Classifications

• • 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
  • 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
  • C08G73/16—Polyester-imides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1003—Preparatory processes
  • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
  • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
  • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
• • 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
  • 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
  • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
  • C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1067—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
• • 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
• • 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 polyamic acid composition, a polyimide, a polyimide film, a laminate, an electronic device, a method for producing a polyimide, a method for producing a laminate, and a method for producing an electronic device.
• the present invention further relates to electronic device materials using polyimide, thin film transistor (TFT) substrates, flexible display substrates, color filters, printed matter, optical materials, image display devices (more specifically, liquid crystal display devices, organic electroluminescence, electronic paper, etc.), 3D displays, solar cells, touch panels, transparent conductive film substrates, and alternative materials for components that currently use glass.
• TFT thin film transistor
• various electronic elements such as thin-film transistors and transparent electrodes, are formed on the substrate, and high-temperature processes are required to form these electronic elements.
• Polyimide has sufficient heat resistance to be suitable for high-temperature processes, and its coefficient of linear expansion (CTE) is close to that of glass substrates and electronic elements, making it less susceptible to internal stress and suitable for use as a substrate material for flexible displays, etc.
• Polyimides obtained from polyamic acid compositions containing polyamic acid and organic solvents are used as substitutes for glass substrates in electronic devices, insulating films used in semiconductor devices, protective coating agents, etc., as well as planarizing films for TFT substrates for display devices (see, for example, Patent Document 1). It is also known that materials such as acrylic resins, siloxanes, and photosensitive polyimides are used as planarizing films for TFT substrates (see, for example, Patent Documents 2 and 3).
• the process temperature for organic EL display devices and semiconductor devices can become high due to factors such as larger substrates and improved productivity, leaving room for further improvement in the heat resistance of existing insulating films and planarizing films. Furthermore, high-temperature processes can reduce the adhesion between the polyimide film and the inorganic oxide film provided on the substrate.
• polyamic acid compositions may be stored in solution form for a period of time in a coating device such as a slit coater or spin coater. If the viscosity of the polyamic acid composition changes while stored in the coating device, it may become difficult to obtain a coating film that is smooth and has a uniform thickness. For this reason, a polyamic acid composition with excellent storage stability is desired.
• the present invention has been achieved in view of the above circumstances, and aims to provide a polyamic acid composition capable of producing a polyimide having excellent storage stability, heat resistance, and adhesion to an inorganic oxide film. Another aim of the present invention is to provide a polyimide, a polyimide film, a laminate, and an electronic device produced using the polyamic acid composition. Furthermore, the present invention also aims to provide a method for producing a polyimide, a method for producing a laminate, and a method for producing an electronic device using the polyamic acid composition.
• the present invention includes the following aspects.
• a polyamic acid composition containing a polyamic acid and an organic solvent The polyamic acid has a tetracarboxylic dianhydride residue and a diamine residue
• the tetracarboxylic dianhydride residue includes a 3,3',4,4'-biphenyltetracarboxylic dianhydride residue and a spiro[11H-difuro[3,4-b:3',4'-i]xanthene-11,9'-[9H]fluorene]-1,3,7,9-tetrone residue
• the diamine residue comprises a p-phenylenediamine residue
• At least one of the tetracarboxylic dianhydride residue and the diamine residue further contains a residue having an ester bond
• At least one of the tetracarboxylic dianhydride residue and the diamine residue further contains a residue having a diphenyl ether structure.
• X is a divalent organic group represented by the following general formula (3), a divalent organic group represented by the following general formula (4), a divalent organic group represented by the following general formula (5), a divalent organic group represented by the following chemical formula (6), or a divalent organic group represented by the following chemical formula (7).
• R 1 , R 2 , and R 3 each independently represent a hydrogen atom, a methyl group, an ethyl group, or a trifluoromethyl group, and a plurality of R 1s may be the same or different from each other, a plurality of R 2s may be the same or different from each other, and a plurality of R 3s may be the same or different from each other.
• Y and Z are each independently a divalent organic group represented by the following general formula (11), a divalent organic group represented by the following general formula (12), or a divalent organic group represented by the following general formula (13).
• R 4 , R 5 , and R 6 each independently represent a hydrogen atom, a methyl group, an ethyl group, or a trifluoromethyl group, and a plurality of R 4s may be the same or different from each other, a plurality of R 5s may be the same or different from each other, and a plurality of R 6s may be the same or different from each other.
• R 7 , R 8 and R 9 each independently represent a monovalent organic group having 1 or more carbon atoms or a hydrogen atom, and at least one of R 7 , R 8 and R 9 represents a monovalent organic group having 2 or more carbon atoms.
• the electrochemical cell further comprises an inorganic oxide film interposed between the support and the polyimide film, The laminate according to the above [13], wherein a peel strength between the polyimide film and the inorganic oxide film is 0.10 N/cm or more.
• a method for producing a polyimide which comprises imidizing the polyamic acid contained in the polyamic acid composition described in any one of [1] to [9] above.
• a method for producing a laminate having a support and a polyimide film comprising the steps of: A method for producing a laminate, comprising applying the polyamic acid composition according to any one of items [1] to [9] above onto a support to form a coating film containing the polyamic acid, and heating the coating film to imidize the polyamic acid.
• a method for manufacturing an electronic device comprising forming a laminate having a support and a polyimide film by the method described in [17] above, and forming an electronic element on the polyimide film.
• the present invention can provide a polyamic acid composition capable of producing a polyimide having excellent storage stability, heat resistance, and adhesion to an inorganic oxide film.
• the present invention can also provide a polyimide, a polyimide film, a laminate, and an electronic device produced using the polyamic acid composition.
• the present invention can also provide a method for producing a polyimide, a method for producing a laminate, and a method for producing an electronic device using the polyamic acid composition.
• Structural unit refers to a repeating unit that constitutes a polymer.
• Polyamic acid is a polymer that contains a structural unit represented by the following general formula (15) (hereinafter, sometimes referred to as “structural unit (15)”).
• A1 represents a tetracarboxylic dianhydride residue (a tetravalent organic group derived from a tetracarboxylic dianhydride), and A2 represents a diamine residue (a divalent organic group derived from a diamine).
• the content of structural unit (15) relative to all structural units constituting the polyamic acid is, for example, 50 mol% or more and 100 mol% or less, preferably 60 mol% or more and 100 mol% or less, more preferably 70 mol% or more and 100 mol% or less, even more preferably 80 mol% or more and 100 mol% or less, even more preferably 90 mol% or more and 100 mol% or less, and may be 100 mol%.
• linear expansion coefficient refers to the linear expansion coefficient when cooling from 100°C to 300°C.
• the compound name may be followed by “based” to collectively refer to the compound and its derivatives. Also, when the compound name is followed by “based” to represent the name of a polymer, unless otherwise specified, it means that the repeating unit of the polymer is derived from the compound or its derivative. Also, tetracarboxylic acid dianhydrides may be referred to as “acid dianhydrides.”
• the polyamic acid composition according to the present embodiment contains a polyamic acid (hereinafter, may be referred to as "polyamic acid (1)”) and an organic solvent.
• the polyamic acid (1) has a tetracarboxylic dianhydride residue and a diamine residue.
• the tetracarboxylic dianhydride residue includes a 3,3',4,4'-biphenyltetracarboxylic dianhydride residue and a spiro[11H-difuro[3,4-b:3',4'-i]xanthene-11,9'-[9H]fluorene]-1,3,7,9-tetrone residue.
• the polyamic acid (1) contains, as the tetracarboxylic dianhydride residue, a 3,3',4,4'-biphenyltetracarboxylic dianhydride residue and a spiro[11H-difuro[3,4-b:3',4'-i]xanthene-11,9'-[9H]fluorene]-1,3,7,9-tetrone residue.
• the diamine residue includes a p-phenylenediamine residue. That is, the polyamic acid (1) contains a p-phenylenediamine residue as a diamine residue.
• At least one of the tetracarboxylic dianhydride residue and the diamine residue further contains a residue having an ester bond. At least one of the tetracarboxylic dianhydride residue and the diamine residue further contains a residue having a diphenyl ether structure.
• BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
• BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
• Spiro[11H-difuro[3,4-b:3',4'-i]xanthene-11,9'-[9H]fluorene]-1,3,7,9-tetrone may be referred to as "SFDA”.
• p-Phenylenediamine may be referred to as "PDA”.
• a residue having an ester bond may be referred to as an "ester bond-containing residue".
• a residue having a diphenyl ether structure may be referred to as a "diphenyl ether structure-containing residue".
• the SFDA residue is a tetravalent organic group represented by the following chemical formula (16).
• the polyamic acid composition according to this embodiment has excellent storage stability. Furthermore, polyimide produced using the polyamic acid composition according to this embodiment has excellent heat resistance and adhesion to inorganic oxide films. The reasons for this are presumed to be as follows.
• the polyamic acid (1) contained in the polyamic acid composition according to this embodiment has BPDA residues, SFDA residues, and PDA residues.
• the BPDA residues, SFDA residues, and PDA residues all have rigid structures. For this reason, the polyimide produced using the polyamic acid composition according to this embodiment has excellent heat resistance.
• the polyamic acid (1) contained in the polyamic acid composition according to this embodiment contains an SFDA residue having a bulky structure derived from a fluorene structure, so that a polyimide film with excellent gas release properties can be formed.
• the polyamic acid (1) contained in the polyamic acid composition according to this embodiment has an ester bond-containing residue. The ester bond-containing residue tends to easily interact with the inorganic oxide in the inorganic oxide film. For these reasons, the polyimide produced using the polyamic acid composition according to this embodiment has excellent adhesion to the inorganic oxide film.
• the polyamic acid (1) contained in the polyamic acid composition according to this embodiment has a residue containing a diphenyl ether structure.
• the residue containing a diphenyl ether structure tends to increase the solubility in organic solvents. Therefore, the polyamic acid composition according to this embodiment has excellent storage stability.
• only one of the tetracarboxylic dianhydride residue and the diamine residue may have an ester bond-containing residue, or both the tetracarboxylic dianhydride residue and the diamine residue may have an ester bond-containing residue.
• the ester bond-containing residue is preferably one or more selected from the group consisting of tetravalent organic groups represented by the following general formula (1) and tetravalent organic groups represented by the following chemical formula (2).
• X is a divalent organic group represented by the following general formula (3), a divalent organic group represented by the following general formula (4), a divalent organic group represented by the following general formula (5), a divalent organic group represented by the following chemical formula (6), or a divalent organic group represented by the following chemical formula (7).
• R 1 , R 2 , and R 3 each independently represent a hydrogen atom, a methyl group, an ethyl group, or a trifluoromethyl group, and a plurality of R 1s may be the same or different from each other, a plurality of R 2s may be the same or different from each other, and a plurality of R 3s may be the same or different from each other.
• the tetravalent organic group represented by chemical formula (2) is a residue derived from (1,3-dioxoisobenzofuran-5-yl)1,3-dioxoisobenzofuran-5-carboxylate (hereinafter sometimes referred to as "8CI").
• the ester bond-containing residue contained in the tetracarboxylic dianhydride residue is preferably a tetravalent organic group represented by general formula (1), and more preferably a TMHQ residue.
• the ester bond-containing residue is preferably one or more selected from the group consisting of a divalent organic group represented by the following chemical formula (8), a divalent organic group represented by the following general formula (9), and a divalent organic group represented by the following general formula (10).
• Y and Z are each independently a divalent organic group represented by the following general formula (11), a divalent organic group represented by the following general formula (12), or a divalent organic group represented by the following general formula (13).
• R 4 , R 5 , and R 6 each independently represent a hydrogen atom, a methyl group, an ethyl group, or a trifluoromethyl group, and multiple R 4s may be the same or different from each other, multiple R 5s may be the same or different from each other, and multiple R 6s may be the same or different from each other.
• the divalent organic group represented by chemical formula (8) is preferred as the ester bond-containing residue contained in the diamine residue.
• the divalent organic group represented by chemical formula (8) is a residue derived from 4-aminophenyl-4-aminobenzoate (hereinafter sometimes referred to as "4-BAAB").
• only one of the tetracarboxylic dianhydride residue and the diamine residue may have a diphenyl ether structure-containing residue, or both the tetracarboxylic dianhydride residue and the diamine residue may have a diphenyl ether structure-containing residue.
• examples of the diphenyl ether structure-containing residue include 4,4'-oxydianiline residue, 3,4'-oxydianiline residue, 2,2-bis[4-(4-aminophenoxy)phenyl]propane residue, 1,4-bis(4-aminophenoxy)benzene residue, 1,3-bis(4-aminophenoxy)benzene residue, 1,3-bis(3-aminophenoxy)benzene residue, 4,4'-bis(4-aminophenoxy)biphenyl residue, bis[4-(4-aminophenoxy)phenyl]sulfone residue, and bis[4-(3-aminophenoxy)phenyl]sulfone residue.
• 4,4'-oxydianiline residue is preferred in order to obtain a polyamic acid composition with superior storage stability.
• 4,4'-oxydianiline may be referred to as "ODA”.
• an acid dianhydride other than the above-mentioned acid dianhydride (other acid dianhydride) may be used.
• other acid dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, dicyclohexyl-3,3',4,4'-tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane t
• the content of BPDA residues relative to the total acid dianhydride residues (100 mol%) constituting polyamic acid (1) is preferably 50 mol% or more and 95 mol% or less, and more preferably 60 mol% or more and 93 mol% or less.
• the content of PDA residues relative to the total diamine residues (100 mol%) constituting polyamic acid (1) is preferably 70 mol% or more and 98 mol% or less, and more preferably 80 mol% or more and 97 mol% or less.
• the content of the ester bond-containing residue as an acid dianhydride residue is preferably 1 mol % or more and 30 mol % or less, and more preferably 2 mol % or more and 20 mol % or less, relative to the total acid dianhydride residues (100 mol %) constituting polyamic acid (1).
• the content of the ester bond-containing residue as a diamine residue is preferably 3 mol % or more and 30 mol % or less, and more preferably 5 mol % or more and 20 mol % or less, relative to the total diamine residues (100 mol %) constituting polyamic acid (1).
• the content of diphenyl ether structure-containing residues is preferably 1 mol % or more and 40 mol % or less, and more preferably 3 mol % or more and 30 mol % or less, relative to the total (200 mol %) of all acid dianhydride residues and all diamine residues constituting polyamic acid (1).
• the content of the diphenyl ether structure-containing residue as an acid dianhydride residue is preferably 1 mol% or more and 40 mol% or less, and more preferably 3 mol% or more and 30 mol% or less, relative to the total acid dianhydride residues (100 mol%) constituting polyamic acid (1).
• the content of the diphenyl ether structure-containing residue as a diamine residue is preferably 3 mol% or more and 20 mol% or less, and more preferably 5 mol% or more and 10 mol% or less, relative to the total diamine residues (100 mol%) constituting polyamic acid (1).
• the total content of BPDA residues, SFDA residues, PDA residues, ester bond-containing residues, and diphenyl ether structure-containing residues is preferably 125 mol% or more and 200 mol% or less, more preferably 150 mol% or more and 200 mol% or less, even more preferably 180 mol% or more and 200 mol% or less, even more preferably 190 mol% or more and 200 mol% or less, and may be 200 mol%, based on the total (200 mol%) of all acid dianhydride residues and all diamine residues constituting polyamic acid (1).
• the polyamic acid composition according to the present embodiment preferably satisfies the following condition 1, more preferably satisfies the following condition 2, even more preferably satisfies the following condition 3, and even more preferably satisfies the following condition 4.
• Condition 1 The total content of BPDA residues, SFDA residues, PDA residues, ester bond-containing residues, and diphenyl ether structure-containing residues is 180 mol % or more and 200 mol % or less based on the total (200 mol %) of all acid dianhydride residues and all diamine residues constituting the polyamic acid (1).
• Requirement 2 The above requirement 1 is satisfied, and the content of SFDA residues is 1 mol % or more and 10 mol % or less based on the total acid dianhydride residues (100 mol %) constituting the polyamic acid (1).
• Condition 3 The above condition 2 is satisfied, and the content of the ester bond-containing residue is 1 mol % or more and 30 mol % or less based on the total (200 mol %) of all acid dianhydride residues and all diamine residues constituting the polyamic acid (1).
• Requirement 4 The above requirement 3 is satisfied, and the content of the diphenyl ether structure-containing residue is 1 mol % or more and 40 mol % or less based on the total (200 mol %) of all acid dianhydride residues and all diamine residues constituting the polyamic acid (1).
• Polyamic acid (1) can be synthesized by a known general method, for example, by reacting a diamine with a tetracarboxylic dianhydride in an organic solvent.
• An example of a specific method for synthesizing polyamic acid (1) will be described. First, in an inert gas atmosphere such as argon or nitrogen, a diamine is dissolved or dispersed in a slurry state in an organic solvent to prepare a diamine solution. Then, the tetracarboxylic dianhydride is added to the diamine solution after being dissolved or dispersed in a slurry state in the organic solvent, or in a solid state.
• the desired polyamic acid (1) (polymer of diamine and tetracarboxylic dianhydride) can be obtained by adjusting the amount of diamine (when multiple diamines are used, the amount of each diamine) and the amount of tetracarboxylic dianhydride (when multiple tetracarboxylic dianhydrides are used, the amount of each tetracarboxylic dianhydride).
• the molar fraction of each residue in polyamic acid (1) is, for example, equal to the molar fraction of each monomer (diamine and tetracarboxylic dianhydride) used in the synthesis of polyamic acid (1).
• polyamic acid (1) containing multiple types of tetracarboxylic dianhydride residues and multiple types of diamine residues can be obtained.
• the temperature conditions of the reaction between diamine and tetracarboxylic dianhydride, i.e., the synthesis reaction of polyamic acid (1) are not particularly limited, but are, for example, in the range of 20°C to 150°C.
• the reaction time for the synthesis reaction of polyamic acid (1) is, for example, in the range of 10 minutes to 30 hours.
• the organic solvent used in the synthesis of polyamic acid (1) is preferably a solvent capable of dissolving the tetracarboxylic dianhydride and diamine used, and more preferably a solvent capable of dissolving the resulting polyamic acid (1).
• organic solvents used in the synthesis of polyamic acid (1) include urea-based solvents such as tetramethylurea and N,N-dimethylethylurea; sulfoxide-based solvents such as dimethylsulfoxide; sulfone-based solvents such as diphenylsulfone and tetramethylsulfone; N,N-dimethylacetamide (DMAC), N,N-dimethylformamide (DMF), N,N-diethylacetamide (DEF), N-methyl-2-pyrrolidone (NMP), 3-methoxy-N,N-dimethylpropanamide (MPA), 3-butoxy-N,N-dimethylpropanamide (BPA), N,N-dimethyl
• suitable solvents include amide solvents such as dipropionamide (DMPA) and hexamethylphosphoric triamide; ester solvents such as gamma-butyrolactone; halogenated alkyl solvents such as chloride
• the organic solvent used in the synthesis reaction of polyamic acid (1) is preferably one or more solvents selected from the group consisting of amide solvents, ketone solvents, ester solvents, and ether solvents, and more preferably an amide solvent.
• the synthesis reaction of polyamic acid (1) is preferably carried out under an inert gas atmosphere such as argon or nitrogen.
• the organic solvent contained in the polyamic acid composition according to this embodiment can be any of the organic solvents exemplified as organic solvents usable in the synthesis reaction of polyamic acid (1) above.
• One or more solvents selected from the group consisting of amide-based solvents, ketone-based solvents, ester-based solvents, and ether-based solvents are preferred, with amide-based solvents being more preferred.
• an amide-based solvent is used as the organic solvent contained in the polyamic acid composition according to this embodiment
• an example of an organic solvent that has little effect on the environment and human body and is highly safe is a compound represented by the following general formula (14).
• R 7 , R 8 , and R 9 each independently represent a monovalent organic group having 1 or more carbon atoms or a hydrogen atom, and at least one of R 7 , R 8 , and R 9 represents a monovalent organic group having 2 or more carbon atoms.
• the compound represented by general formula (14) As the organic solvent contained in the polyamic acid composition according to this embodiment, it is preferable to use only the compound represented by general formula (14) as the organic solvent contained in the polyamic acid composition according to this embodiment.
• Examples of the compound represented by general formula (14) include MPA, BPA, DMPA, and DEF.
• MPA is preferred as the compound represented by general formula (14).
• the reaction solution (the solution after the reaction) itself may be used as the polyamic acid composition according to this embodiment.
• the solid polyamic acid (1) obtained by removing the solvent from the reaction solution may be dissolved in an organic solvent to prepare the polyamic acid composition according to this embodiment.
• the content of polyamic acid (1) in the polyamic acid composition according to this embodiment is not particularly limited, but is, for example, 1% by weight or more and 80% by weight or less with respect to the total amount of the polyamic acid composition.
• the viscosity change rate when the polyamic acid composition is stored for 14 days in an environment at a temperature of 23°C and a relative humidity of 55% is preferably within ⁇ 30%, and more preferably within ⁇ 20%.
• the viscosity change rate is measured by the same method as in the examples described below or a method equivalent thereto.
• the weight average molecular weight of polyamic acid (1) is preferably in the range of 10,000 to 1,000,000, more preferably in the range of 20,000 to 500,000, and even more preferably in the range of 30,000 to 200,000, depending on the application. If the weight average molecular weight is 10,000 or more, it is easy to make polyamic acid (1) or a polyimide obtained by using polyamic acid (1) into a coating film or polyimide film. On the other hand, if the weight average molecular weight is 1,000,000 or less, the polyamic acid composition shows sufficient solubility in a solvent, so that a coating film or polyimide film having a smooth surface and a uniform thickness can be obtained by using the polyamic acid composition.
• the weight average molecular weight used here refers to a polyethylene oxide equivalent value measured by gel permeation chromatography (GPC).
• a method for controlling the molecular weight of polyamic acid (1) there are a method of using an excess of either the acid dianhydride or the diamine, and a method of quenching the reaction by reacting with a monofunctional acid anhydride or amine such as phthalic anhydride or aniline.
• a monofunctional acid anhydride or amine such as phthalic anhydride or aniline.
• a polyimide film having sufficient strength can be obtained if the molar ratio of the diamines used in the synthesis of polyamic acid (1) is between 0.95 and 1.05.
• the molar ratio of the diamines used in the synthesis of polyamic acid (1) is the ratio of the total amount of diamines used in the synthesis of polyamic acid (1) to the total amount of diamines used in the synthesis of polyamic acid (1) (total amount of diamines/total amount of dianhydrides).
• total amount of diamines/total amount of dianhydrides total amount of diamines/total amount of dianhydrides.
• the polyimide according to this embodiment is an imidized product of the polyamic acid (1) described above.
• the polyimide according to this embodiment can be obtained by a known method, and the manufacturing method is not particularly limited. An example of a method for obtaining the polyimide according to this embodiment by imidizing the polyamic acid (1) will be described below.
• the imidization is performed by dehydrating and ring-closing the polyamic acid (1). This dehydrating and ring-closing can be performed by an azeotropic method using an azeotropic solvent, a thermal method, or a chemical method.
• the imidization of the polyamic acid (1) to the polyimide can take any ratio of 1% to 100%.
• a polyamic acid (1) that is partially imidized may be synthesized.
• the ring-closing reaction from the polyamic acid (1) to the polyimide and the hydrolysis of the polyamic acid (1) proceed simultaneously, and the molecular weight of the polyimide when it is made may be lower than the molecular weight of the polyamic acid (1). Therefore, from the viewpoint of improving mechanical properties, it is preferable to imidize a part of the polyamic acid (1) in the polyamic acid composition in advance before forming the polyimide film described later.
• polyamic acid that has been partially imidized may also be referred to as "polyamic acid.”
• the dehydration ring closure of polyamic acid (1) can be carried out by heating polyamic acid (1).
• the polyamic acid composition according to the present embodiment described above can be applied to a support such as a glass substrate, an inorganic oxide film (more specifically, a silicon oxide film, etc.), a metal plate, or a PET film (polyethylene terephthalate film), and then the polyamic acid (1) can be heat-treated at a temperature of 40°C to 500°C.
• a laminate according to the present embodiment can be obtained, which has a support and a polyimide film (more specifically, a polyimide film containing an imidized product of polyamic acid (1)) disposed on the support.
• the polyamic acid composition can be directly placed in a container that has been subjected to a release treatment such as coating with a fluorine-based resin, and the polyamic acid composition can be heated and dried under reduced pressure to carry out the dehydration ring closure of polyamic acid (1).
• Polyimide can be obtained by dehydration ring closure of polyamic acid (1) using these methods.
• the heating time for each of the above treatments varies depending on the amount of polyamic acid composition to be treated and the heating temperature, but is generally preferably set to a range of 1 minute to 300 minutes after the treatment temperature reaches the maximum temperature.
• an imidizing agent and/or a dehydration catalyst may be added to the polyamic acid composition, and the polyamic acid composition to which the imidizing agent and/or dehydration catalyst has been added may be heated by the above method to be imidized.
• the imidizing agent is not particularly limited, but a tertiary amine can be used.
• the tertiary amine is preferably a heterocyclic tertiary amine.
• Preferred examples of heterocyclic tertiary amines include pyridine, picoline, quinoline, isoquinoline, and 1,2-dimethylimidazole.
• Preferred examples of the dehydration catalyst include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride.
• the amount of the imidizing agent added is preferably 0.5 to 5.0 molar equivalents relative to the amide group of polyamic acid (1), more preferably 0.7 to 2.5 molar equivalents, and even more preferably 0.8 to 2.0 molar equivalents.
• the amount of the dehydration catalyst added is preferably 0.5 to 10.0 molar equivalents relative to the amide group of polyamic acid (1), more preferably 0.7 to 5.0 molar equivalents, and even more preferably 0.8 to 3.0 molar equivalents.
• the term "amide group of polyamic acid (1)" refers to the amide group generated by the polymerization reaction of diamine and tetracarboxylic dianhydride.
• the imidizing agent and/or the dehydration catalyst When the imidizing agent and/or the dehydration catalyst are added to the polyamic acid composition, they may be added directly without being dissolved in an organic solvent, or they may be added dissolved in an organic solvent. If the imidizing agent and/or dehydration catalyst are added directly without being dissolved in an organic solvent, the reaction may proceed too quickly before the imidizing agent and/or dehydration catalyst can diffuse, resulting in the formation of a gel. Therefore, it is preferable to add a solution obtained by dissolving the imidizing agent and/or dehydration catalyst in an organic solvent to the polyamic acid composition.
• the polyimide film according to this embodiment (specifically, the polyimide film containing the imidized product of polyamic acid (1)) is colorless and transparent with low yellowness and has a glass transition temperature (heat resistance) that can withstand the TFT manufacturing process, and is therefore suitable as a transparent substrate material for flexible displays.
• the content of polyimide (specifically, the imidized product of polyamic acid (1)) in the polyimide film according to this embodiment is, for example, 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more, and may be 100% by weight, based on the total weight of the polyimide film.
• components other than polyimide in the polyimide film include additives (more specifically, fine particles, etc.) described below.
• the electronic device according to this embodiment (e.g., a flexible device, etc.) has the polyimide film according to this embodiment and electronic elements disposed directly or indirectly on this polyimide film.
• a polyimide film is formed on an inorganic substrate such as glass as a support.
• electronic elements such as TFTs are disposed (formed) on the polyimide film to form an electronic device on the support.
• the process of forming TFTs is generally carried out over a wide temperature range of 150°C to 650°C, but in order to actually achieve the desired performance, the oxide semiconductor layer and a-Si layer are formed at 300°C or higher, and in some cases, the a-Si, etc. may be further crystallized using a laser or the like.
• the 1% weight loss temperature of the polyimide is preferably 450°C or higher, and more preferably 500°C or higher.
• the upper limit of the 1% weight loss temperature of the polyimide is the higher the better, but it is, for example, 580°C.
• the 1% weight loss temperature can be adjusted, for example, by changing the content of residues having a rigid structure (more specifically, BPDA residues, PDA residues, etc.).
• an inorganic film such as a silicon oxide film (SiOx film) or a silicon nitride film (SiNx film) is formed as a barrier film on the polyimide film.
• SiOx film silicon oxide film
• SiNx film silicon nitride film
• the polyimide and the inorganic film may peel off due to volatile components such as polyimide decomposition gas during the high-temperature process after lamination of the inorganic film.
• the weight loss rate when the polyimide is isothermally held at a temperature in the range of 400°C to 450°C is 1% or less.
• the glass transition temperature (Tg) of the polyimide is significantly lower than the process temperature, there is a possibility that misalignment may occur during the formation of the electronic elements, so the Tg of the polyimide is preferably 300°C or higher, more preferably 350°C or higher, and even more preferably 400°C or higher.
• the upper limit of the Tg of the polyimide is, for example, 450°C, although the higher the better.
• the linear expansion coefficient of the glass substrate is generally smaller than that of the resin, internal stress occurs between the glass substrate and the polyimide film.
• the internal stress generated in the laminate of the polyimide film and the glass substrate is preferably 30 MPa or less, more preferably 25 MPa or less, and even more preferably 20 MPa or less.
• the polyimide according to this embodiment can be suitably used as a material for display substrates such as TFT substrates and touch panel substrates.
• a method is often adopted in which an electronic device (more specifically, an electronic device in which electronic elements are formed on a polyimide film) is formed on a support as described above, and then the polyimide film is peeled off from the support.
• alkali-free glass is suitably used as a material for the support.
• an inorganic oxide film such as a SiOx film may be formed on the support, and then a polyimide film may be formed on the inorganic oxide film.
• the polyamic acid composition according to this embodiment is applied onto a support to form a coating film-containing laminate consisting of a coating film containing polyamic acid (1) and a support.
• the coating film-containing laminate is heated, for example, at a temperature of 40° C. or higher and 200° C. or lower.
• the heating time is, for example, 3 minutes or longer and 120 minutes or shorter.
• a multi-stage heating process may be provided, such as heating the coating film-containing laminate at a temperature of 50° C. for 30 minutes and then at a temperature of 100° C. for 30 minutes.
• the coating film-containing laminate is heated, for example, at a maximum temperature of 200° C.
• the heating time (heating time at the maximum temperature) is, for example, 1 minute or longer and 300 minutes or shorter. At this time, it is preferable to gradually increase the temperature from a low temperature to the maximum temperature.
• the heating rate is preferably 2° C./min or higher and 10° C./min or lower, and more preferably 4° C./min or higher and 10° C./min or lower.
• the maximum temperature is preferably in the range of 250°C or more and 450°C or less. If the maximum temperature is 250°C or more, the imidization proceeds sufficiently, and if the maximum temperature is 450°C or less, the thermal deterioration and coloring of the polyimide can be suppressed.
• any temperature may be maintained for any time until the maximum temperature is reached.
• the imidization reaction can be carried out in air, under reduced pressure, or in an inert gas such as nitrogen, but in order to develop higher transparency, it is preferable to carry out the reaction under reduced pressure or in an inert gas such as nitrogen.
• a heating device a known device such as a hot air oven, an infrared oven, a vacuum oven, an inert oven, or a hot plate can be used.
• a heating device a known device such as a hot air oven, an infrared oven, a vacuum oven, an inert oven, or a hot plate can be used.
• a laminate i.e., the laminate according to this embodiment
• the polyimide film a film containing an imidized product of the polyamic acid (1)
• an imidization agent or a dehydration catalyst may be added to the polyamic acid composition, and the solution may be heated by the above method to be imidized.
• the polyimide film can be peeled off from the obtained laminate of the support and the polyimide film by any known method. For example, it may be peeled off by hand, or by using a mechanical device such as a drive roll or a robot. Furthermore, it is also possible to employ a method in which a peeling layer is provided between the support and the polyimide film, or a method in which a silicon oxide film is formed on a substrate having a large number of grooves, a polyimide film is formed using the silicon oxide film as a base layer, and a silicon oxide etching solution is infiltrated between the substrate and the silicon oxide film to peel off the polyimide film. It is also possible to employ a method in which the polyimide film is separated by irradiation with laser light.
• the polyimide film may peel off during the formation of electronic elements, or the yield may decrease when the polyimide film is peeled off after the formation of electronic elements.
• the term "floating" refers to a state in which poor adhesion occurs between the polyimide film and other material layers (more specifically, glass substrate, barrier film, inorganic oxide film, etc.) due to outgassing or residual solvent generated during imidization.
• floating include a state in which the polyimide film floats up from the glass substrate, a state in which a part of the polyimide film is destroyed and interlayer delamination occurs between the polyimide film and other material layers, and a state in which an inorganic oxide film floats up from the polyimide film.
• a polyimide film with excellent gas release properties can be formed as described above, and therefore the occurrence of floating can be suppressed.
• the transparency of a polyimide film can be evaluated by the total light transmittance (TT) according to JIS K7361-1:1997 and the haze according to JIS K7136-2000.
• the total light transmittance of the polyimide film is preferably 75% or more, more preferably 80% or more.
• the haze of the polyimide film is preferably 1.5% or less, more preferably 1.2% or less, even more preferably less than 1.0%, and may be 0%.
• the polyimide film In applications requiring high transparency, the polyimide film is required to have high transmittance in the entire wavelength range, but the polyimide film tends to easily absorb light on the short wavelength side, and the film itself is often colored yellow. In order to use a polyimide film in an application requiring high transparency, it is preferable that the coloring of the polyimide film is reduced. Specifically, in order to use the polyimide film in applications requiring high transparency, the yellowness index (YI) of the polyimide film is preferably 20 or less, more preferably 18 or less, even more preferably 15 or less, even more preferably 12 or less, particularly preferably 8 or less, and may be 0. YI can be measured according to JIS K7373-2006.
• YI can be adjusted, for example, by changing the content of SFDA residues in polyamic acid (1).
• the polyimide film with reduced coloration and transparency is suitable for transparent substrates for glass replacement applications, etc., and substrates on which sensors or camera modules are provided on the back surface.
• the top emission method in which light is extracted from the front side of the TFT
• the bottom emission method in which light is extracted from the back side of the TFT.
• the top emission method is characterized by the fact that the aperture ratio is easily increased because light is not blocked by the TFT, and high-definition image quality can be obtained
• the bottom emission method is characterized by the ease of alignment between the TFT and the pixel electrode, making it easy to manufacture. If the TFT is transparent, it is possible to improve the aperture ratio even in the bottom emission method, so there is a tendency for the bottom emission method, which is easy to manufacture, to be adopted for large displays.
• the polyimide film according to this embodiment has a low YI and excellent heat resistance, so it can be applied to either of the above light extraction methods.
• a polyamic acid composition is applied onto a support, heated to imidize, electronic elements, etc. are formed, and then the polyimide film is peeled off
• the adhesion between the support and the polyimide film is low, the polyimide film may peel off from the support during the electronic element formation process, which may adversely affect the formation of the electronic elements.
• the adhesion between the inorganic oxide film and the polyimide film is excellent.
• the adhesion here means adhesion strength.
• the peel strength between the polyimide film and the inorganic oxide film is preferably 0.05 N/cm or more, more preferably 0.10 N/cm or more, and even more preferably 0.10 N/cm or more and 1.00 N/cm or less.
• the peel strength is measured by the same method as in the examples described below or a method equivalent thereto.
• the polyimide film when peeling off the polyimide film from the laminate of the support and the polyimide film, the polyimide film is often peeled off from the support by laser irradiation.
• the cutoff wavelength of the polyimide film is required to be longer than the wavelength of the laser light used for peeling. Since a XeCl excimer laser with a wavelength of 308 nm is often used for laser peeling, the cutoff wavelength of the polyimide film is preferably 312 nm or more, and more preferably 330 nm or more.
• the cutoff wavelength of the polyimide film is preferably 420 nm or less.
• the cutoff wavelength of the polyimide film is preferably 320 nm or more and 410 nm or less, and more preferably 330 nm or more and 400 nm or less.
• the cutoff wavelength refers to the wavelength at which the transmittance is 0.1% or less, as measured by an ultraviolet-visible spectrophotometer.
• the polyamic acid composition and polyimide according to this embodiment may be used as is in a coating or molding process for producing a product or component, but may also be used as a material for further coating or other treatment of a film-shaped molded product.
• the polyamic acid composition or polyimide may be dissolved or dispersed in an organic solvent as necessary, and further blended with a photocurable component, a thermosetting component, a non-polymerizable binder resin, and other components as necessary to prepare a composition containing polyamic acid (1) or polyimide.
• various organic or inorganic low molecular weight compounds or polymeric compounds may be blended as additives into the polyamic acid composition.
• additives that can be used include dyes, surfactants, leveling agents, plasticizers, silicones, fine particles, and sensitizers.
• the fine particles include organic fine particles made of polystyrene, polytetrafluoroethylene, and the like, and inorganic fine particles made of colloidal silica, carbon, layered silicates, and the like, and may have a porous structure or a hollow structure.
• the function and form of the fine particles are not particularly limited, and may be, for example, a pigment, a filler, or a fibrous particle.
• Imidazoles can also be added to the polyamic acid composition according to this embodiment as an additive for imparting the above-mentioned functionality.
• imidazoles refer to compounds having a 1,3-diazole ring (1,3-diazole ring structure).
• Imidazoles are not particularly limited, but examples include 1H-imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-phenylimidazole.
• 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, and 2-phenylimidazole are preferred, and 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, and 2-phenylimidazole are more preferred.
• the content of imidazoles is preferably 0.005 mol or more and 0.1 mol or less, more preferably 0.01 mol or more and 0.08 mol or less, and even more preferably 0.015 mol or more and 0.050 mol or less, per 1 mol of amide groups in polyamic acid (1).
• the content of imidazoles is preferably 0.005 mol or more and 0.1 mol or less, more preferably 0.01 mol or more and 0.08 mol or less, and even more preferably 0.015 mol or more and 0.050 mol or less, per 1 mol of amide groups in polyamic acid (1).
• the method of mixing the polyamic acid (1) and the imidazole is not particularly limited. From the viewpoint of ease of controlling the molecular weight of the polyamic acid (1), it is preferable to add the imidazole to the polyamic acid (1) after polymerization. At this time, the imidazole may be added directly to the polyamic acid (1), or the imidazole may be dissolved in a solvent in advance and this solution may be added to the polyamic acid (1), and the addition method is not particularly limited.
• the polyamic acid composition according to this embodiment may be prepared by adding the imidazole to a solution containing the polyamic acid (1) after polymerization (solution after reaction).
• various inorganic thin films such as metal oxide thin films and transparent electrodes may be formed.
• the method for forming these inorganic thin films is not particularly limited, and examples include PVD methods such as sputtering, vacuum deposition, and ion plating, and CVD methods.
• the polyimide film according to the present embodiment is preferably used in fields and products where these properties are effective, since it has heat resistance, low thermal expansion, transparency, and the internal stress generated when it is laminated with a glass substrate is small, and it can ensure adhesion with inorganic materials during high-temperature processes.
• the polyimide film according to the present embodiment is preferably used in image display devices such as liquid crystal displays, organic electroluminescence (EL), and electronic paper, printed matter, color filters, flexible displays, optical films, 3D displays, touch panels, transparent conductive film substrates, solar cells, and more preferably as a replacement material for parts where glass is currently used.
• the thickness of the polyimide film is, for example, 1 ⁇ m or more and 200 ⁇ m or less, and preferably 3 ⁇ m or more and 100 ⁇ m or less.
• the thickness of the polyimide film can be measured using a laser hologram.
• the warpage of the laminate in a nitrogen atmosphere at a temperature of 25 ° C. was measured using a thin film stress measuring device (KLA Tencor Corporation "FLX-2320-S"). Then, the internal stress generated between the glass substrate and the polyimide film was calculated by the Stoney formula from the warpage of the glass substrate before the polyimide film was formed and the warpage of the laminate.
• TD1 1% weight loss temperature
• CTE Coefficient of Linear Expansion
• a SiOx film (thickness: 1 ⁇ m) was laminated on a Corning glass substrate (product name: Eagle XG, material: alkali-free glass, thickness: 0.7 mm, size: 100 mm ⁇ 100 mm) by plasma CVD.
• each polyamic acid composition prepared in the examples and comparative examples described later was applied on the SiOx film by a spin coater, heated in air at 80 ° C. for 30 minutes, and then heated in a nitrogen atmosphere at 350 ° C. for 60 minutes to obtain a laminate in which a SiOx film and a polyimide film (thickness: 6 ⁇ m) were laminated on the glass substrate in this order.
• the viscosity obtained here is referred to as “post-storage viscosity”.
• A excellent storage stability
• B not excellent storage stability
• MPA 3-methoxy-N,N-dimethylpropanamide
• BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
• ODPA 4,4'-oxydiphthalic anhydride
• SFDA spiro[11H-difuro[3,4-b:3',4'-i]xanthene-11,9'-[9H]fluorene]-1,3,7,9-tetrone
• TMHQ p-phenylenebis(trimellitic acid monoester acid anhydride)
• 8CI (1,3-dioxoisobenzofuran-5-yl) 1,3-dioxoisobenzofuran-5-carboxylate
• BPAF 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride
• PDA p-phenylenediamine 4-BAAB: 4-aminophenyl-4-aminobenzoate
• Example 1 In a 300 mL glass separable flask equipped with a stirrer with a stainless steel stirring rod and a nitrogen inlet tube, 60.0 g of MPA was placed as an organic solvent for polymerization. Then, while stirring the contents of the flask, 3.466 g of PDA and 0.804 g of 4-BAAB were placed in the flask and dissolved. Then, 0.832 g of SFDA, 1.092 g of ODPA and 8.806 g of BPDA were added to the contents of the flask, and the contents of the flask were stirred for 4 hours under an atmosphere at a temperature of 40° C.
• the obtained polyamic acid composition was applied to a Corning glass substrate (product name: Eagle XG, material: alkali-free glass, thickness: 0.7 mm, size: 100 mm x 100 mm) using a spin coater, and heated in air at 80°C for 30 minutes, and then heated in a nitrogen atmosphere at 350°C for 60 minutes to obtain a laminate (laminate of Example 1) having a 6 ⁇ m-thick polyimide film on the glass substrate.
• the ratio of the total substance amount of the diamines used to the total substance amount of the acid dianhydrides used was 101/100.
• Laminates of Examples 2 to 15 and Comparative Examples 1 to 6 were obtained in the same manner as Example 1, except that the acid dianhydrides used and their charging ratios, and the diamines used and their charging ratios were as shown in Table 1, and the thicknesses of the polyimide films were as shown in Table 2. Note that in each of Examples 2 to 15 and Comparative Examples 1 to 6, the total substance amount of the acid dianhydrides was the same as that of Example 1. Note that in each of Examples 2 to 15 and Comparative Examples 1 to 6, the total substance amount of the diamines was the same as that of Example 1.
• Table 1 shows the acid dianhydrides used and their charging ratios, and the diamines used and their charging ratios for Examples 1 to 15 and Comparative Examples 1 to 6.
• Table 2 also shows the evaluation results for the thickness, internal stress, CTE, TD1, peel strength, and storage stability of the polyimide film for Examples 1 to 15 and Comparative Examples 1 to 6.
• the polyamic acid in the prepared polyamic acid composition contained BPDA residues, SFDA residues, PDA residues, ester bond-containing residues, and diphenyl ether structure-containing residues.
• Examples 1 to 15 As shown in Table 2, in Examples 1 to 15, TD1 was 450°C or higher. Thus, the polyimides obtained in Examples 1 to 15 had excellent heat resistance. In Examples 1 to 15, the peel strength was 0.10 N/cm or higher. Thus, the polyimide films obtained in Examples 1 to 15 had excellent adhesion to the inorganic oxide film. In Examples 1 to 15, the evaluation result for storage stability was A. Thus, the polyamic acid compositions prepared in Examples 1 to 15 had excellent storage stability.
• the polyamic acid in the prepared polyamic acid composition did not have an SFDA residue.
• the polyamic acid in the prepared polyamic acid composition did not have a PDA residue.
• the polyamic acid in the prepared polyamic acid composition did not have an ester bond-containing residue.
• the polyamic acid in the prepared polyamic acid composition did not have a diphenyl ether structure-containing residue.
• the present invention can provide a polyamic acid composition capable of producing a polyimide having excellent storage stability, heat resistance, and adhesion to an inorganic oxide film.

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