing angle was 2°.
  • CTE Coefficient of linear thermal expansion
  • 1% weight loss temperature A polyimide film having a thickness of about 10 ⁇ m was used as a test piece, and the temperature was raised from 25° C. to 600° C. at a heating rate of 10° C./min in a nitrogen stream using a calorimeter measuring device (Q5000IR) manufactured by TA Instruments. From the obtained weight curve, the 1% weight loss temperature was determined with the weight at 150° C. as 100%.
  • a 6-inch silicon wafer (625 ⁇ m thick, (100) substrate) was used as a reference substrate for polyimide film evaluation.
  • a polyimide precursor composition is applied onto a silicon wafer using a spin coater, and heated directly on the silicon wafer from room temperature to the same temperature as in Examples and Comparative Examples in a nitrogen atmosphere (oxygen concentration 200 ppm or less) to thermally form an imide.
  • a polyimide film/reference base material laminate is obtained. The thickness of the polyimide film in the laminate is approximately 10 ⁇ m.
  • the radius of curvature of the polyimide film/silicon wafer laminate obtained according to the description in Japanese Patent No. 6798633 was measured at temperatures of 150°C, 140°C, 130°C, 120°C and 110°C. Measured using FLX-2320. Measure 20 times at each temperature and calculate the average value. The radius of curvature of a single silicon wafer is also measured at the same temperature. From the obtained radius of curvature, the residual stress (S) at each temperature is calculated according to Equation 1 below, and the residual stress at 23° C. is determined by linear approximation using the least squares method.
  • PMDA Pyromellitic dianhydride
  • DSDA 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride
  • ODPA 4,4'-oxydiphthalic dianhydride
  • s-BPDA 3,3',4 , 4'-biphenyltetracarboxylic dianhydride
  • 6FDA 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride
  • KBM-103 Phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • KBM-202SS Diphenyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • HIVAC-F-5 1,3,5-trimethyl-1,1,3,5,5-pentaphenyltrisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Table 1-1 shows the tetracarboxylic acid component and diamine component
  • Table 1-2 shows the structural formula of the imidazole compound.
  • polyimide film/base material laminate As a glass substrate, a 6-inch Eagle-XG (registered trademark) manufactured by Corning (500 ⁇ m thick) was used. A polyimide precursor composition is applied onto a glass substrate using a spin coater, and thermally imidized by heating from room temperature to 420°C on the glass substrate in a nitrogen atmosphere (oxygen concentration 200 ppm or less) to form a polyimide film. /A base material laminate was obtained. Peel strength was measured by creating test samples with a width of 5 mm from the obtained polyimide film/glass laminate.
  • the polyimide film was peeled off from the glass substrate by soaking the laminate in water at 40°C (for example, in a temperature range of 20°C to 100°C), and after drying, the properties of the polyimide film were evaluated.
  • the thickness of the polyimide film is approximately 10 ⁇ m. The evaluation results are shown in Table 2.
  • Examples 2 to 6 Comparative Examples 1 to 4> A polyimide precursor composition was obtained in the same manner as in Example 1, except that the tetracarboxylic acid component and the diamine component were changed to the compounds and amounts (molar ratios) shown in Table 2. Thereafter, a polyimide film was produced in the same manner as in Example 1, and the physical properties of the film were evaluated.
  • Example 7 ⁇ Examples 7, 11, Comparative Examples 6 to 8>
  • the tetracarboxylic acid component and the diamine component were changed to the compounds and amounts (molar ratios) shown in Table 3, and the reaction was carried out in the same manner as in Example 1 to obtain a polyimide precursor composition.
  • a polyimide film was produced in the same manner as in Example 1, except that the maximum heating temperature for imidization was changed to 450°C, and the physical properties of the film were evaluated.
  • Example 1 the tetracarboxylic acid component and the diamine component were changed to the compounds and amounts (molar ratios) shown in Table 3, and the reaction was carried out in the same manner as in Example 1 to obtain a polyimide precursor solution.
  • 2-phenylimidazole as an imidazole compound was dissolved in 4 times the mass of N-methyl-2-pyrrolidone to obtain a homogeneous solution having a solid concentration of 2-phenylimidazole of 20% by mass.
  • Example 1 ⁇ Examples 12 to 25, Comparative Examples 9 and 10>
  • the tetracarboxylic acid component and the diamine component were changed to the compounds and amounts (molar ratios) shown in Table 4 or 5, and the reaction was carried out in the same manner as in Example 1 to obtain a polyimide precursor solution.
  • the imidazole compound was changed to the compound shown in Table 4 or 5, and the solution of the imidazole compound and the polyimide precursor solution synthesized above were mixed so that the amount was as shown in Table 4 or 5, and the mixture was heated at room temperature. After stirring for 3 hours, a uniform and viscous polyimide precursor composition was obtained.
  • Example 2 Thereafter, a polyimide film was produced in the same manner as in Example 1, except that the maximum heating temperature for imidization was 420° C. or 450° C. (as described in Table 4 or 5), and the film properties were evaluated. Note that in Comparative Example 9, no imidazole compound was added.
  • the imidazole compound when added in an amount of 0.01 mol or more and less than 1 mol, when the total of ODPA and s-BPDA in the tetracarboxylic acid component is 70 mol% or more (the proportion of ODPA is less than 50 mol%), However, the effects of high peel strength, high 450 nm light transmittance, and low yellow index (YI) were confirmed.
  • Example 7 [Example of addition of silane compound] ⁇ Examples 29 to 34, 40 to 43, Reference Example 13> As in Example 7, the tetracarboxylic acid component and the diamine component were changed to the compounds and amounts (molar ratios) shown in Table 7, and the reaction was carried out in the same manner as in Example 1 to obtain a polyimide precursor solution.
  • a silane compound the compound and amount shown in Table 7 (parts by mass based on 100 parts by mass of the tetracarboxylic acid component and diamine component) were mixed with the polyimide precursor solution synthesized above, stirred at room temperature for 3 hours, and then uniformly A viscous polyimide precursor composition was obtained. Using the obtained polyimide precursor composition, a polyimide film was produced in the same manner as in Example 1 except that the maximum heating temperature for imidization was 450°C, and the film physical properties were evaluated.
  • Example 35 to 39> Similar to Example 8, etc., in Example 1, the tetracarboxylic acid component and the diamine component were changed to the compounds and amounts (molar ratios) shown in Table 8, and the polyimide precursor solution was reacted in the same manner as in Example 1. After that, the imidazole compound solution and the polyimide precursor solution were mixed so that the amount of the imidazole compound was as shown in Table 8.
  • Example 36 to 39 as a silane compound, the compound and amount shown in Table 8 (parts by mass based on 100 parts by mass of the tetracarboxylic acid component and diamine component) were mixed with the polyimide precursor solution synthesized above, The mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide precursor composition. Using the obtained polyimide precursor composition, a polyimide film was produced in the same manner as in Example 1, except that the maximum heating temperature for imidization was 450°C, and the physical properties of the film were evaluated. For comparison, Example 35 had the same composition as Examples 36 to 39 except that no silane compound was added, but Example 35 is an example of the present application.
  • Example 44 to 50> Similarly to Examples 7 and 8, in Example 1, the tetracarboxylic acid component and the diamine component were changed to the compounds and amounts (molar ratios) shown in Table 9, and the polyimide precursor was obtained by reacting in the same manner as in Example 1. After obtaining the body solution, for Examples 47 and 48, the imidazole compound solution and the polyimide precursor solution were mixed so that the amount of the imidazole compound was as shown in Table 9. For Examples 45, 46, 48 to 50, the compounds and amounts shown in Table 9 (parts by mass based on the total of 100 parts by mass of the tetracarboxylic acid component and diamine component) were used as the silane compound in the polyimide precursor solution synthesized above.
  • Example 44 and 47 are examples in which no silane compound was added for comparison, but are examples of the present application.
  • Example 52 and 53 as a silane compound, the compound and amount shown in Table 10 (parts by mass based on 100 parts by mass in total of the tetracarboxylic acid component and diamine component) were mixed with the polyimide precursor solution synthesized above, The mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide precursor composition. Using the obtained polyimide precursor composition, a polyimide film was produced in the same manner as in Example 1, except that the maximum heating temperature for imidization was 450°C, and the physical properties of the film were evaluated. Note that Example 51 is an example in which no silane compound was added for comparison, but is an example of the present application.
  • Example 51 to 53 a peel strength test on the glass laminate and measurement of residual stress on the silicon wafer laminate were conducted in the same manner as in Example 1. Furthermore, peeling between the polyimide film and the glass substrate and between the polyimide film and the SiOx film was observed in the same manner as in [Adhesion Test 2 after Inorganic Thin Film Formation]. The measurement and evaluation results are shown in Table 10.
  • Example 7 compared to Example 7, the 450 nm light transmittance was further improved in the Examples in which the silane compounds (KBM-103 and KBM-202SS) were added.
  • the 450 nm light transmittance was improved, but the 1% weight loss temperature was significantly lowered and the heat resistance was poor.
  • Table 8 it was confirmed that even in the system containing the imidazole compound, the 450 nm light transmittance was improved by adding the silane compound. Similar trends were observed in Tables 9 and 10.
  • the present invention can be suitably applied to the manufacture of flexible electronic devices, for example, flexible displays such as liquid crystal displays and organic EL displays, display devices such as electronic paper, and light receiving devices such as solar cells and CMOS.
  • flexible displays such as liquid crystal displays and organic EL displays
  • display devices such as electronic paper
  • light receiving devices such as solar cells and CMOS.

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