Classifications

• • 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
• • 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
  • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
  • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
  • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
  • G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
• • 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
• • 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 polyamic acids, polyamic acid compositions, polyimides, polyimide films, laminates, methods for producing laminates, and electronic devices.
• the present invention further provides 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 EL, electronic paper, etc.), 3D displays, solar cells, touch panels, transparent conductive film substrates, and substitute materials for members currently using 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 adapt to high-temperature processes, and its coefficient of thermal expansion (CTE) is similar to that of glass substrates and electronic devices. be.
• Aromatic polyimides are generally colored yellowish brown due to intramolecular conjugation and formation of charge transfer (CT) complexes. Transparency is not required, and conventional aromatic polyimides have been used. However, in cases where the light emitted from the display element passes through the substrate, such as in transparent displays, bottom-emission organic EL, and liquid crystal displays, and in smartphones, etc., where full-screen displays (notchless) are required, sensors and When the camera module is arranged on the back surface of the substrate, the substrate is also required to have high optical properties (more specifically, transparency, etc.).
• CT charge transfer
• Patent Documents 1 and 2 In order to reduce the coloring of polyimide, a technique for suppressing the formation of a CT complex using an aliphatic monomer (Patent Documents 1 and 2), and a technique for improving transparency by using a monomer having a fluorine atom (Patent Document 3) )It has been known. Also, in order to obtain a low CTE polyimide, a polyimide having a naphthalene skeleton with high planarity has been studied (Patent Document 4).
• JP 2016-29177 A JP 2012-41530 A JP 2014-70139 A WO2016/166961
• Patent Documents 1 and 2 have high transparency and a low CTE, but because they have an aliphatic structure, they have a low thermal decomposition temperature and are difficult to apply to high-temperature processes when forming electronic elements.
• the present invention has been accomplished in view of the above circumstances, and an object of the present invention is to provide a polyimide having excellent heat resistance and high transmittance for light with a wavelength of 400 nm, and a polyamic acid as a precursor thereof. Another object of the present invention is to provide a product or member that is produced using the polyimide and polyamic acid and that requires heat resistance and transparency. In particular, it is an object of the present invention to provide a product or member in which the polyimide film of the present invention is formed on the surface of an inorganic material such as glass, metal, metal oxide, or single crystal silicon.
• the present invention includes the following aspects.
• a polyamic acid having a tetracarboxylic dianhydride residue and a diamine residue The tetracarboxylic dianhydride residue, 3,3',4,4'-biphenyltetracarboxylic dianhydride residue, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride residue a 4,4′-oxydiphthalic anhydride residue, and spiro[11H-diflo[3,4-b:3′,4′-i]xanthene-11,9′-[9H]fluorene]-1, containing one or more residues selected from the group consisting of 3,7,9-tetronic residues and a 2,3,6,7-naphthalenetetracarboxylic dianhydride residue, the diamine residue comprises a 2,2′-bis(trifluoromethyl)benzidine residue, The content of the 2,3,6,7-naphthalenetetracarboxylic dianhydr
• the diamine residue different from the 2,2′-bis(trifluoromethyl)benzidine residue is 4-aminophenyl-4-aminobenzoate residue, 9,9-bis(4-aminophenyl)fluorene and 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether residue, the polyamic acid according to [2] above.
• the content of diamine residues different from the 2,2'-bis(trifluoromethyl)benzidine residues is 1 mol% or more and 50 mol% or less with respect to the total amount of the diamine residues.
• the content of the 3,3',4,4'-biphenyltetracarboxylic dianhydride residue is 30 mol% or more and 50 mol% of the total amount of the tetracarboxylic dianhydride residue.
• the average value of the lowest unoccupied molecular orbital level of the tetracarboxylic dianhydride forming the tetracarboxylic dianhydride residue and the average value of the highest occupied molecular orbital level of the diamine forming the diamine residue is 2.25 eV or more, the polyamic acid according to any one of the above [1] to [5].
• a polyimide which is an imidized polyamic acid according to any one of [1] to [6].
• a laminate comprising a support and the polyimide film according to any one of [13] to [15].
• [17] A method for producing a laminate having a support and a polyimide film, By coating the polyamic acid composition according to any one of [7] to [10] on a support, a coating film containing the polyamic acid is formed, and the coating film is heated to form the polyamide A method for producing a laminate by imidating an acid.
• An electronic device comprising the polyimide film according to any one of [13] to [15] and an electronic element disposed on the polyimide film.
• the polyimide produced using the polyamic acid according to the present invention has excellent heat resistance and high transmittance of light with a wavelength of 400 nm. Therefore, the polyimide produced using the polyamic acid according to the present invention is suitable as a material for electronic devices that require heat resistance and transparency.
• a “structural unit” refers to a repeating unit that constitutes a polymer.
• a “polyamic acid” is a polymer containing a structural unit represented by the following general formula (1) (hereinafter sometimes referred to as “structural unit (1)").
• a 1 represents a tetracarboxylic dianhydride residue (tetravalent organic group derived from tetracarboxylic dianhydride)
• a 2 represents a diamine residue (divalent organic group derived from diamine organic group).
• the content of the structural unit (1) with respect 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%. 100 mol % or more, 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 %.
• 1% weight loss temperature is the measurement temperature when the weight of polyimide at a measurement temperature of 150°C is taken as the reference (100% by weight), and the weight is reduced by 1% by weight with respect to the reference weight.
• the method for measuring the 1% weight loss temperature is the same method as in Examples described later or a method based thereon.
• Plasticizer refers to a material that exists as a liquid during the imidization of at least a portion of polyamic acid.
• system may be added after the name of the compound to generically refer to the compound and its derivatives.
• polymer name is expressed by adding "system” after the compound name, it means that the repeating unit of the polymer is derived from the compound or its derivative.
• a tetracarboxylic dianhydride may be described as an "acid dianhydride”.
• the components, functional groups, and the like exemplified in this specification may be used alone or in combination of two or more.
• Polyamic acid according to the present embodiment (hereinafter sometimes referred to as "polyamic acid (1)”) has a tetracarboxylic dianhydride residue and a diamine residue.
• the tetracarboxylic dianhydride residue is 3,3′,4,4′-biphenyltetracarboxylic dianhydride residue, 9,9-bis(3,4-dicarboxyphenyl ) fluorene dianhydride residue, 4,4′-oxydiphthalic anhydride residue, and spiro[11H-difuro[3,4-b:3′,4′-i]xanthene-11,9′-[9H ]fluorene]-1,3,7,9-tetrone residues and 2,3,6,7-naphthalenetetracarboxylic acid dianhydride residues.
• the polyamic acid (1) contains, as tetracarboxylic dianhydride residues, 3,3′,4,4′-biphenyltetracarboxylic dianhydride residues, 9,9-bis(3,4-di carboxyphenyl)fluorene dianhydride residue, 4,4′-oxydiphthalic anhydride residue, and spiro[11H-difuro[3,4-b:3′,4′-i]xanthene-11,9′- [9H]fluorene]-1,3,7,9-tetrone residue and one or more residues selected from the group consisting of 2,3,6,7-naphthalenetetracarboxylic acid dianhydride residue include.
• the diamine residue includes a 2,2'-bis(trifluoromethyl)benzidine residue. That is, polyamic acid (1) contains a 2,2'-bis(trifluoromethyl)benzidine residue as a diamine residue.
• 3,3′,4,4′-biphenyltetracarboxylic dianhydride residue is 3,3′,4,4′-biphenyltetracarboxylic dianhydride (hereinafter sometimes referred to as “BPDA” ) is the partial structure derived from 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride residue is 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (hereinafter referred to as "BPAF” is a partial structure derived from The 4,4'-oxydiphthalic anhydride residue is a partial structure derived from 4,4'-oxydiphthalic anhydride (hereinafter sometimes referred to as "ODPA").
• Spiro[11H-diflo[3,4-b:3′,4′-i]xanthene-11,9′-[9H]fluorene]-1,3,7,9-tetrone residue is spiro[11H- Diflo[3,4-b:3′,4′-i]xanthene-11,9′-[9H]fluorene]-1,3,7,9-tetrone (hereinafter sometimes referred to as “SFDA” ) is the partial structure derived from 2,3,6,7-naphthalenetetracarboxylic dianhydride residue is a portion derived from 2,3,6,7-naphthalenetetracarboxylic dianhydride (hereinafter sometimes referred to as "NTCDA”) Structure.
• NTCDA 2,3,6,7-naphthalenetetracarboxylic dianhydride
• the 2,2'-bis(trifluoromethyl)benzidine residue is a partial structure derived from 2,2'-bis(trifluoromethyl)benzidine (hereinafter sometimes referred to as "TFMB").
• the SFDA residue is a tetravalent organic group represented by the following chemical formula (2).
• the content of NTCDA residues is 5 mol% or more and 90 mol% or less with respect to the total amount of tetracarboxylic dianhydride residues. Furthermore, in polyamic acid (1), the content of TFMB residues is 50 mol% or more relative to the total amount of diamine residues.
• polyimides obtained from polyamic acids having NTCDA residues and TFMB residues have a high 1% weight loss temperature (TD1) (excellent heat resistance) and a low CTE due to their rigid structures.
• TD1 excellent heat resistance
• internal stress hereinafter sometimes simply referred to as "internal stress”
• Polyimide using NTCDA as an acid dianhydride monomer has a transmittance of light with a wavelength of 400 nm (hereinafter referred to as "400 nm transmittance" compared to polyimide using pyromellitic dianhydride as an acid dianhydride monomer. ) tend to be higher.
• the 400 nm transmittance of polyimide obtained from polyamic acid having only NTCDA residue as tetracarboxylic dianhydride residue and only TFMB residue as diamine residue is used for applications requiring high transparency. is insufficient.
• one or more residues selected from the group consisting of BPDA residues, BPAF residues, ODPA residues and SFDA residues (hereinafter referred to as "specific acid dianhydride residues" may be described), an NTCDA residue, and a TFMB residue, and the content of the NTCDA residue and the TFMB residue is a polyimide obtained from a polyamic acid (polyamic acid (1)) having a specific range , and found that the 400 nm transmittance is high while being excellent in heat resistance.
• the content of the NTCDA residue is 5 mol% or more and 90 mol% or less with respect to the total amount of the tetracarboxylic dianhydride residue, and the content of the TFMB residue The ratio is 50 mol % or more with respect to the total amount of diamine residues.
• the content of the NTCDA residue is preferably 10 mol % or more, more preferably 15 mol % or more, and even more preferably 20 mol % or more.
• the content of NTCDA residues is 85 mol% or less with respect to the total amount of tetracarboxylic dianhydride residues constituting polyamic acid (1). preferably 80 mol % or less.
• the content of the specific acid dianhydride residue is the total amount of the tetracarboxylic acid dianhydride residue constituting the polyamic acid (1).
• it is preferably 10 mol % or more and 95 mol % or less, more preferably 10 mol % or more and 90 mol % or less, and even more preferably 10 mol % or more and 80 mol % or less.
• the "content rate of specific acid dianhydride residues" is the total content of multiple types of specific acid dianhydride residues. represents
• a BPDA residue is preferable as the specific acid dianhydride residue in order to obtain a polyimide with superior heat resistance.
• the specific acid dianhydride residue is preferably one or more residues selected from the group consisting of BPAF residues, ODPA residues and SFDA residues.
• the specific acid dianhydride residue is preferably one or more residues selected from the group consisting of BPAF residues and SFDA residues.
• the content of one or more residues selected from the group consisting of BPAF residues and SFDA residues is preferably 10 mol% or more and 50 mol% or less, relative to the total amount of tetracarboxylic dianhydride residues constituting the polyamic acid (1), and 20 mol% or more and 50 It is more preferably mol % or less, and even more preferably 30 mol % or more and 50 mol % or less.
• the content of the BPDA residue must be less than the tetracarboxylic acid dicarboxylic acid constituting the polyamic acid (1). It is preferably 5 mol% or more and 90 mol% or less, more preferably 5 mol% or more and 70 mol% or less, and 5 mol% or more and 50 mol% or less, relative to the total amount of the anhydride residue. is more preferred.
• the content of the BPAF residue must be less than the tetracarboxylic acid dicarboxylic acid constituting the polyamic acid (1). It is preferably 1 mol% or more and 50 mol% or less, more preferably 1 mol% or more and 40 mol% or less, and 1 mol% or more and 30 mol% or less, relative to the total amount of the anhydride residue. is more preferred.
• the content of the ODPA residue must be less than the tetracarboxylic acid dicarboxylic acid constituting the polyamic acid (1). It is preferably 5 mol% or more and 30 mol% or less, more preferably 5 mol% or more and 20 mol% or less, and 5 mol% or more and 10 mol% or less, relative to the total amount of the anhydride residue. is more preferred.
• the content of the SFDA residue must be less than the tetracarboxylic acid dicarboxylic acid constituting the polyamic acid (1). It is preferably 1 mol% or more and 50 mol% or less, more preferably 1 mol% or more and 40 mol% or less, and 1 mol% or more and 30 mol% or less, relative to the total amount of the anhydride residue. is more preferred.
• the content of TFMB residues is 55 mol% or more with respect to the total amount of diamine residues constituting polyamic acid (1). is preferably 60 mol% or more, more preferably 65 mol% or more, even more preferably 70 mol% or more, 75 mol% or more, 80 mol% or more, 85 mol % or more, 90 mol % or more, 95 mol % or more, or 100 mol %.
• acid dianhydrides other than NTCDA and specific acid dianhydrides may be used as monomers within a range that does not impair its performance.
• acid dianhydrides other than NTCDA and specific acid dianhydrides include pyromellitic dianhydride, p-phenylenebis(trimellitate anhydride), and 1,2,5,6-naphthalenetetracarboxylic dianhydride.
• the total content of NTCDA residues and specific acid dianhydride residues is a tetracarboxylic acid dianhydride that constitutes polyamic acid (1) It is preferably 70 mol% or more, more preferably 75 mol% or more, still more preferably 80 mol% or more, and even more preferably 85 mol% or more, relative to the total amount of the residue. Preferably, it may be 90 mol % or more, 95 mol % or more, or 100 mol %.
• a diamine other than TFMB may be used as a monomer within a range that does not impair its performance.
• diamines other than TFMB include p-phenylenediamine, 4-aminophenyl-4-aminobenzoate (hereinafter sometimes referred to as “BAAB”), 9,9-bis(4-aminophenyl)fluorene ( hereinafter sometimes referred to as “BAFL”), 2,2′-bis(trifluoromethyl)-4,4′-diaminodiphenyl ether (hereinafter sometimes referred to as “6FODA”), 1,4- cyclohexanediamine, 4,4'-diaminobenzanilide, m-phenylenediamine, 4,4'-oxydianiline, 3,4'-oxydianiline, N,N'-bis(4-aminophenyl)terephthalamide, 4,4'-diaminodiphenylsul
• BAAB 4-aminopheny
• any As the diamine residue is preferably a residue derived from diamine of ⁇ 5.20 eV or less, and a residue derived from diamine of ⁇ 5.30 eV or less. More preferred are residues, more preferred are those derived from diamines of -5.40 eV or less, and even more preferred are those derived from diamines of -5.50 eV or less.
• the polyamic acid (1) has an arbitrary diamine residue
• the polyamic acid (1) in order to obtain a polyimide with a higher 400 nm transmittance, has a HOMO of ⁇ 5.20 eV or less as an arbitrary diamine residue. It is preferred to have only diamine-derived residues.
• the optional diamine residue is preferably a diamine-derived residue with a HOMO of ⁇ 6.20 eV or more.
• diamine-derived residues with a HOMO of -5.20 eV or less examples include BAAB residues, BAFL residues, 6FODA residues, and the like. That is, when polyamic acid (1) has an optional diamine residue, in order to obtain a polyimide with a higher 400 nm transmittance, the optional diamine residue is a group consisting of BAAB residue, BAFL residue and 6FODA residue One or more selected residues are preferred.
• the polyamic acid (1) when the polyamic acid (1) has an optional diamine residue, in order to obtain a polyimide with a higher 400 nm transmittance, the polyamic acid (1) may contain, as optional diamine residues, a BAAB residue, a BAFL residue and It is preferred to have only one or more residues selected from the group consisting of 6FODA residues.
• the content of the arbitrary diamine residue (when having multiple types of arbitrary diamine residues is preferably 1 mol% or more and 50 mol% or less, and 1 mol% or more and 40 mol% or less with respect to the total amount of diamine residues constituting the polyamic acid (1). is more preferably 1 mol% or more and 30 mol% or less, even more preferably 1 mol% or more and 20 mol% or less, 1 mol% or more and 15 mol% or less or 5 mol% or more and 15 mol % or less.
• the polyamic acid (1) has an arbitrary diamine residue, and the content of the arbitrary diamine residue (the total content when there are multiple types of arbitrary diamine residues) is the diamine residue constituting the polyamic acid (1) When it is 1 mol% or more and 50 mol% or less with respect to the total amount of the groups, in order to obtain a polyimide having excellent heat resistance, the content of the BPDA residue is the tetracarboxylic dianhydride that constitutes the polyamic acid (1). It is preferably 30 mol % or more and 50 mol % or less with respect to the total amount of the residue.
• the lowest unoccupied orbital level of the tetracarboxylic dianhydride that forms the tetracarboxylic dianhydride residue in the polyamic acid (1) (hereinafter referred to as "LUMO"
• the difference between the average value of HOMO of the diamine that forms the diamine residue in polyamic acid (1) and the average value of HOMO (hereinafter sometimes referred to as “average level difference”) is , is preferably 2.25 eV or more, more preferably 2.30 eV or more, still more preferably 2.35 eV or more, and may be 2.40 eV or more.
• Both the LUMO of the tetracarboxylic dianhydride and the HOMO of the diamine are values calculated by density functional theory (DFT).
• Average LUMO of tetracarboxylic dianhydride is obtained by multiplying the LUMO of NTCDA by the mole fraction of NTCDA and the LUMO of the specific acid dianhydride by the mole fraction of the specific acid dianhydride.
• the numerical value (when using multiple types of specific acid dianhydrides, each numerical value) and the LUMO of other acid dianhydrides used as needed were multiplied by the mole fraction of other acid dianhydrides. It is a value obtained by summing up numerical values (each numerical value when multiple kinds of other acid dianhydrides are used).
• the "average HOMO value of diamine” is also calculated by the same method as the above-described "average LUMO value of tetracarboxylic dianhydride".
• the average level difference is preferably 2.80 eV or less, more preferably 2.70 eV or less. It is more preferably 60 eV or less.
• the polyamic acid (1) preferably satisfies the following condition 1, and more preferably satisfies the following condition 2. It is more preferable to satisfy condition 3 below.
• Condition 1 The content of NTCDA residues is 10 mol% or more and 90 mol% or less with respect to the total amount of tetracarboxylic dianhydride residues constituting polyamic acid (1), and the content of TFMB residues is 90 mol % or more and 100 mol % or less with respect to the total amount of diamine residues constituting the polyamic acid (1).
• Condition 2 Condition 1 above is satisfied, and the specific acid dianhydride residue is one or more residues selected from the group consisting of BPAF residues and SFDA residues.
• Condition 3 Content of one or more residues that satisfy Condition 2 above and are selected from the group consisting of BPAF residues and SFDA residues (when both BPAF residues and SFDA residues are present, their total content ratio) is 10 mol % or more and 50 mol % or less with respect to the total amount of tetracarboxylic dianhydride residues constituting polyamic acid (1).
• Polyamic acid (1) can be synthesized by a known general method, and can be obtained, for example, by reacting a diamine and a tetracarboxylic dianhydride in an organic solvent.
• An example of a specific method for synthesizing polyamic acid (1) will be described.
• a diamine solution is prepared by dissolving or dispersing a diamine in an organic solvent in an inert gas atmosphere such as argon or nitrogen.
• the tetracarboxylic dianhydride is added to the diamine solution after dissolving it in an organic solvent or dispersing it in a slurry state, or in a solid state.
• the substance amount of the diamine when using multiple types of diamines, the substance amount of each diamine
• the substance amount of the tetracarboxylic dianhydride When using multiple types of tetracarboxylic dianhydrides, the amount of each tetracarboxylic dianhydride is adjusted to obtain the desired polyamic acid (polymer of diamine and tetracarboxylic dianhydride ) can be obtained.
• the molar fraction of each residue in polyamic acid (1) matches, for example, the molar fraction of each monomer (diamine and tetracarboxylic dianhydride) used in synthesizing polyamic acid (1).
• Polyamic acid (1) containing multiple types of tetracarboxylic dianhydride residues and multiple types of diamine residues can also be obtained by blending two types of polyamic acids.
• the temperature conditions for the reaction between the diamine and the tetracarboxylic dianhydride, that is, the synthesis reaction of the polyamic acid (1) are not particularly limited, but are, for example, in the range of 20°C or higher and 150°C or lower.
• the reaction time for the synthetic reaction of polyamic acid (1) is, for example, in the range of 10 minutes or more and 30 hours or less.
• the organic solvent used for synthesizing polyamic acid (1) is preferably a solvent capable of dissolving the tetracarboxylic dianhydride and diamine used, and more preferably a solvent capable of dissolving polyamic acid (1) to be produced.
• organic solvents used for synthesizing polyamic acid (1) include urea-based solvents such as tetramethylurea and N,N-dimethylethylurea; sulfoxide-based solvents such as dimethylsulfoxide; diphenylsulfone and tetramethylsulfone.
• Sulfone-based solvents such as; N,N-dimethylacetamide (DMAC), N,N-dimethylformamide (DMF), N,N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), 3-methoxy-N , N-dimethylpropanamide (MPA), hexamethylphosphoric triamide and other amide solvents; ⁇ -butyrolactone and other ester solvents; chloroform, methylene chloride and other halogenated alkyl solvents; benzene, toluene and other aromatic carbonization Hydrogen-based solvents; phenolic solvents such as phenol and cresol; ketone-based solvents such as cyclopentanone; Ether-based solvents such as cresol methyl ether are included.
• DMAC N,N-dimethylacetamide
• DMF N,N-dimethylformamide
• NMP N,N-diethylacetamide
• NMP N-methyl-2-pyr
• the organic solvent used in the synthetic reaction of the polyamic acid (1) consists of amide solvents, ketone solvents, ester solvents and ether solvents.
• amide solvents more specifically, DMF, DMAC, NMP, MPA, etc.
• the synthetic reaction of polyamic acid (1) is preferably carried out in an inert gas atmosphere such as argon or nitrogen.
• the weight average molecular weight of the polyamic acid (1) is preferably in the range of 10,000 or more and 1,000,000 or less, and more preferably in the range of 20,000 or more and 500,000 or less, depending on the application. More preferably, it is in the range of 30,000 or more and 200,000 or less. If the weight-average molecular weight is 10,000 or more, polyamic acid (1) or polyimide obtained using polyamic acid (1) can be easily formed into a coating film or a polyimide film (film). On the other hand, when the weight-average molecular weight is 1,000,000 or less, it exhibits sufficient solubility in a solvent, so a coating film or polyimide film having a smooth surface and a uniform thickness using a polyamic acid composition described later is obtained.
• the weight average molecular weight used here means a polyethylene oxide equivalent value measured using gel permeation chromatography (GPC).
• a method for controlling the molecular weight of the polyamic acid (1) a method of using either an acid dianhydride or a diamine in excess, a monofunctional acid anhydride such as phthalic anhydride or aniline, or an amine A method of quenching the reaction by reacting is included.
• a polyimide film having sufficient strength can be obtained if the molar ratio of these charged is between 0.95 and 1.05.
• the molar ratio of the charge is the ratio of the total amount of diamines used in the synthesis of polyamic acid (1) to the total amount of acid dianhydrides used in the synthesis of polyamic acid (1) (total amount of diamines amount/total substance amount of acid dianhydride). Further, by terminal-capping with phthalic anhydride, maleic anhydride, aniline, or the like, coloring of the polyimide obtained using the polyamic acid (1) can be further reduced.
• the polyamic acid composition according to the present embodiment contains polyamic acid (1) and an organic solvent.
• the organic solvent contained in the polyamic acid composition according to the present embodiment include the organic solvents exemplified as the organic solvent that can be used in the synthesis reaction of the polyamic acid (1), such as amide solvents and ketone solvents. , ester solvents and ether solvents are preferable, and amide solvents (more specifically, DMF, DMAC, NMP, MPA, etc.) are more preferable.
• the reaction solution solution after reaction itself may be used as the polyamic acid composition according to the present 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 the present embodiment.
• the content of polyamic acid (1) in the polyamic acid composition according to the present embodiment is not particularly limited, but is, for example, 1% by weight or more and 80% by weight or less based on the total amount of the polyamic acid composition.
• the polyamic acid composition according to the present embodiment may contain an imidization accelerator and/or a dehydration catalyst in order to shorten the heating time and develop properties.
• a tertiary amine can be used as the imidization accelerator.
• a heterocyclic tertiary amine is preferred as the tertiary amine.
• Preferable specific examples of heterocyclic tertiary amines include pyridine, picoline, quinoline, isoquinoline and imidazoles.
• Preferred specific examples of the dehydration catalyst include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride.
• the amount of the imidization accelerator is preferably 0.1 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the polyamic acid (1). It is more preferably 0.5 parts by weight or more and 5 parts by weight or less.
• the amount of the dehydration catalyst is preferably 0.1 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the polyamic acid (1). It is more preferably 0.5 parts by weight or more and 5 parts by weight or less.
• imidazoles are preferable.
• imidazoles refer to compounds having a 1,3-diazole ring (1,3-diazole ring structure).
• the imidazoles that can be added to the polyamic acid composition according to the present embodiment are not particularly limited. imidazole, 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 preferred, and 1,2-dimethylimidazole and 1-benzyl-2-methylimidazole are more preferred. .
• the content of the imidazole is preferably 0.005 mol or more and 0.1 mol or less, and 0.01 mol or more and 0.08 mol or less, relative to 1 mol of the amide group of the polyamic acid (1). is more preferably 0.015 mol or more and 0.050 mol or less.
• amide group of polyamic acid (1) refers to an amide group produced by a polymerization reaction of diamine and tetracarboxylic dianhydride.
• the method of mixing polyamic acid (1) and imidazoles is not particularly limited. From the viewpoint of ease of controlling the molecular weight of polyamic acid (1), it is preferable to add imidazoles to polyamic acid (1) after polymerization. At this time, the imidazole may be added as it is 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). Not restricted.
• the polyamic acid composition according to the present embodiment may be prepared by adding imidazoles to a solution containing polyamic acid (1) after polymerization (solution after reaction).
• additives may be added as additives to the polyamic acid composition according to the present embodiment.
• additives include plasticizers, antioxidants, dyes, surfactants, leveling agents, silicones, fine particles, and sensitizers.
• the fine particles include organic fine particles made of polystyrene, polytetrafluoroethylene, etc., inorganic fine particles made of colloidal silica, carbon, layered silicate, etc. They 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, pigments, fillers, or fibrous particles.
• the colored polyimide had an imidization reaction temperature of 300°C. At an imidization reaction temperature of 350°C, the imidation was 90% or more, and nearly 100%. However, a clear difference in the imidization rate was observed.
• the driving force during the dehydration ring closure from polyamic acid to polyimide by thermal imidization is largely due to the molecular motion caused by heat and the plasticizing effect of the solvent. should be treated.
• a rigid acid dianhydride such as NTCDA
• TFMB TFMB
• the resulting polyimide has a glass transition temperature exceeding 400° C., and sometimes the glass transition temperature is higher than the heat treatment temperature during film formation. Therefore, in the imidization reaction between a rigid acid dianhydride such as NTCDA and TFMB, the imidization may not proceed completely.
• the plasticizer As a plasticizer that can be used in this embodiment, a material that dissolves in the solvent used for imidizing the polyamic acid (1) is preferable. Moreover, the plasticizer preferably does not volatilize at low temperatures in order to impart sufficient molecular mobility to the polyamic acid (1) during imidization. Therefore, the boiling point of the plasticizer is preferably 50°C or higher, more preferably 100°C or higher, and even more preferably 150°C or higher. Moreover, the plasticizer preferably does not have a decomposition temperature below the boiling point in order to impart sufficient molecular mobility to the polyamic acid (1) during imidization.
• the amount of plasticizer is preferably 10 parts by weight or less with respect to 100 parts by weight of polyamic acid (1).
• the amount of the plasticizer is 0.001 weight per 100 parts by weight of the polyamic acid (1) from the viewpoint of imparting sufficient molecular mobility to the polyamic acid (1) and avoiding decomposition of the plasticizer itself. parts by weight or more and 10 parts by weight or less, more preferably 0.01 parts by weight or more and 10 parts by weight or less, still more preferably 0.01 parts by weight or more and 8 parts by weight or less, and 0.1 parts by weight Part or more and 6 parts by weight or less is even more preferable.
• the plasticizer should be selected from the group consisting of phosphorus-containing compounds (phosphorus-containing compounds), polyalkylene glycols, and aliphatic dibasic acid esters. It is preferable to use one or more of the phosphorus-containing compounds (phosphorus-containing compounds), polyalkylene glycols, and aliphatic dibasic acid esters. It is preferable to use one or more of the phosphorus-containing compounds (phosphorus-containing compounds), polyalkylene glycols, and aliphatic dibasic acid esters. It is preferable to use one or more of the group consisting of phosphorus-containing compounds (phosphorus-containing compounds), polyalkylene glycols, and aliphatic dibasic acid esters. It is preferable to use one or more of the phosphorus-containing compounds (phosphorus-containing compounds), polyalkylene glycols, and aliphatic dibasic acid esters. It is preferable to use one or more of the phosphorus-containing compounds (phosphorus-containing compounds), polyalkylene glyco
• Phosphorus-containing compounds include compounds represented by the following general formulas (3-1) to (3-10).
• R 5 , R 6 and R 7 each independently represent a hydrogen atom, a monovalent organic group or a polyvalent organic group
• R 8 is , represents a polyvalent organic group
• n represents the degree of polymerization.
• Preferred examples of phosphorus-containing compounds include phosphoric acid compounds, phosphorous acid compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine compounds, phosphine oxide compounds, phosphorane compounds, phosphazene compounds, and the like.
• the phosphorus-containing compound may be an ester of the compounds listed above or a condensate thereof, may contain a cyclic structure, or may form a salt with an amine or the like. Further, some of these phosphorus-containing compounds have a tautomeric relationship, such as a phosphorous acid-based compound and a phosphonic acid-based compound, but they may exist in either state.
• phosphoric acid compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl ) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyl oxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-meth
• phosphorous acid compounds include triphenylphosphite, trisnonylphenylphosphite, tricresylphosphite, triethylphosphite, triisobutylphosphite, tris(2-ethylhexyl)phosphite and tridecylphosphite.
• trilauryl phosphite tris (tridecyl) phosphite, diphenyl phosphite, diethyl phosphite, dibutyl phosphite, dimethyl phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl mono (tridecyl) phosphites, trilauryl trithiophosphite, diethyl hydrogen phosphite, bis(2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyl dipropylene glycol diphosphite, bis (decyl) pentaerythritol diphosphite, bis (tride
• condensates include condensed phosphate esters.
• specific examples of the condensed phosphate include trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly(di-2,6-xylyl) phosphate, hydroquinone poly(2,6-xylyl) phosphate, and the like.
• Commercially available condensed phosphate esters include, for example, "CR-733S” manufactured by Daihachi Chemical Industry Co., Ltd., "CR-741” manufactured by Daihachi Chemical Industry Co., Ltd., "PX-200” manufactured by Daihachi Chemical Industry Co., Ltd., and ADEKA. and "FP-600” manufactured by K.K.
• phosphazene-based compounds include phenoxycyclophosphazene (“FP-110” manufactured by Fushimi Pharmaceutical Co., Ltd.), cyclic cyanophenoxyphosphazene (“FP-300” manufactured by Fushimi Pharmaceutical Co., Ltd.), and the like.
• polyalkylene glycol examples include polypropylene glycol and polyethylene glycol.
• aliphatic dibasic acid esters include dibutyl adipate, diisobutyl adipate, bis(2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, bis[2-(2-butoxyethoxy)ethyl]adipate, bis(2- ethylhexyl)azelate, dibutyl sebacate, bis(2-ethylhexyl) sebacate, diethyl succinate and the like.
• the plasticizer may be a low-molecular-weight organic compound or a thermoplastic resin as long as it exhibits a plasticizing effect.
• the low-molecular-weight organic compounds include organic compounds having a molecular weight of about 1,000 or less, such as phenolic compounds; Phthalimide compounds; maleimide compounds such as N,Np-phenylenebismaleimide and 2,2'-(ethylenedioxy)bis(ethylmaleimide).
• the thermoplastic resin include polyimide and polyamide having an asymmetric structure.
• the polyamic acid composition according to the present embodiment can contain a silane coupling agent in order to exhibit appropriate adhesion to the support.
• a silane coupling agent known ones can be used without particular limitation, but compounds containing an amino group are particularly preferred from the viewpoint of reactivity with polyamic acid (1).
• the mixing ratio of the silane coupling agent to 100 parts by weight of polyamic acid (1) is preferably 0.01 parts by weight or more and 0.50 parts by weight or less, and 0.01 parts by weight or more and 0.10 parts by weight or less. more preferably 0.01 parts by weight or more and 0.05 parts by weight or less.
• the polyimide according to this embodiment is an imidized product of polyamic acid (1) described above.
• the polyimide according to this embodiment can be obtained by a known method, and the production method is not particularly limited. An example of a method for imidating the polyamic acid (1) to obtain the polyimide according to the present embodiment will be described below. Imidation is carried out by dehydration and ring closure of polyamic acid (1). This dehydration ring closure can be carried out by an azeotropic method using an azeotropic solvent, a thermal method, or a chemical method.
• imidization of polyamic acid (1) to polyimide can take any ratio of 1% or more and 100% or less. That is, a partially imidized polyamic acid (1) may be synthesized.
• the dehydration ring closure of the polyamic acid (1) may be performed by heating the polyamic acid (1).
• the method of heating the polyamic acid (1) is not particularly limited, but for example, the polyamic acid composition according to the present embodiment is applied onto a support such as a glass substrate, a metal plate, or a PET film (polyethylene terephthalate film). After that, the polyamic acid (1) may be heat-treated at a temperature in the range of 40°C or higher and 500°C or lower. According to this method, a laminate according to the present embodiment, which has a support and a polyimide film (specifically, a polyimide film containing an imidized product of polyamic acid (1)) disposed on the support, is obtained. be done.
• a polyimide film specifically, a polyimide film containing an imidized product of polyamic acid (1)
• the polyamic acid composition is directly put into a container that has been subjected to release treatment such as coating with a fluororesin, and the polyamic acid composition is heated and dried under reduced pressure to effect dehydration ring closure of the polyamic acid (1).
• release treatment such as coating with a fluororesin
• Polyimide can be obtained by dehydration ring closure of polyamic acid (1) by these techniques.
• the heating time for each of the above treatments varies depending on the amount of the polyamic acid composition to be subjected to dehydration ring closure and the heating temperature, but is generally 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
• the polyimide film according to the present embodiment (specifically, the polyimide film containing the imidized product of polyamic acid (1)) is colorless and transparent, has a low degree of yellowness, and has a glass transition temperature (heat resistance) that can withstand the TFT manufacturing process. Therefore, it is suitable as a transparent substrate material for flexible displays.
• the content of polyimide (specifically, imidized polyamic acid (1)) in the polyimide film according to the present embodiment is, for example, 70% by weight or more, and 80% by weight or more with respect to the total amount of the polyimide film. is preferable, more preferably 90% by weight or more, and may be 100% by weight.
• Components other than polyimide in the polyimide film include, for example, the additives described above (more specifically, fine particles and the like).
• An electronic device (more specifically, a flexible device or the like) according to this embodiment has a polyimide film according to this embodiment and an electronic element directly or indirectly arranged on this polyimide film.
• an inorganic substrate such as glass is used as a support, and a polyimide film is formed thereon.
• an electronic device is formed on the support by arranging (forming) an electronic element such as a TFT on the polyimide film.
• the process of forming a TFT is generally carried out in a wide temperature range of 150° C. or higher and 650° C. or lower. is formed, and in some cases, a-Si or the like is further crystallized by a laser or the like.
• the 1% weight loss temperature of polyimide is preferably 500° C. or higher because there is a possibility that a barrier film (to be described later) and electronic elements may peel off.
• the upper limit of the 1% weight loss temperature of polyimide is preferably 600° C., for example, although the higher the better.
• the 1% weight loss temperature can be adjusted, for example, by changing the content of residues having a rigid structure (more specifically, NTCDA 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.
• SiOx film silicon oxide film
• SiNx film silicon nitride film
• the polyimide and the inorganic film are separated from each other. 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 isothermally at a temperature within the range of 400° C. or higher and 450° C. or lower must be less than 1%. desirable.
• the glass transition temperature (Tg) of the polyimide is significantly lower than the process temperature, there is a possibility that misalignment or the like may occur during the formation of the electronic device. It is more preferably 350° C. or higher, still more preferably 400° C. or higher, and even more preferably 420° C. or higher.
• the upper limit of Tg of polyimide is preferably 500° C., although the higher the better.
• the coefficient of thermal expansion of the glass substrate is generally smaller than that of resin, internal stress is generated between the glass substrate and the polyimide film.
• the laminated body including the polyimide film expands in the TFT formation process at a high temperature and then shrinks when cooled to room temperature.
• the internal stress between the polyimide film and the glass substrate is preferably 40 MPa or less, more preferably 35 MPa or less, still more preferably 30 MPa or less, and even more preferably 25 MPa or less.
• the method for measuring the internal stress is the same method as in Examples described later or a method based thereon.
• the polyimide film may peel off during the formation of the electronic device, or the yield may decrease when the polyimide film is peeled off after the electronic device is formed.
• floating refers to the adhesion between the polyimide film and other material layers (more specifically, glass substrates, barrier films, etc.) due to secondary components and residual solvents generated during imidization. Refers to a state in which a defect has occurred.
• floating include a state in which the polyimide film is lifted from the glass substrate, a state in which a portion of the polyimide film is destroyed and delamination occurs between the polyimide film and another material layer, and a barrier from the polyimide film. A state in which the film is lifted may be mentioned.
• a polyimide film obtained from a polyamic acid having BPDA residues and BAAB residues has densely packed molecular chains and poor outgassing properties. is likely to occur.
• polyamic acid having a BPAF residue or an SFDA residue can achieve both good outgassing properties and a high glass transition temperature due to its bulky structure.
• the polyimide according to this embodiment can be suitably used as a material for display substrates such as TFT substrates and touch panel substrates.
• an electronic device (more specifically, an electronic device having electronic elements formed on a polyimide film) is formed on a support as described above, and then the polyimide film is peeled off from the support. often adopted.
• alkali-free glass is preferably used as the material of the support.
• the polyamic acid composition according to the present embodiment is applied (cast) onto a support to form a coated film-containing laminate comprising a coated film containing polyamic acid (1) and the support.
• the coated film-containing layered product is heated, for example, at 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 process may be provided, such as heating the coating film-containing laminate at a temperature of 50° C. for 30 minutes and then heating it 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. 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. At this time, it is preferable to gradually raise the temperature from the low temperature to the maximum temperature.
• the heating rate is preferably 2° C./min or more and 10° C./min or less, 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. When the maximum temperature is 250° C.
• imidization proceeds sufficiently, and when the maximum temperature is 450° C. or lower, thermal deterioration and coloration of the polyimide can be suppressed. Also, any temperature may be maintained for any length of 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 preferred.
• the heating device known devices such as a hot air oven, an infrared oven, a vacuum oven, an inert oven, and a hot plate can be used.
• Polyamic acid (1) in the coating film is imidized through these steps, and a laminate of a support and a polyimide film (a film containing an imidized product of polyamic acid (1)) (that is, according to the present embodiment) laminate) can be obtained.
• a known method can be used to peel off the polyimide film from the obtained laminate of the support and the polyimide film. For example, it may be peeled off by hand, or may be peeled off using a mechanical device such as a driving roll or a robot. Furthermore, a method of providing a peeling layer between a support and a polyimide film, a method of forming a silicon oxide film on a support having a large number of grooves, forming a polyimide film using the silicon oxide film as a base layer, and forming a polyimide film on the support It is also possible to adopt a method of exfoliating the polyimide film by infiltrating a silicon oxide etchant between the film and the silicon oxide film. Alternatively, a method of separating the polyimide film by laser light irradiation may be employed.
• the transparency of the polyimide film can be evaluated by total light transmittance (TT) according to JIS K7361-1:1997 and 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 below, and may be 0%.
• Haze can be adjusted, for example, by changing the content of TFMB residues in polyamic acid (1).
• polyimide films are required to have high transmittance over the entire wavelength range. often colored.
• the polyimide film is less colored.
• the yellowness index (YI) of the polyimide film is preferably 25 or less, more preferably 20 or less, It can be 0. YI can be measured according to JIS K7373-2006.
• the polyimide film with reduced coloration and imparted with transparency is suitable for transparent substrates such as glass substitutes, and substrates on which a sensor or camera module is provided on the back surface.
• the transmittance of blue light (light near the wavelength of 470 nm) is high. is required to have high light transmittance (400 nm transmittance).
• the 400 nm transmittance of the polyimide film is preferably 40% or more, more preferably 45% or more.
• the upper limit of the 400 nm transmittance of the polyimide film is not particularly limited, and may be 100%.
• the top emission method in which light is extracted from the front surface of the TFT
• the bottom emission method in which light is extracted from the back surface of the TFT.
• the top-emission method is easy to increase the aperture ratio because the light is not blocked by the TFT, and high-definition image quality can be obtained. Characteristic. If the TFT is transparent, it is possible to improve the aperture ratio even in the bottom emission method, so there is a tendency to adopt the bottom emission method, which is easy to manufacture, for large displays. Since the polyimide film according to this embodiment has a low YI and excellent heat resistance, it can be applied to either of the above light extraction methods.
• a polyamic acid composition is applied to a support such as a glass substrate, heated to imidize, an electronic element or the like is formed, and then the polyimide film is peeled off, the support and the like are used.
• Adhesion means adhesion strength.
• the manufacturing process of peeling off the polyimide film on which the electronic elements and the like are formed from the support after forming the electronic elements on the polyimide film on 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 between the support and the polyimide film should be as high as possible from the viewpoint of improving productivity.
• the peel strength is preferably 0.05 N/cm or more, more preferably 0.1 N/cm or more.
• the polyimide film when peeling 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 longer, more preferably 330 nm or longer.
• the cutoff wavelength of the polyimide film is preferably 390 nm or less.
• the cutoff wavelength of the polyimide film is preferably 320 nm or more and 390 nm or less, more preferably 330 nm or more and 380 nm or less, from the viewpoint of achieving both transparency (low degree of yellowness) and workability of laser peeling.
• the term "cutoff wavelength" as used herein means a 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 the present embodiment may be used as they are for coating and molding processes for producing products and members, but the molded product molded in the form of a film is further subjected to coating and other treatments. It can also be used as a material for For use in coating or molding processes, the polyamic acid composition or polyimide, optionally dissolved or dispersed in an organic solvent, and optionally a photocurable component, a thermosetting component, a non-polymeric binder, A composition comprising polyamic acid (1) or polyimide may be prepared by blending the resin and other ingredients.
• inorganic thin films such as metal oxide thin films and transparent electrodes may be formed on the surface of the polyimide film according to this embodiment.
• the method for forming these inorganic thin films is not particularly limited, and examples thereof include PVD methods such as sputtering, vacuum deposition, and ion plating, and CVD methods.
• the polyimide film according to the present embodiment In addition to heat resistance, low thermal expansion, and transparency, the polyimide film according to the present embodiment generates little internal stress when forming a laminate with a glass substrate, ensuring adhesion with inorganic materials during high-temperature processes. Therefore, it is preferably used in fields and products where these properties are useful.
• the polyimide film according to the present embodiment can be used for liquid crystal display devices, organic EL devices, image display devices such as electronic paper, printed matter, color filters, flexible displays, optical films, 3D displays, touch panels, transparent conductive film substrates, solar cells, and the like. It is more preferable to use it as a substitute 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, preferably 5 ⁇ m or more and 100 ⁇ m or less.
• the thickness of the polyimide film can be measured using a laser hologram.
• the polyamic acid composition according to the present embodiment is prepared by coating the polyamic acid composition on a support, imidizing it by heating, forming an electronic element or the like, and then peeling off the polyimide film for batch-type device fabrication. It can be suitably used for the process. Therefore, in the present embodiment, the production of an electronic device including the step of applying a polyamic acid composition on a support, imidizing it by heating, and forming an electronic element or the like on a polyimide film formed on the support A method is also included. Moreover, the method for producing such an electronic device may further include a step of peeling off the polyimide film on which the electronic elements and the like are formed from the support.
• Total light transmittance (TT) For the polyimide film peeled from each laminate obtained in Examples and Comparative Examples described later, using an integrating sphere haze meter ("HM-150N” manufactured by Murakami Color Research Laboratory Co., Ltd.), JIS K7361-1: 1997 Total light transmittance (TT) was measured by the method described in .
• TD1 1% weight loss temperature
• Glass transition temperature (Tg) A polyimide film having a width of 3 mm and a length of 10 mm was sampled from each laminate obtained in Examples and Comparative Examples, which will be described later, and used as a sample for Tg measurement. Using a thermal analysis device ("TMA/SS7100" manufactured by Hitachi High-Tech Science), a load of 98.0 mN was applied to the sample, the temperature was raised from 20 ° C. to 470 ° C. at 10 ° C./min, and the temperature and strain amount (elongation ) to obtain the TMA curve. The temperature at 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).
• TMA/SS7100 manufactured by Hitachi High-Tech Science
• NMP N-methyl-2-pyrrolidone
• NTCDA 2,3,6,7-naphthalenetetracarboxylic dianhydride
• PMDA pyromellitic dianhydride
• BPDA 3,3',4,4'-biphenyltetracarboxylic acid
• ODPA 4,4'-oxydiphthalic anhydride
• DODA 4,4'-dioxydiphthalic anhydride
• SFDA spiro[11H - diflo[3,4-b:3′,4′-i]xanthene-11,9′-[9H]fluorene]-1,3,7,9-tetrone
• TFMB 2,2′-bis(trifluoro methyl)benzidine
• BAAB 4-aminophenyl-4-aminobenzoate
• BAFL 9,9-bis(4-aminophenyl)
• Example 1 A 300 mL glass separable flask equipped with a stirrer equipped with a stainless steel stir bar and a nitrogen inlet was charged with 40.0 g of NMP as an organic solvent for polymerization. 5.272 g of TFMB was then added to the flask and dissolved while stirring the flask contents. After adding 3.973 g of NTCDA and 0.755 g of BPAF to the contents of the flask, the contents of the flask were stirred for 24 hours under an atmosphere of 25° C. to obtain a polyamic acid composition.
• the resulting polyamic acid composition was applied onto a glass substrate (manufactured by Corning, material: non-alkali glass, thickness: 0.7 mm, size: 100 mm x 100 mm) using a spin coater, and coated in air at 120°C. After heating for 30 minutes, it was heated at 430° C. for 30 minutes in a nitrogen atmosphere to obtain a laminate (laminate of Example 1) having a polyimide film having a thickness of 10 ⁇ m on a glass substrate.
• Example 2 A 300 mL glass separable flask equipped with a stirrer equipped with a stainless steel stir bar and a nitrogen inlet was charged with 40.0 g of NMP as an organic solvent for polymerization. 5.272 g of TFMB was then added to the flask and dissolved while stirring the flask contents. After adding 3.973 g of NTCDA and 0.755 g of BPAF to the contents of the flask, the contents of the flask were stirred for 24 hours under an atmosphere of 25°C. Then, TPPi as a plasticizer was added to the contents of the flask to obtain a polyamic acid composition.
• the amount of TPPi added was 1 part by weight per 100 parts by weight of polyamic acid in the contents of the flask.
• the resulting polyamic acid composition was applied onto a glass substrate (manufactured by Corning, material: non-alkali glass, thickness: 0.7 mm, size: 100 mm x 100 mm) using a spin coater, and coated in air at 120°C. After heating for 30 minutes, it was heated at 430° C. for 30 minutes in a nitrogen atmosphere to obtain a laminate (laminate of Example 2) having a polyimide film having a thickness of 10 ⁇ m on a glass substrate.
• Examples 3 to 30 and Comparative Examples 1 to 7 Examples 3 to 6 and 8 were prepared in the same manner as in Example 1 except that the acid dianhydride used and its charging ratio, and the diamine used and its charging ratio were as shown in Tables 3 and 4. , 10 to 27 and 29, and laminates of Comparative Examples 1 to 7, respectively.
• the same method as in Example 2 except that the acid dianhydride used and its charging ratio, the diamine used and its charging ratio, and the type of plasticizer were as shown in Tables 3 and 4, Laminates of Examples 7, 9, 28 and 30 were obtained, respectively.
• the total substance amount of the acid dianhydride when preparing the polyamic acid composition was the same as in Examples 1 and 2.
• the total substance amount of diamines in preparing polyamic acid compositions was the same as in Examples 1 and 2.
• Tables 3 and 4 show the monomers and plasticizers used for Examples 1 to 30 and Comparative Examples 1 to 7, respectively.
• "-" means that the component was not used.
• the numerical values in the "acid dianhydride” column are the content of each acid dianhydride relative to the total amount of acid dianhydride used (unit: mol %).
• the numerical values in the "diamine” column are the content of each diamine relative to the total amount of diamines used (unit: mol %).
• the numerical value in the "Plasticizer” column is the amount of plasticizer (unit: parts by weight) per 100 parts by weight of polyamic acid. Further, in all of Examples 1 to 30 and Comparative Examples 1 to 7, the molar fraction of each residue of polyamic acid in the prepared polyamic acid composition was different from each monomer (diamine and tetracarboxylic dianhydride).
• Table 5 shows the average level difference and physical property measurement results for Examples 1 to 30 and Comparative Examples 1 to 7. In Table 5, "-" means not measured.
• the polyamic acid in the polyamic acid composition prepared in Examples 1 to 30 contains one or more residues selected from the group consisting of BPDA residues, BPAF residues, ODPA residues and SFDA residues, and NTCDA residues and TFMB residues.
• the content of NTCDA residues was 5 mol% or more and 90 mol% or less with respect to the total amount of tetracarboxylic dianhydride residues. rice field.
• the content of TFMB residues was 50 mol% or more based on the total amount of diamine residues.
• Examples 1 to 30 the 400 nm transmittance was 40% or more. Therefore, the polyimides obtained in Examples 1 to 30 had high transmittance for light with a wavelength of 400 nm. In Examples 1-30, TD1 was above 500°C. Therefore, the polyimides obtained in Examples 1 to 30 were excellent in heat resistance.
• the content of NTCDA residues in the polyamic acid composition prepared in Comparative Example 1 exceeded 90 mol% relative to the total amount of tetracarboxylic dianhydride residues.
• the polyamic acids in the polyamic acid compositions prepared in Comparative Examples 2, 4, 6 and 7 did not have NTCDA residues.
• the polyamic acids in the polyamic acid compositions prepared in Comparative Examples 3 and 5 had a content of TFMB residues of less than 50 mol % with respect to the total amount of diamine residues.
• Comparative Examples 1 to 7 As shown in Table 5, in Comparative Examples 1 to 7, the 400 nm transmittance was less than 40%. Therefore, the polyimides obtained in Comparative Examples 1 to 7 did not have high transmittance for light with a wavelength of 400 nm.

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