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WO2021261177A1 - Poly(acide amique), solution de poly(acide amique), polyimide, film de polyimide, produit stratifié, procédé de production de produit stratifié et dispositif électronique - Google Patents

Poly(acide amique), solution de poly(acide amique), polyimide, film de polyimide, produit stratifié, procédé de production de produit stratifié et dispositif électronique Download PDF

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Publication number
WO2021261177A1
WO2021261177A1 PCT/JP2021/020630 JP2021020630W WO2021261177A1 WO 2021261177 A1 WO2021261177 A1 WO 2021261177A1 JP 2021020630 W JP2021020630 W JP 2021020630W WO 2021261177 A1 WO2021261177 A1 WO 2021261177A1
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Prior art keywords
polyamic acid
polyimide
polyimide film
less
film
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PCT/JP2021/020630
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English (en)
Japanese (ja)
Inventor
博文 中山
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Kaneka Corp
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Kaneka Corp
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Priority to CN202180045105.7A priority Critical patent/CN115803365B/zh
Priority to JP2022532465A priority patent/JP7756085B2/ja
Priority to KR1020237000492A priority patent/KR20230027146A/ko
Publication of WO2021261177A1 publication Critical patent/WO2021261177A1/fr
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • 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
    • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
    • C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a polyamic acid, a polyamic acid solution, a polyimide, a polyimide film, a laminate, a method for manufacturing the laminate, and an electronic device.
  • the present invention further relates to an electronic device material using polyimide, a thin film transistor (TFT) substrate, a flexible display substrate, a color filter, a printed matter, an optical material, an image display device (more specifically, a liquid crystal display device, an organic EL, an electron). Paper, etc.), 3D displays, solar cells, touch panels, transparent thin-film transistor substrates, and alternative materials for members for which glass is currently used.
  • TFT thin film transistor
  • various electronic elements such as thin film transistors and transparent electrodes are formed on the substrate, and a high temperature process is required to form these electronic elements.
  • Polyimide has sufficient heat resistance to adapt to high temperature processes, and its coefficient of thermal expansion (CTE) is close to that of glass substrates and electronic elements, so internal stress is unlikely to occur and it is suitable for substrate materials such as flexible displays. be.
  • aromatic polyimide is colored yellowish brown due to intramolecular conjugation and formation of charge transfer (CT) complex, but in top emission type organic EL etc., light is taken out from the opposite side of the substrate, so it is on the substrate. Transparency is not required, and conventional aromatic polyimides have been used.
  • a display element such as a transparent display, bottom emission type organic EL, or liquid crystal display
  • a full-scale display notchless
  • a sensor or the like is used.
  • the substrate is also required to have high optical characteristics (more specifically, transparency, etc.).
  • Patent Documents 1 and 2 A technique for suppressing the formation of a CT complex by using an aliphatic monomer in order to reduce the coloring of polyimide (Patent Documents 1 and 2), and a technique for enhancing transparency by using a monomer having a fluorine atom or a sulfur atom (Patent). Document 3) is known.
  • Patent Documents 1 and 2 have high transparency and low CTE, but have an aliphatic structure and therefore have a low thermal decomposition temperature, and are difficult to apply to a high temperature process for forming an electronic element.
  • the polyimide described in Patent Document 3 has high transparency, since it contains a fluorine atom, the adhesion to the barrier membrane and the electronic element formed on the polyimide substrate is lowered due to the decrease in the surface free energy, and the high temperature process is performed. It was found by the study of the present inventor that peeling may occur at the interface with the polyimide. Further, the polyimide described in Patent Document 3 may have poor adhesion between the polyimide and the barrier membrane or the electronic element due to the fluorine-based decomposition gas generated in the high temperature process. It was found by the inventor's examination.
  • the present invention has been achieved in view of the above circumstances, has excellent transparency, has high heat resistance, and is used with an inorganic material (more specifically, a glass substrate, a barrier membrane, etc.) in a high temperature process. It is an object of the present invention to provide a polyimide capable of ensuring adhesion and a polyamic acid as a precursor thereof. Another object of the present invention is to provide a product or member manufactured by using the polyimide and the polyamic acid, which is required to have heat resistance and transparency. In particular, it is an object of the present invention to provide a product or member formed on the surface of an inorganic substance such as glass, metal, metal oxide and single crystal silicon.
  • a polyimide obtained by imidizing a specific polyamic acid having a fluorene skeleton (fluorene structure) has excellent transparency, high heat resistance, and a glass substrate in a high temperature process.
  • the present invention has been completed by finding that adhesion with a barrier membrane can be ensured.
  • the polyamic acid according to the present invention contains a structural unit represented by the following chemical formula (1).
  • the polyamic acid according to the embodiment of the present invention further contains a structural unit represented by the following general formula (2).
  • X represents a tetravalent organic group different from the tetracarboxylic dianhydride residue in the chemical formula (1).
  • X in the general formula (2) is a tetravalent organic group represented by the following chemical formula (3) and a tetravalent organic group represented by the following chemical formula (4). It is one or more selected from the group consisting of organic groups.
  • the content of the structural unit represented by the chemical formula (1) is 1 mol% or more with respect to all the structural units.
  • the amount of substance ratio obtained by dividing the total amount of substance of the tetracarboxylic acid dianhydride residue by the total amount of substance of the diamine residue is 0.900 or more and less than 1.100. ..
  • the polyamic acid solution according to the present invention contains the polyamic acid according to the present invention and an organic solvent.
  • the polyimide according to the present invention is an imidized product of the polyamic acid according to the present invention.
  • the polyimide according to the present invention preferably has a 1% weight loss temperature of 500 ° C. or higher. Further, the polyimide according to the present invention preferably has a glass transition temperature of 400 ° C. or higher.
  • the polyimide film according to the present invention includes the polyimide according to the present invention.
  • the polyimide film according to the present invention preferably has a yellowness of 25 or less. Further, the polyimide film according to the present invention preferably has a haze of less than 1.0%.
  • the laminate according to the present invention has a support and a polyimide film according to the present invention.
  • a coating film containing the polyamic acid is formed by applying the polyamic acid solution according to the present invention onto a support, and the coating film is heated to imide the polyamic acid. To become.
  • the electronic device according to the present invention has a polyimide film according to the present invention and an electronic element arranged on the polyimide film.
  • the polyimide produced using the polyamic acid according to the present invention has excellent transparency and heat resistance, and can secure adhesion to an inorganic material in a high temperature process. Therefore, the polyimide produced by using the polyamic acid according to the present invention is required to have transparency and heat resistance, and is suitable as a material for an electronic device manufactured through a high temperature process.
  • the "structural unit” means a repeating unit constituting the polymer.
  • the "polyamic acid” is a polymer containing a structural unit represented by the following general formula (5) (hereinafter, may be referred to as “structural unit (5)").
  • A represents a tetracarboxylic acid dianhydride residue (a tetravalent organic group derived from a tetracarboxylic acid dianhydride), and B represents a diamine residue (a divalent organic derived from a diamine). Represents the group).
  • the content of the structural unit (5) with respect to all the 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, and more preferably 70 mol% or less. It is 100 mol% or less, more preferably 80 mol% or more and 100 mol% or less, still more preferably 90 mol% or more and 100 mol% or less, and may be 100 mol%.
  • the "1% weight reduction temperature” is the measured temperature when the weight of the polyimide at a measurement temperature of 150 ° C. is used as a reference (100% by weight) and the weight is reduced by 1% by weight with respect to the above standard weight.
  • the method for measuring the 1% weight loss temperature is the same method as in the examples described later or a method according to the same method.
  • the compound and its derivatives may be collectively referred to by adding "system” after the compound name.
  • the polymer name is represented by adding "system” after the compound name, it means that the repeating unit of the polymer is derived from the compound or its derivative.
  • the tetracarboxylic dianhydride may be referred to as "acid dianhydride”.
  • the polyamic acid according to this embodiment contains a structural unit represented by the following chemical formula (1) (hereinafter, may be referred to as “structural unit (1)”).
  • the structural unit (1) is a partial structure derived from 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride (hereinafter, may be referred to as "BPAF”) and 4-aminophenyl-4.
  • BPAF 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride
  • -Has a partial structure derived from aminobenzoate hereinafter, may be referred to as "4-BAAB”
  • the structural unit (1) has a BPAF residue as A in the above-mentioned general formula (5) and a 4-BAAB residue as B in the general formula (5).
  • 4-BAAB has a rigid structure, it is suitable as a raw material (monomer) for polyimide having a high glass transition temperature (excellent in heat resistance). Further, 4-BAAB having a rigid structure is also suitable as a raw material (monomer) for polyimide having high mechanical strength while suppressing the generation of internal stress. Since BPAF has a bulky fluorene structure, it is suitable as a raw material (monomer) for polyimide having excellent heat resistance and transparency.
  • a diamine other than 4-BAAB may be used as a monomer as long as its performance is not impaired.
  • diamines other than 4-BAAB include 1,4-diaminocyclohexane, p-phenylenediamine, m-phenylenediamine, 4,4'-oxydianiline, 3,4'-oxydianiline, and 2,2'.
  • the diamine other than 4-BAAB is preferably one or more selected from the group consisting of p-phenylenediamine and 4,4'-diaminobenzanilide, and p-. Phenylenediamine is more preferred.
  • the content of 4-BAAB residues with respect to all diamine residues constituting the polyamic acid is preferably 50 mol% or more, and is 70. It is more preferably mol% or more, further preferably 80 mol% or more, and may be 100 mol%.
  • the polyamic acid according to this embodiment has a structural unit represented by the following general formula (2) in addition to the structural unit (1) (hereinafter, "structural unit (2)". It may be described as).
  • structural unit (2) a structural unit represented by the following general formula (2) in addition to the structural unit (1)
  • structural unit (2) a structural unit represented by the following general formula (2) in addition to the structural unit (1)
  • structural unit (2) a structural unit represented by the following general formula (2) in addition to the structural unit (1)
  • structural unit (2) the arrangement of the structural unit (1) and the structural unit (2) in the polyamic acid may be random or block.
  • X represents a tetravalent organic group different from the tetracarboxylic dianhydride residue in the chemical formula (1).
  • X may be one kind or two or more kinds.
  • a suitable example of the acid dianhydride for forming the structural unit (2) is pyromellitic acid dianhydride (hereinafter, "PMDA"). (May be described), 3,3'4,4'-biphenyltetracarboxylic acid dianhydride (hereinafter, may be referred to as "BPDA”), p-phenylenebis (trimeritate anhydride), 2,3.
  • PMDA pyromellitic acid dianhydride
  • BPDA 3,3'4,4'-biphenyltetracarboxylic acid dianhydride
  • BPDA 3,3'4,4'-biphenyltetracarboxylic acid dianhydride
  • p-phenylenebis trimeritate anhydride
  • the acid dianhydride giving X in the general formula (2) is preferably one or more selected from the group consisting of PMDA and BPDA, and BPDA is more preferable. ..
  • PMDA is used as the acid dianhydride
  • X in the general formula (2) is a tetravalent organic group represented by the following chemical formula (3).
  • BPDA is used as the acid dianhydride
  • X in the general formula (2) is a tetravalent organic group represented by the following chemical formula (4).
  • the total acid dianhydride constituting the polyamic acid is obtained from the viewpoint of improving transparency, heat resistance, mechanical strength and internal stress.
  • the total content of BPAF residue, PMDA residue and BPDA residue with respect to the substance residue is preferably 60 mol% or more, more preferably 70 mol% or more, and more preferably 80 mol% or more. Is more preferable, and 100 mol% may be used.
  • the BPAF residue has a bulky structure derived from the fluorene structure, which contributes to the improvement of heat resistance, the improvement of transparency and the reduction of yellowness, and can suppress the crystallization of polyimide even if it is contained in a small amount. .. Therefore, the content of the structural unit (1) containing the BPAF residue is preferably 1 mol% or more, preferably 3 mol% or more, based on the total structural unit of the polyamic acid according to the present embodiment. More preferably, it is more preferably 5 mol% or more, and even more preferably 10 mol% or more.
  • the content of the structural unit (1) containing the BPAF residue is preferably 50 mol% or less, preferably 50 mol% or less, based on the total structural unit of the polyamic acid according to the present embodiment. It is more preferably mol% or less, and even more preferably 30 mol% or less.
  • the polyamic acid according to the present embodiment contains the structural unit (1) and the structural unit (2), all the structural units constituting the polyamic acid are considered from the viewpoints of improving transparency, heat resistance, mechanical strength and internal stress.
  • the total content of the structural unit (1) and the structural unit (2) is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more. , 100 mol% may be used.
  • the polyamic acid according to the present embodiment preferably satisfies the following condition 1 and is described below. It is more preferable to satisfy the condition 2, it is further preferable to satisfy the following condition 3, and it is further preferable to satisfy the following condition 4.
  • Condition 1 Polyamic acid contains at least one of PMDA residue and BPDA residue, and total content of BPAF residue, PMDA residue and BPDA residue with respect to all tetracarboxylic acid dianhydride residues constituting the polyamic acid. The rate is 100 mol%.
  • Condition 2 The content of 4-BAAB residues with respect to all the diamine residues constituting the polyamic acid satisfying the above condition 1 is 50 mol% or more and 100 mol% or less.
  • Condition 3 The above condition 1 is satisfied, and the content of the structural unit (1) is 1 mol% or more and 30 mol% or less with respect to all the structural units of the polyamic acid.
  • Condition 4 The above condition 2 is satisfied, and the content of the structural unit (1) is 1 mol% or more and 30 mol% or less with respect to all the structural units of the polyamic acid.
  • Amount of substance ratio (molar ratio) obtained by dividing the total amount of substance of tetracarboxylic acid dianhydride residue by the total amount of substance of diamine residue from the viewpoint of suppressing the decrease in transparency due to the residual unreacted monomer during polyimide formation. ) Is preferably 0.900 or more and less than 1.100, more preferably 0.950 or more and 1.080 or less, and further preferably 1.000 or more and 1.050 or less. By adjusting the substance amount ratio within the above range, a polyimide having excellent transparency can be obtained.
  • the polyamic acid of the present invention can be synthesized by a known general method, and can be obtained, for example, by reacting a diamine with a tetracarboxylic dianhydride in an organic solvent.
  • An example of a specific method for synthesizing polyamic acid will be described. First, in an atmosphere of an inert gas such as argon or nitrogen, diamine is dissolved in an organic solvent or dispersed in a slurry to prepare a diamine solution. Then, the tetracarboxylic dianhydride is added to the diamine solution after being dissolved in an organic solvent or dispersed in a slurry, or in a solid state.
  • an inert gas such as argon or nitrogen
  • the amount of diamine when using multiple diamines, the amount of each diamine
  • the amount of tetracarboxylic acid dianhydride When using multiple types of tetracarboxylic acid dianhydride, the amount of each tetracarboxylic acid dianhydride is adjusted) to obtain the desired polyamic acid (polymer of diamine and tetracarboxylic acid dianhydride). ) Can be obtained.
  • the amount of substance ratio (molar ratio) of each residue in the polyamic acid is, for example, the same as the amount of substance ratio of each monomer (diamine and tetracarboxylic acid dianhydride) used for the synthesis of the polyamic acid. Further, by blending two kinds of polyamic acids, a polyamic acid containing a plurality of kinds of tetracarboxylic acid dianhydride residues and a plurality of kinds of diamine residues can also be obtained.
  • the temperature condition of the reaction between the diamine and the tetracarboxylic dianhydride, that is, the synthetic reaction of the polyamic acid is not particularly limited, but is, for example, in the range of 20 ° C. or higher and 150 ° C. or lower.
  • the reaction time of the polyamic acid synthesis reaction is, for example, in the range of 10 minutes or more and 30 hours or less.
  • the organic solvent used for the synthesis of the polyamic acid is preferably a solvent capable of dissolving the tetracarboxylic acid dianhydride and the diamine used, and more preferably a solvent capable of dissolving the resulting polyamic acid.
  • examples of the organic solvent used for the synthesis of polyamic acid include urea-based solvents such as tetramethylurea and N, N-dimethylethylurea; sulfoxide-based solvents such as dimethylsulfoxide; and diphenylsulfones and tetramethylsulfones.
  • Solvent-based solvent such as N, N-dimethylacetamide (DMAC), N, N-dimethylformamide (DMF), N, N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), hexamethylphosphate triamide, etc.
  • Ester solvent such as ⁇ -butyrolactone
  • Alkyl halide solvent such as chloroform and methylene chloride
  • Aromatic hydrocarbon solvent such as benzene and toluene
  • Phenolic solvent such as phenol and cresol
  • Cyclopentanone and the like Ketone-based solvent examples thereof include ether-based solvents such as tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, dimethyl ether, diethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, and p-cresol methyl ether.
  • these solvents are used alone, but if necessary, two or more kinds may be used in combination as appropriate.
  • the organic solvent used in the synthetic reaction of polyamic acid in order to enhance the solubility and reactivity of polyamic acid is one or more selected from the group consisting of amide-based solvents, ketone-based solvents, ester-based solvents and ether-based solvents. Is preferable, and amide-based solvents (more specifically, DMF, DMAC, NMP, etc.) are more preferable. Further, the synthetic reaction of polyamic acid is preferably carried out in an atmosphere of an inert gas such as argon or nitrogen.
  • the weight average molecular weight of the polyamic acid according to the present embodiment is preferably in the range of 10,000 or more and 1,000,000 or less, and is preferably in the range of 20,000 or more and 500,000 or less, although it depends on the intended use. More preferably, it is more preferably in the range of 30,000 or more and 200,000 or less.
  • the weight average molecular weight is 10,000 or more, the polyamic acid or the polyimide obtained by using the polyamic acid can be easily used as a coating film or a polyimide film (film).
  • the weight average molecular weight used here means a polyethylene oxide equivalent value measured by gel permeation chromatography (GPC).
  • the polyimide according to the present embodiment is an imidized product of the polyamic acid according to the above-mentioned embodiment.
  • the polyimide according to this embodiment can be obtained by a known method, and the manufacturing method thereof is not particularly limited.
  • Imidization is performed by dehydrating and ring-closing the polyamic acid. This dehydration ring closure can be performed by an azeotropic method using an azeotropic solvent, a thermal method, or a chemical method.
  • the imidization of the polyamic acid to the polyimide can take any ratio of 1% or more and 100% or less.
  • a partially imidized polyamic acid may be synthesized.
  • the ring-closing reaction from the polyamic acid to the polyimide and the hydrolysis of the polyamic acid proceed at the same time, and the molecular weight of the polyimide is lower than the molecular weight of the polyamic acid, or water is added. Since there is a possibility of coloring due to the oxidation of diamine produced by hydrolysis, it is recommended to imidize a part of the polyamic acid in the polyamic acid solution in advance before forming the polyimide film described later to improve transparency and machine. It is preferable from the viewpoint of improving the characteristics.
  • a partially imidized polyamic acid may also be referred to as "polyamic acid".
  • the polyamic acid solution according to the present embodiment contains the above-mentioned polyamic acid according to the present embodiment and an organic solvent.
  • the organic solvent contained in the polyamic acid solution include organic solvents exemplified as organic solvents that can be used in the synthesis reaction of the polyamic acid, and include amide-based solvents, ketone-based solvents, ester-based solvents, and ethers.
  • One or more solvents selected from the group consisting of based solvents are preferable, and amide-based solvents (more specifically, DMF, DMAC, NMP, etc.) are more preferable.
  • the reaction solution solution after the reaction
  • the solid polyamic acid obtained by removing the solvent from the reaction solution may be dissolved in the solvent to prepare the polyamic acid solution according to the present embodiment.
  • the content of the polyamic acid in the polyamic acid solution according to the present 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 solution.
  • the dehydration ring closure of the polyamic acid may be performed by heating the polyamic acid.
  • the method for heating the polyamic acid is not particularly limited, but for example, the temperature after applying the polyamic acid solution according to the present embodiment described above on a support such as a glass substrate, a metal plate, or a PET film (polyethylene terephthalate film).
  • the heat treatment of the polyamic acid may be performed within the range of 40 ° C. or higher and 500 ° C. or lower.
  • the laminate according to the present embodiment has a support and a polyimide film (specifically, a polyimide film containing an imidized polyamic acid according to the present embodiment) arranged on the support. Is obtained.
  • the polyamic acid can be dehydrated and ring-closed by directly placing the polyamic acid solution in a container that has been subjected to a mold release treatment such as coating with a fluororesin, and heating and drying the polyamic acid solution under reduced pressure.
  • Polyimide can be obtained by dehydration ring closure of polyamic acid by these methods.
  • the heating time of each of the above treatments varies depending on the treatment amount and the heating temperature of the polyamic acid solution for dehydration and ring closure, but generally, it is in the range of 1 minute or more and 300 minutes or less after the treatment temperature reaches the maximum temperature. It is preferable to do so.
  • an imidizing agent and / or a dehydration catalyst is added to the polyamic acid solution, and the polyamic acid solution to which the imidizing agent and / or the dehydration catalyst is added is heated by the above method. May be imidized.
  • the imidizing agent is not particularly limited, but a tertiary amine can be used.
  • a tertiary amine a heterocyclic tertiary amine is preferable.
  • Preferred specific examples of the heterocyclic tertiary amine include pyridine, picoline, quinoline, isoquinoline, 1,2-dimethylimidazole and the like.
  • Preferred specific examples of the dehydration catalyst include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic acid anhydride, and trifluoroacetic anhydride.
  • the amount of the imidizing agent added is preferably 0.5 times molar equivalent or more and 5.0 times molar equivalent or less, and 0.7 times molar equivalent or more and 2.5 times molar equivalent or less with respect to the amide group of polyamic acid. More preferably, it is more preferably 0.8 times molar equivalent or more and 2.0 times molar equivalent or less.
  • the amount of the dehydration catalyst added is preferably 0.5 times molar equivalent or more and 10.0 times molar equivalent or less, and 0.7 times molar equivalent or more and 5.0 times molar equivalent or less with respect to the amide group of polyamic acid. Is more preferable, and more preferably 0.8 times molar equivalent or more and 3.0 times molar equivalent or less.
  • the "amide group of polyamic acid” refers to an amide group generated by the polymerization reaction of diamine and tetracarboxylic acid dianhydride.
  • the imidizing agent and / or the dehydration catalyst may be added directly without being dissolved in an organic solvent, or those dissolved in an organic solvent may be added.
  • the reaction may proceed rapidly before the imidizing agent and / or the dehydration catalyst diffuses, and a gel may be formed. Therefore, it is more preferable to add the solution obtained by dissolving the imidizing agent and / or the dehydration catalyst in an organic solvent to the polyamic acid solution.
  • the polyimide film according to this embodiment (specifically, the polyimide film containing an imidized polyamic acid according to this embodiment) is colorless and transparent, has a low yellowness, and has a glass transition temperature (heat resistance) that can withstand the TFT manufacturing process. Since it has, it is suitable as a transparent substrate material for flexible displays.
  • the content of the polyimide (specifically, the imidized polyamic acid according to the present embodiment) in the polyimide film according to the present embodiment is, for example, 70% by weight or more, and 80% by weight or more, based on the total amount of the polyimide film. It is preferably 90% by weight or more, and may be 100% by weight.
  • the component other than the polyimide in the polyimide film include additives (more specifically, nanosilica particles and the like) described later.
  • the electronic device according to the present embodiment has a polyimide film according to the present embodiment and an electronic element arranged on the polyimide film.
  • an inorganic base material such as glass is used as a support, and a polyimide film is formed on the support.
  • an electronic element such as a TFT
  • the step of forming the TFT is generally carried out in a wide temperature range of 150 ° C. or higher and 650 ° C. or lower, but in order to actually achieve the desired performance, the oxide semiconductor layer or the a-Si layer is carried out at 300 ° C. or higher. In some cases, a—Si and the like may be further crystallized by a laser or the like.
  • the 1% weight loss temperature of the polyimide is preferably 500 ° C. or higher because the barrier membrane and the like described later) and the electronic element may be peeled off.
  • the 1% weight loss temperature can be adjusted, for example, by changing the content of residues having a rigid structure (more specifically, 4-BAAB residues, BPDA 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. If the heat resistance of the polyimide is low, the polyimide and the inorganic film may be peeled off due to volatile components such as decomposition gas of the polyimide in a high temperature process after laminating the inorganic film. Therefore, in addition to the 1% weight loss temperature of the polyimide being 500 ° C. or higher, the weight loss rate when the polyimide is kept at an isothermal temperature within the range of 400 ° C. or higher and 450 ° C. or lower is less than 1%. desirable.
  • the polyimide film has a low fluorine atom content, and it is more preferable that the polyimide is derived from a monomer that does not contain a fluorine atom.
  • the Tg of the polyimide is preferably 300 ° C. or higher. It is more preferably 350 ° C. or higher, and even more preferably 400 ° C. or higher. The higher the upper limit of Tg of polyimide, the better, but it is, for example, 450 ° C. Further, since the coefficient of thermal expansion of the glass substrate is generally smaller than that of the resin, an internal stress is generated 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 further preferably 20 MPa or less.
  • the polyimide according to this embodiment can be suitably used as a material for a display substrate such as a TFT substrate or a touch panel substrate.
  • a method of forming an electronic device (specifically, an electronic device in which an electronic element is formed on a polyimide film) on a support as described above and then peeling the polyimide film from the support. In many cases, it is adopted.
  • the material of the support non-alkali glass is preferably used.
  • the polyamic acid solution according to the present embodiment is applied onto the support to form a coating film-containing laminate composed of a coating film containing polyamic acid and the support.
  • the coating film-containing laminate is heated under conditions of, for example, a temperature of 40 ° C. or higher and 200 ° C. or lower.
  • the heating time at this time is, for example, 3 minutes or more and 120 minutes or less.
  • a multi-step heating step may be provided, for example, the coating film-containing laminate may be heated at a temperature of 50 ° C. for 30 minutes and then heated at a temperature of 100 ° C. for 30 minutes.
  • the coating film-containing laminate is heated, for example, under the conditions of a maximum temperature of 200 ° C. or higher and 500 ° C. or lower.
  • the heating time (heating time at the maximum temperature) at this time is, for example, 1 minute or more and 300 minutes or less.
  • the rate of temperature rise is preferably 2 ° C./min or more and 10 ° C./min or less, and more preferably 4 ° C./min or more and 10 ° C./min or less.
  • the maximum temperature is preferably in the range of 250 ° C. or higher and 450 ° C. or lower.
  • the maximum temperature is 250 ° C. or higher, imidization proceeds sufficiently, and when the maximum temperature is 450 ° C. or lower, thermal deterioration and coloring of the polyimide can be suppressed. Further, it may be held at an arbitrary temperature for an arbitrary time until the maximum temperature is reached.
  • the imidization reaction can be carried out under air, under reduced pressure, or in an inert gas such as nitrogen, but in order to develop higher transparency, it is carried out under reduced pressure or in an inert gas such as nitrogen. Is preferable.
  • 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.
  • the polyamic acid in the coating film is imidized, and a laminate of the support and the polyimide film (imidized product of the polyamic acid) can be obtained. Further, in order to shorten the heating time and develop the characteristics, an imidizing agent or a dehydration catalyst may be added to the polyamic acid solution, and this solution may be heated by the above method for imidization.
  • a known method can be used as a method for peeling the polyimide film from the laminate of the obtained support and the polyimide film. For example, it may be peeled off by hand, or it may be peeled off using a mechanical device such as a drive roll or a robot. Further, a method of providing a release layer between the support and the polyimide film, 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 the substrate and the polyimide film are oxidized. It is also possible to adopt a method of peeling off the polyimide film by infiltrating an etching solution of silicon oxide between the film and the silicon film. Further, a method of separating the polyimide film by irradiation with a laser beam can also be adopted.
  • the polyimide film may peel off during the formation of the electronic element, or the yield may decrease when the polyimide film is peeled off after the electronic element is formed.
  • floating is caused by the auxiliary component (more specifically, the desorption component, etc.) generated at the time of imidization and the residual solvent, and the polyimide film and other material layers (more specifically, glass). It refers to a state in which poor adhesion has occurred with the substrate, barrier membrane, etc.).
  • floating includes a state in which the polyimide film is lifted from the glass substrate, a state in which a part of the polyimide film is destroyed and delamination occurs between the polyimide film and another material layer, and a barrier from the polyimide film.
  • the state where the film is raised and the like can be mentioned.
  • highly oriented molecular chains are tightly packed, and the subcomponents generated during imidization have poor gas release property and are prone to floating. According to the study of the present inventor, it has been found that floating can be prevented by introducing a bulky structure in the molecular chain or at the end.
  • the transparency of the 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, and 1.0%. It is more preferably less than, and may be 0%.
  • the polyimide film In applications where high transparency is required, the polyimide film is required to have high transmittance in the entire wavelength region, but the polyimide film tends to absorb light on the short wavelength side, and the film itself turns yellow. Often colored.
  • the yellowness (YI) of the polyimide film is preferably 25 or less, more preferably 20 or less, and more preferably 15 or less. Is more preferable, and may be 0. YI can be measured according to JIS K7373-2006.
  • the polyimide film to which transparency is imparted in this way is suitable for a transparent substrate for use as a substitute for glass and a substrate on which a sensor and a camera module are provided on the back surface.
  • a top emission method that extracts light from the TFT element side
  • a bottom emission method that extracts light from the back surface side of the TFT element.
  • the top emission method has the feature that the aperture ratio can be easily increased because the light is not blocked by the TFT element, and high-definition image quality can be obtained. It has the characteristic of being easy. If the TFT element is transparent, the aperture ratio can be improved even in the bottom emission method, so that the bottom emission method, which is easy to manufacture, tends to be adopted for large displays. Since the polyimide film according to this embodiment has a low YI and is excellent in heat resistance, it can be applied to either of the above light extraction methods.
  • the support and the polyimide are used. It is more preferable that the adhesion between the film and the film is excellent. Adhesion here means adhesion strength. In the manufacturing process of forming an electronic element or the like on the polyimide film on the support and then peeling off the polyimide film on which the electronic element or the like is formed from the support, if the adhesion between the polyimide film and the support is excellent, the electronic element Etc. can be formed or implemented more accurately.
  • the peel strength is preferably 0.05 N / cm or more, and more preferably 0.1 N / cm or more.
  • the polyimide film is often peeled 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 having 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. On the other hand, when the cutoff wavelength is a long wavelength, the polyimide film tends to be colored yellow.
  • the cutoff wavelength of the polyimide film is preferably 390 nm or less. From the viewpoint of achieving both transparency (low degree of yellowness) and processability of laser peeling, the cutoff wavelength of the polyimide film is preferably 320 nm or more and 390 nm or less, and more preferably 330 nm or more and 380 nm or less.
  • the cutoff wavelength in the present specification means a wavelength having a transmittance of 0.1% or less as measured by an ultraviolet-visible spectrophotometer.
  • the polyamic acid and polyimide according to the present embodiment may be used as they are in a coating or molding process for producing a product or a member, but for further coating or the like on a molded product formed into a film. It can also be used as a material.
  • Polyamic acid or polyimide is dissolved or dispersed in an organic solvent as needed for use in the coating or molding process, and further, photocurable components, thermosetting components, non-polymerizable binder resins and as required. Other components may be blended to prepare a polyamic acid composition or a polyimide resin composition.
  • various organic or inorganic low molecular weight compounds or high molecular weight compounds may be blended as additives.
  • a dye, a surfactant, a leveling agent, a plasticizer, silicone, fine particles, a sensitizer and the like can be used as the additive.
  • the fine particles include organic fine particles made of polystyrene, polytetrafluoroethylene and the like, inorganic fine particles made of colloidal silica, carbon, layered silicate and the like, and these 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 fibrous particles.
  • nanosilica particles may be used as the above additive, and the polyamic acid and the nanosilica particles may be combined.
  • the average primary particle diameter of the nanosilica particles is preferably 200 nm or less, more preferably 100 nm or less, further preferably 50 nm or less, and more preferably 30 nm or less. You may.
  • the average primary particle diameter of the nanosilica particles is preferably 5 nm or more, and more preferably 10 nm or more.
  • a known method can be used, and examples thereof include a method using an organosilica sol in which the nanosilica particles are dispersed in an organic solvent.
  • the polyamic acid may be synthesized and then the synthesized polyamic acid and the organosilica sol may be mixed, but the nanosilica particles may be more highly polyamic acid. In order to disperse in it, it is preferable to synthesize the polyamic acid in the organosilica sol.
  • the nanosilica particles can be surface-treated with a surface treatment agent.
  • a surface treatment agent a known one such as a silane coupling agent can be used.
  • the silane coupling agent an alkoxysilane compound having an amino group, a glycidyl group or the like as a functional group is widely known and can be appropriately selected.
  • the amino group-containing alkoxysilane is preferable as the silane coupling agent.
  • amino group-containing alkoxysilanes examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, and 3- (2-aminoethyl).
  • Examples of the surface treatment method for the nanosilica particles include a method of stirring a mixture in which a silane coupling agent is added to a dispersion liquid (organosilica sol) at an atmospheric temperature of 20 ° C. or higher and 80 ° C. or lower.
  • the stirring time at this time is, for example, 1 hour or more and 10 hours or less.
  • a catalyst or the like that promotes the reaction may be added.
  • the nanosilica particle-containing polyamic acid composition in which the polyamic acid and the nanosilica particles are composited preferably contains the nanosilica particles in a range of 1 part by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the polyamic acid. It is more preferable to include it in the range of 1 part by weight or more and 20 parts by weight or less.
  • the content of the nanosilica particles is 1 part by weight or more, the heat resistance of the polyimide containing the nanosilica particles can be improved and the internal stress can be sufficiently reduced, and when the content of the nanosilica particles is 30 parts by weight or less, the heat resistance can be sufficiently reduced. It is possible to suppress adverse effects on the mechanical properties and transparency of the polyimide containing nanosilica particles.
  • Imidazoles can also be added to the polyamic acid according to the present embodiment as the above-mentioned additive for imparting functionality.
  • imidazoles refer to compounds having a 1,3-diazole ring (1,3-diazol ring structure).
  • the imidazoles to be added to the polyamic acid according to the present embodiment are not particularly limited, and are, for example, 1H-imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and the like.
  • Examples thereof include 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole and the like.
  • 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole and 1-benzyl-2-phenylimidazole are preferable, and 1,2-dimethylimidazole and 1-benzyl-2-methylimidazole are more preferable. ..
  • the content of imidazoles is preferably 0.005 mol or more and 0.1 mol or less, and more preferably 0.01 mol or more and 0.08 mol or less, with respect to 1 mol of the amide group of polyamic acid. , 0.015 mol or more and 0.050 mol or less is more preferable.
  • 0.005 mol or more of imidazoles the film strength and transparency of the polyimide can be improved, and by setting the content of imidazoles to 0.1 mol or less, the storage stability of the polyamic acid is maintained. However, Tg and heat resistance can be improved.
  • a polymerization solvent such as NMP forms a complex with a carboxy group of a polyamic acid by a hydrogen bond, and when the imidization rate is slow, NMP or the like is contained in the polyimide film. It remains and may cause coloring by oxidizing or decomposing.
  • the imidazoles coordinate with the carboxy group of the polyamic acid and promote imidization, so that NMP and the like are less likely to remain in the polyimide film and at the same time suppress the decomposition of the polyamic acid in the thermal imidization process. Therefore, it is considered that the transparency is improved.
  • the mixing method of polyamic acid and imidazoles is not particularly limited. From the viewpoint of ease of controlling the molecular weight of the polyamic acid, it is preferable to add imidazoles to the polyamic acid after the polymerization. At this time, the imidazoles may be added to the polyamic acid as they are, or the imidazoles may be dissolved in a solvent in advance and this solution may be added to the polyamic acid, and the addition method is not particularly limited. The imidazoles may be added to the solution containing the polyamic acid after the polymerization (the solution after the reaction) to prepare the polyamic acid solution (solution containing the polyamic acid and the imidazoles) according to the present embodiment.
  • the polyamic acid solution according to the present embodiment may contain a silane coupling agent in order to develop appropriate adhesion to the support.
  • a silane coupling agent known ones can be used without particular limitation, but a compound containing an amino group is particularly preferable from the viewpoint of reactivity with the polyamic acid.
  • the mixing ratio of the silane coupling agent to 100 parts by weight of polyamic acid is preferably 0.01 parts by weight or more and 0.50 parts by weight or less, and more preferably 0.01 parts by weight or more and 0.10 parts by weight or less. It is preferably 0.01 parts by weight or more and 0.05 parts by weight or less.
  • inorganic thin films such as metal oxide thin films and transparent electrodes may be formed on the surface of the polyimide film according to the present embodiment.
  • the method for forming the inorganic thin film is not particularly limited, and examples thereof include a PVD method such as a CVD method, a sputtering method, a vacuum vapor deposition method, and an ion plating method.
  • the polyimide film according to this embodiment has a small internal stress generated when a laminated body is formed with a glass substrate, ensuring adhesion to an inorganic material in a high-temperature process. Therefore, it is preferable to use it in the field and product in which these characteristics are effective.
  • the polyimide film according to the present embodiment includes a liquid crystal display device, an organic EL, an image display device such as electronic paper, a printed matter, a color filter, a flexible display, an optical film, a 3D display, a touch panel, a transparent conductive film substrate, a solar cell, and the like. It is preferable to use it as a substitute material for the portion where glass is currently used.
  • the thickness of the polyimide film is preferably, for example, 1 ⁇ m or more and 200 ⁇ m or less, and preferably 5 ⁇ m or more and 100 ⁇ m or less.
  • the thickness of the polyimide film can be measured using a laser holo gauge.
  • the polyamic acid solution according to the present embodiment is used in a batch-type device manufacturing process in which a polyamic acid solution is applied on a support, heated to imidize, an electronic element or the like is formed, and then the polyimide film is peeled off. It can be suitably used. Therefore, the present embodiment also includes a method for manufacturing an electronic device, which comprises a step of applying a polyamic acid solution on a support, heating and imidizing the support, and forming an electronic element or the like on a polyimide film formed on the support. included. Further, the method for manufacturing such an electronic device may further include a step of peeling the polyimide film on which the electronic element or the like is formed from the support.
  • haze was measured by the method described in JIS K7136-2000 using an integrating sphere type haze meter (“HM-150N” manufactured by Murakami Color Technology Research Institute). did.
  • each polyamic acid solution prepared in Examples and Comparative Examples described later was placed on a glass substrate (material: non-alkali glass, thickness: 0.7 mm, size: 100 mm ⁇ 100 mm) manufactured by Corning Inc. for which the amount of warpage was measured in advance. It was applied with a spin coater and heated at 120 ° C. for 30 minutes in air, and then heated at 430 ° C. for 30 minutes in a nitrogen atmosphere to obtain a laminate having a polyimide film having a thickness of 10 ⁇ m on a glass substrate. In order to eliminate the influence of water absorption of the polyimide film, the laminate was dried at 120 ° C.
  • the amount of warpage of the laminate under a nitrogen atmosphere at a temperature of 25 ° C. was measured by a thin film stress measuring device (manufactured by KLA Tencor). It was measured using "FLX-2320-S"). Then, the internal stress generated between the glass substrate and the polyimide film was calculated from the amount of warping of the glass substrate and the amount of warping of the laminated body before the formation of the polyimide film by Stony's formula.
  • Glass transition temperature (Tg) The polyimide films obtained in Examples and Comparative Examples described later were sampled to a width of 3 mm and a length of 10 mm to obtain a sample for Tg measurement. Using a thermal analyzer (Hitachi High-Tech Science "TMA / SS7100"), a load of 98.0 mN was applied to the obtained sample, the temperature was raised from 20 ° C to 450 ° C at 10 ° C / min, and the temperature and strain were increased. The amount (elongation) was plotted to obtain a TMA curve. The temperature of the inflection point of the obtained TMA curve (the temperature corresponding to the peak in the differential curve of the TMA curve) was defined as the glass transition temperature (Tg).
  • Tg Glass transition temperature
  • TD1 1% weight loss temperature
  • a differential thermogravimetric simultaneous measuring device (“TG / DTA7200” manufactured by Hitachi High-Tech Science Co., Ltd.) was used, and the conditions were 20 ° C./min under a nitrogen atmosphere. The temperature is raised from 25 ° C. to 650 ° C., and the measured temperature is 1% weight loss temperature (TD1) when the sample weight is reduced by 1% by weight with respect to the standard weight based on the sample weight at the measurement temperature of 150 ° C. did.
  • NMP N-Methyl-2-pyrrolidone
  • BPAF 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride
  • BPDA 3,3'-4,4'-biphenyltetracarboxylic acid dianhydride
  • PMDA Piromellitic Acid Dianhydride 4-BAAB: 4-Aminophenyl-4-aminobenzoate
  • PDA p-phenylenediamine
  • TFMB 2,2'-bis (trifluoromethyl) benzidine
  • DMI 1,2-dimethylimidazole
  • Example 3 39.6 g of NMP was placed as an organic solvent for polymerization in a 300 mL glass separable flask equipped with a stirrer equipped with a stainless steel stir bar and a nitrogen introduction tube. Then, while stirring the contents of the flask, 3.030 g of 4-BAAB was placed in the flask and dissolved. Next, 0.183 g of BPAF was added to the flask contents, 3.788 g of BPDA was added, and the flask contents were stirred for 24 hours in an atmosphere at a temperature of 25 ° C. to obtain a polyamic acid solution.
  • the obtained polyamic acid solution was applied onto a glass substrate (manufactured by Corning, material: non-alkali glass, thickness: 0.7 mm, size: 100 mm ⁇ 100 mm) using a spin coater, and 30 at 120 ° C. in air. After heating for 30 minutes, the mixture was heated at 430 ° C. for 30 minutes in a nitrogen atmosphere to obtain a laminate having a polyimide film having a thickness of 10 ⁇ m on a glass substrate.
  • Example 4 39.6 g of NMP was placed as an organic solvent for polymerization in a 300 mL glass separable flask equipped with a stirrer equipped with a stainless steel stir bar and a nitrogen introduction tube. Then, while stirring the contents of the flask, 3.030 g of 4-BAAB was placed in the flask and dissolved. Next, 0.183 g of BPAF was added to the flask contents, 3.788 g of BPDA was added, and the flask contents were stirred for 24 hours under an atmosphere of a temperature of 25 ° C.
  • a polyamic acid solution 1 part by weight of DMI was added to the flask with respect to 100 parts by weight of the polyamic acid in the contents of the flask to obtain a polyamic acid solution.
  • the obtained polyamic acid solution was applied onto a glass substrate (manufactured by Corning, material: non-alkali glass, thickness: 0.7 mm, size: 100 mm ⁇ 100 mm) using a spin coater, and 30 at 120 ° C. in air. After heating for 30 minutes, the mixture was heated at 430 ° C. for 30 minutes in a nitrogen atmosphere to obtain a laminate having a polyimide film having a thickness of 10 ⁇ m on a glass substrate.
  • Examples 1, 5, 7, 9 and 11 A laminate having a polyimide film having a thickness of 10 ⁇ m on a glass substrate was obtained by the same method as in Example 3 except that the charging ratio of BPAF and BPDA was changed to the ratio shown in Table 1. In each of Examples 1, 5, 7, 9 and 11, the total amount of substance of acid dianhydride was the same as that of Example 3.
  • Example 2 A laminate having a polyimide film having a thickness of 10 ⁇ m on a glass substrate was obtained by the same method as in Example 4 except that the charging ratio of BPAF and BPDA was changed to the ratio shown in Table 1.
  • the total amount of substance of acid dianhydride was the same as that of Example 4.
  • Examples 13 and 15 Except for changing the charging ratio of BPAF and BPDA to the ratio shown in Table 1 and using 4-BAAB and PDA as diamines for the synthesis of polyamic acid in the ratio shown in Table 1, the same as in Example 3. By the same method, a laminate having a polyimide film having a thickness of 10 ⁇ m on a glass substrate was obtained. In each of Examples 13 and 15, the total amount of substance of acid dianhydride and the total amount of substance of diamine were the same as in Example 3.
  • Example 14 and 16 Except for changing the charging ratio of BPAF and BPDA to the ratio shown in Table 1 and using 4-BAAB and PDA as diamines for synthesizing the polyamic acid in the ratio shown in Table 1, the same as in Example 4. By the same method, a laminate having a polyimide film having a thickness of 10 ⁇ m on a glass substrate was obtained. In each of Examples 14 and 16, the total amount of substance of acid dianhydride and the total amount of substance of diamine were the same as in Example 4.
  • Example 17 A laminate having a polyimide film with a thickness of 10 ⁇ m was prepared on a glass substrate by the same method as in Example 4 except that PMDA was used instead of BPDA and BPAF and PMDA were used in the preparation ratios shown in Table 1. Obtained.
  • the total amount of substance of the acid dianhydride used in Example 17 was the same as the total amount of substance of the acid dianhydride used in Example 4.
  • the obtained polyamic acid solution was applied onto a glass substrate (manufactured by Corning, material: non-alkali glass, thickness: 0.7 mm, size: 100 mm ⁇ 100 mm) using a spin coater, and 30 at 120 ° C. in air. After heating for 30 minutes, the mixture was heated at 430 ° C. for 30 minutes in a nitrogen atmosphere to obtain a laminate having a polyimide film having a thickness of 10 ⁇ m on a glass substrate.
  • the obtained polyamic acid solution was applied onto a glass substrate (manufactured by Corning, material: non-alkali glass, thickness: 0.7 mm, size: 100 mm ⁇ 100 mm) using a spin coater, and 30 at 120 ° C. in air. After heating for 30 minutes, the mixture was heated at 430 ° C. for 30 minutes in a nitrogen atmosphere to obtain a laminate having a polyimide film having a thickness of 10 ⁇ m on a glass substrate.
  • Comparative Example 3 A laminate having a polyimide film having a thickness of 10 ⁇ m on a glass substrate was obtained by the same method as in Comparative Example 1 except that PDA was used instead of 4-BAAB. The amount of substance of PDA used in Comparative Example 3 was the same as the amount of substance of 4-BAAB used in Comparative Example 1.
  • Comparative Example 4 A laminate having a polyimide film having a thickness of 10 ⁇ m on a glass substrate was obtained by the same method as in Comparative Example 2 except that TFMB was used instead of 4-BAAB. The amount of substance of TFMB used in Comparative Example 4 was the same as the amount of substance of 4-BAAB used in Comparative Example 2.
  • Example 5 A polyimide film having a thickness of 10 ⁇ m was formed on a glass substrate by the same method as in Example 4 except that TFMB was used instead of 4-BAAB and the charging ratio of BPAF and BPDA was changed to the ratio shown in Table 1. Obtained a laminate to be provided.
  • the amount of substance of TFMB used in Comparative Example 5 was the same as the amount of substance of 4-BAAB used in Example 4.
  • the total amount of substance of the acid dianhydride used in Comparative Example 5 was the same as the total amount of substance of the acid dianhydride used in Example 4.
  • Example 1 For each of Examples 1 to 17 and Comparative Examples 1 to 5, the materials used and their ratios are shown in Table 1, and the physical properties and evaluations are shown in Table 2. In addition, in Table 1, "-" means that the said component was not used. Further, in Table 1, the numerical value in the column of "acid dianhydride” is the content ratio (unit: mol%) of each acid dianhydride with respect to the total amount of acid dianhydride used. The numerical value in the column of "diamine” is the content ratio (unit: mol%) of each diamine with respect to the total amount of diamines used. The numerical value in the column of "additive” is the amount of the additive added (unit: parts by weight) to 100 parts by weight of the polyamic acid in the flask contents.
  • the polyimide obtained from the polyamic acid according to the present invention has excellent transparency and heat resistance, and can secure adhesion to an inorganic material in a high temperature process.

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Abstract

L'invention concerne un poly(acide amique) comprenant un motif structural représenté par la formule chimique (1) ; une solution de poly(acide amique) comprenant un solvant organique et un poly(acide amique) comprenant un motif structural représenté par la formule chimique (1) ; un polyimide qui est un produit d'imidisation d'un poly(acide amique) comprenant un motif structural représenté par la formule chimique (1) ; un film de polyimide comprenant un produit d'imidisation d'un poly(acide amique) comprenant un motif structural représenté par la formule chimique (1) ; un produit stratifié comprenant un support et un film de polyimide comprenant un produit d'imidisation d'un poly(acide amique) comprenant un motif structural représenté par la formule chimique (1) ; et un dispositif électronique comprenant un film de polyimide comprenant un produit d'imidisation d'un poly(acide amique) comprenant un motif structural représenté par la formule chimique (1) et un élément électronique disposé sur le film de polyimide.
PCT/JP2021/020630 2020-06-23 2021-05-31 Poly(acide amique), solution de poly(acide amique), polyimide, film de polyimide, produit stratifié, procédé de production de produit stratifié et dispositif électronique Ceased WO2021261177A1 (fr)

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CN202180045105.7A CN115803365B (zh) 2020-06-23 2021-05-31 聚酰胺酸、聚酰胺酸溶液、聚酰亚胺、聚酰亚胺膜、层叠体、层叠体的制造方法及电子器件
JP2022532465A JP7756085B2 (ja) 2020-06-23 2021-05-31 ポリアミド酸、ポリアミド酸溶液、ポリイミド、ポリイミド膜、積層体、積層体の製造方法及び電子デバイス
KR1020237000492A KR20230027146A (ko) 2020-06-23 2021-05-31 폴리아미드산, 폴리아미드산 용액, 폴리이미드, 폴리이미드막, 적층체, 적층체의 제조 방법 및 전자 디바이스

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CN115803365A (zh) 2023-03-14
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TWI896686B (zh) 2025-09-11
CN115803365B (zh) 2024-07-30
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