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
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/30—Processes for applying liquids or other fluent materials performed by gravity only, i.e. flow coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
  • B05D3/0254—After-treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
  • B05D3/0406—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being air
  • B05D3/0413—Heating with air
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
  • B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
  • B29C39/22—Component parts, details or accessories; Auxiliary operations
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
  • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
• • 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
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
• • 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
  • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
  • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
  • C08G73/0644—Poly(1,3,5)triazines
• • 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
  • C08G73/1075—Partially aromatic polyimides
  • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
• • C—CHEMISTRY; METALLURGY
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  • 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
  • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
• • 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
  • C08G73/14—Polyamide-imides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
  • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
  • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
  • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
  • H01L31/03926—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
  • H01M14/005—Photoelectrochemical storage cells
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
  • B29K2079/08—PI, i.e. polyimides or derivatives thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
  • B29K2995/0016—Non-flammable or resistant to heat
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
  • B29K2995/0026—Transparent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0037—Other properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0037—Other properties
  • B29K2995/0082—Flexural strength; Flexion stiffness
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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

Definitions

• the present invention relates to a polyimide having excellent properties such as transparency, bending resistance and high heat resistance in combination with an extremely low coefficient of linear thermal expansion and excellent solvent resistance, and a precursor thereof.
• the present invention also relates to a polyimide having excellent properties such as transparency, bending resistance and high heat resistance in combination with an extremely low coefficient of linear thermal expansion, excellent solvent resistance and flame resistance, and a precursor thereof.
• optical materials such as an optical fiber and an optical waveguide in the field of optical communications and optical materials such as a liquid crystal orientation film and a color-filter protective film in the field of display devices has been advanced.
• a light and excellently flexible plastic substrate has been studied as an alternative for a glass substrate, and development of a display which can be bent and rolled has been aggressively made.
• a higher performance optical material that can be used for such purposes has been demanded.
• Polyimides are essentially colored in yellowish brown by intramolecular conjugation and charge-transfer complex formation.
• a means to reduce the coloration for example, a method of expressing transparency by inhibiting formation of intramolecular conjugation and charge-transfer complex by introducing fluorine, providing flexibility to the main chain, or introducing a bulky side chain is proposed.
• methods of expressing transparency by using semi-alicyclic or wholly alicyclic polyimide resins that do not, in principle, form charge-transfer complexes are proposed.
• Patent Document 1 discloses that a thin-film transistor substrate is obtained by forming a thin-film transistor on a transparent-film substrate of a polyimide having an aliphatic group as a tetracarboxylic acid component residue by use of a conventional film-forming process in order to obtain a thin, light and rarely broken active matrix display device.
• the polyimide specifically used herein is prepared from 1,2,4,5-cyclohexanetetracarboxylic dianhydride as a tetracarboxylic acid component and 4,4′-diaminodiphenyl ether as a diamine component.
• Patent Document 2 discloses a method for manufacturing a colorless transparent resin film formed of a polyimide excellent in colorless, transparency, heat resistance and planarity and used as a transparent substrate, a thin-film transistor substrate and a flexible wire substrate for liquid crystal display devices and organic EL display devices, by a solvent casting method using a particular drying step.
• the polyimide used herein is prepared from 1,2,4,5-cyclohexanetetracarboxylic dianhydride as a tetracarboxylic acid component and ⁇ , ⁇ ′-bis(4-aminophenyl)-1,4-diisopropylbenzene and 4,4′-bis(4-aminophenoxy)biphenyl as diamine components.
• Patent Documents 3 and 4 disclose a polyimide soluble in an organic solvent, in which dicyclohexyltetracarboxylic acid is used as a tetracarboxylic acid component and diaminodiphenyl ether, diaminodiphenyl methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]ether or metaphenylenediamine is used as a diamine component.
• Such a semi-alicyclic polyimide in which an alicyclic tetracarboxylic dianhydride is used as a tetracarboxylic acid component and an aromatic diamine is used as a diamine component, has transparency, bending resistance and high heat resistance in combination.
• a semi-alicyclic polyimide generally has a coefficient of linear thermal expansion as high as 50 ppm/K or more, which greatly differs from a coefficient of linear thermal expansion of a conductive material such as a metal, with the result that a failure such as large warpage may probably occur in a process of forming a circuitboard.
• a process for forming a fine circuit for use in displays is not easily made.
• the present invention was made in the aforementioned circumstances, and an object thereof is to improve the coefficient of linear thermal expansion and solvent resistance of a semi-alicyclic polyimide in which an alicyclic tetracarboxylic dianhydride is used as a tetracarboxylic acid component and an aromatic diamine is used as a diamine component. Furthermore, an object of the present invention is to improve the coefficient of linear thermal expansion, solvent resistance and flame resistance of a polyimide in which an aliphatic tetracarboxylic dianhydride is used as a tetracarboxylic acid component.
• an object of the present invention is to provide a polyimide having excellent properties such as transparency, bending resistance and high heat resistance in combination with an extremely low coefficient of linear thermal expansion and excellent solvent resistance and a precursor thereof.
• Another object of the present invention is to provide a polyimide having excellent properties such as transparency, bending resistance and high heat resistance in combination with an extremely low coefficient of linear thermal expansion, excellent solvent resistance and flame resistance, and a precursor thereof.
• the present invention relates to the following items.
• a polyimide precursor comprising a repeating unit represented by the following chemical formula (1):
• A is a tetravalent group having at least one aliphatic six-membered ring and no aromatic ring in the chemical structure
• B is a divalent group having at least one amide bond and an aromatic ring in the chemical structure
• A is an aliphatic tetravalent group and B is a divalent group having at least one chemical structure represented by the following chemical formula (2) in the chemical structure:
• X 1 and X 2 are each independently hydrogen, a C 1-6 alkyl group or a C 3-9 alkylsilyl group.
• A is at least one selected from the group consisting of the following chemical formulae (3-1) to (3-4):
• R1 is a direct bond, a CH 2 group, a C(CH 3 ) 2 group, an SO 2 group, an Si(CH 3 ) 2 group, a C(CF 3 ) 2 group, an oxygen atom or an sulfur atom;
• R2 is a CH 2 group, a CH 2 CH 2 group, an oxygen atom or a sulfur atom
• R3 and R4 are each independently a CH 2 group, a CH 2 CH 2 group, an oxygen atom or a sulfur atom.
• Ar 1 , Ar 2 and Ar 3 are each independently a divalent group having an aromatic ring having 6 to 18 carbon atoms; and n1 is an integer of 0 to 5;
• Ar 4 , Ar 5 , Ar 6 , Ar 7 and Ar 8 are each independently a divalent group having an aromatic ring having 6 to 18 carbon atoms; and n2 is an integer of 0 to 5;
• Ar 9 , Ar 10 , Ar 11 , Ar 12 and Ar 13 are each independently a divalent group having an aromatic ring having 6 to 18 carbon atoms; and n3 is an integer of 0 to 5;
• the polyimide precursor according to the above item 4 wherein the diamine component comprises at least one of p-phenylenediamine, benzidine, 2,2′-bis(trifluoromethyl)benzidine, 3,3′-dimethylbenzidine, 2,2′-dimethylbenzidine or trans-cyclohexanediamine in an amount of 30 mole % or less, in addition to the diamine component providing the repeating unit represented by chemical formula (1).
• the polyimide precursor according to any one of the above items 1 to 8 having a light transmittance of 40% or more at a wavelength of 400 nm and an optical path length of 1 cm as a 10% by mass solution in a solvent selected from N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide and water.
• a solvent selected from N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide and water.
• a polyimide precursor solution composition comprising the polyimide precursor according to any one of the above items 1 to 9 dissolved in a solvent, wherein the solvent has a light transmittance of 89% or more at a wavelength of 400 nm and an optical path length of 1 cm.
• A is a tetravalent group having at least one aliphatic six-membered ring and no aromatic ring in the chemical structure and B is a divalent group having at least one amide bond and an aromatic ring in the chemical structure; or A is an aliphatic tetravalent group and B is a divalent group having at least one chemical structure represented by the aforementioned chemical formula (2) in the chemical structure.
• the polyimide according to the above item 11 having an total light transmittance (average light transmittance from 380 nm to 780 nm) of 70% or more, preferably 80% or more, more preferably 85% or more, when formed into a film having a thickness of 10 ⁇ m. 13.
• a in the chemical formula (5) is an aliphatic tetravalent group
• B is a divalent group having at least one chemical structure represented by the chemical formula (2) in the chemical structure
• the polyimide has an oxygen index of 22% (volume fraction) or more.
• a polyimide having excellent properties such as transparency, bending resistance and high heat resistance in combination with an extremely low coefficient of linear thermal expansion and excellent solvent resistance and a precursor thereof.
• the polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention have high transparency and a low coefficient of linear thermal expansion allowing a fine circuit to be easily formed, and solvent resistance in combination. Therefore, they are suitably used for forming substrates for use in displays.
• the polyimides of the present invention can be suitably used also for forming substrates for touch panels and solar batteries.
• a polyimide having excellent properties such as transparency, bending resistance and high heat resistance in combination with an extremely low coefficient of linear thermal expansion, excellent solvent resistance and flame resistance, and a precursor thereof.
• the polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention have high transparency and a low coefficient of linear thermal expansion allowing a fine circuit to be easily formed, solvent resistance, and flame resistance in combination. Therefore, they are suitably used for forming substrates for displays and substrates for touch panels and solar batteries.
• the polyimide precursor of the present invention is a polyimide precursor containing a repeating unit represented by the above chemical formula (1) in a structure.
• the polyimide precursor of the present invention is a semi-alicyclic polyimide precursor (A), which is obtained from an alicyclic tetracarboxylic acid component having at least one aliphatic six-membered ring and no aromatic ring in the chemical structure, and an aromatic diamine component having at least one amide bond and an aromatic ring in the chemical structure; or a polyimide precursor (B), which is obtained from an aliphatic tetracarboxylic acid component and a diamine component having at least one chemical structure represented by the above chemical formula (2) in the chemical structure.
• the polyimide precursor of the present invention may be a polyimide precursor obtained by using other tetracarboxylic acid component(s) and/or diamine component(s).
• a polyimide precursor may be obtained from a tetracarboxylic acid component providing a repeating unit represented by chemical formula (1) (more specifically, in the case of a polyimide precursor (A), an alicyclic tetracarboxylic acid component having at least one aliphatic six-membered ring and no aromatic ring in the chemical structure, and in the case of a polyimide precursor (B), an aliphatic tetracarboxylic acid component) in an amount of 70 mole % or more and the other tetracarboxylic acid component(s) in an amount of 30 mole % or less based on 100 mole % of the total tetracarboxylic acid components, and a diamine component providing a repeating unit represented by chemical formula (1) (more specifically, in the case of a polyimi
• a tetracarboxylic acid component and a diamine component of the polyimide precursor (A) of the present invention will be described.
• the tetracarboxylic acid component to be used in the polyimide precursor (A) of the present invention is an alicyclic tetracarboxylic acid component having at least one aliphatic six-membered ring and no aromatic ring in the chemical structure.
• the six-membered ring contained in the tetracarboxylic acid component may also be plural and a plurality of six-membered rings may have two or more common carbon atoms as constituents.
• carbon atoms (within the six-membered ring) constituting a six-membered ring may chemically bind to each other to form another ring.
• the six-membered ring may have a crosslinked cyclic form.
• the tetracarboxylic acid component have a highly symmetric six-membered ring structure, because a polymer chain can be densely packed and the resultant polyimide has excellent solvent resistance, heat resistance and mechanical strength. Furthermore, it is more preferable that the tetracarboxylic acid component is a polyalicyclic type having a plurality of six-membered rings having two or more common carbon atoms as constituents, or the tetracarboxylic acid component is a crosslinked cyclic type having a six-membered ring, in which carbon atoms constituting the ring chemically bind to each other to form another ring, because satisfactory heat resistance, solvent resistance and a low coefficient of linear thermal expansion of the resultant polyimide can be easily attained.
• the tetravalent group derived from the tetracarboxylic acid component represented by A in the above chemical formula (1) for example, groups represented by the above chemical formulae (3-1) to (3-4) are preferable; a group represented by the above chemical formula (3-3) or (3-4) is more preferable; and a group represented by the above chemical formula (3-4) is particularly preferable.
• the groups represented by the above chemical formulae (3-3) and (3-4) are more preferable because they are a crosslinked cyclic type and thus the heat resistance of the polyimide is excellent and the coefficient of linear thermal expansion thereof is low.
• the group represented by the above chemical formula (3-4) is particularly preferable because it is a polyalicyclic/crosslinked cyclic type and thus the heat resistance of the polyimide is more excellent.
• tetracarboxylic acid components to introduce the chemical structure of the above chemical formulae (3-1) and (3-2) include cyclohexane-1,2,4,5-tetracarboxylic acid, [1,1′-bi(cyclohexane)]-3,3′,4,4′-tetracarboxylic acid, [1,1′-bi(cyclohexane)]-2,3,3′,4′-tetracarboxylic acid, [1,1′-bi(cyclohexane)]-2,2′,3,3′-tetracarboxylic acid, 4,4′-methylenebis(cyclohexane-1,2-dicarboxylic acid), 4,4′-(propane-2,2-diyl)bis(cyclohexane-1,2-dicarboxylic acid), 4,4′-oxybis(cyclohexane-1,2-dicarboxylic acid), 4,4′-thiobis(cyclohexane-1,2-dicar
• these tetracarboxylic components may be subjected to separation and refinement and the like, so that the percentage of particular stereoisomer(s) may be 80% or more, more preferably 90% or more, particularly preferably 95% or more, which increase the heat resistance and the solvent resistance of the polyimide.
• the percentage of particular stereoisomer(s) preference is given to:
• PMTA-HS 1R,2S,4S,5R-cyclohexane tetracarboxylic acid
• PMDA-HS dianhydride
• PMTA-HH 1S,2S,4R,5R-cyclohexane tetracarboxylic acid
• PMDA-HH dianhydride
• trans-DCTA (1R,1′S,3R,3′S,4R,4′S)dicyclohexyl-3,3′,4,4′-tetracarboxylic acid
• trans-DCDA dianhydride
• tetracarboxylic acid components of crosslinked cyclic type or polyalicyclic/crosslinked cyclic type to introduce the chemical structure of the above chemical formulae (3-3) and (3-4) include derivatives of octahydropentalene-1,3,4,6-tetracarboxylic acid, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid, 6-(carboxymethyl)bicyclo[2.2.1]heptane-2,3,5-tricarboxylic acid, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid, bicyclo[2.2.2]octa-5-ene-2,3,7,8-tetracarboxylic acid, tricyclo[4.2.2.02,5]decane-3,4,7,8-tetracarboxylic acid, tricyclo[4.2.2.02,5]deca-7-ene-3,4,9,10-tetracarboxylic acid, 9
• bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid preference is given to derivatives of bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid, decahydro-1,4:5,8-dimethanonaphthalene-2,3,6,7-tetracarboxylic acid and dianhydrides of these because they allows easy production of polyimide and they provide polyimides having excellent heat resistance.
• these tetracarboxylic components may be subjected to separation and refinement and the like, so that the percentage of particular stereoisomer(s) may be 70% or more, more preferably 90% or more, particularly preferably 95% or more, which allows the production of a polyimide having low coefficient of linear thermal expansion.
• the particular stereoisomer(s) preference is given to:
• the abovementioned tetracarboxylic acid components may be used alone or in combination of two or more.
• aromatic or aliphatic tetracarboxylic acid components generally employed for polyimides may be used together in a small amount within the range that the properties of the polyimide of the present invention can be achieved (preferably 30% by mole or less, more preferably 10% by mole or less, further preferably less than 10% by mole).
• aromatic or aliphatic tetracarboxylic acid components include derivatives of 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, oxydiphthalic acid, biscarboxyphenyldimethyl silane, bisdicarboxyphenoxy diphenyl sulfide, sulfonyldiphthalic acid, cyclobutanetetracarboxylic acid, isopropylidene phenoxybisphthalic acid and the like, and dianhydrides of these.
• the tetracarboxylic acid component to be used in the present invention is not particularly limited; however, it preferably has a purity of 99% or more, and preferably 99.5% or more (in the case that plural stereoisomers are contained, the purity is determined by regarding the stereoisomers as a single component without distinguishing them; in the case of using a plurality of types of tetracarboxylic acid components, it is the value of a tetracarboxylic acid component having the highest purity, or it is an average purity value obtained by individually obtaining the purities of all tetracarboxylic acid components to be used and weighing them each by the mass ratio of the use amount thereof is regarded as the purity, namely, for example, when a tetracarboxylic acid component having a purity of 100% is used in an amount of 70 parts by mass and a tetracarboxylic acid component having a purity of 90% is used in an amount of 30 parts by mass, the purity of the tetracarboxylic acid
• the purity is less than 98%, the molecular weight of the resultant polyimide precursor is not sufficiently increased and the heat resistance of the resultant polyimide is sometimes inferior.
• the purity is a value obtained by gas chromatographic analysis or 1 H-NMR analysis.
• the purity thereof can be obtained in terms of tetracarboxylic acid obtained by hydrolyzing the tetracarboxylic dianhydride.
• the tetracarboxylic acid component to be used in the present invention is not particularly limited; however, it preferably has a light transmittance of 70% or more, preferably 80% or more and more preferably 90% or more (in the case of using a plurality of types of tetracarboxylic acid components, it is the value of a tetracarboxylic acid component having the most excellent light transmittance, or it is an average light transmittance value obtained by individually obtaining the purities of all tetracarboxylic acid components to be used and weighing them each by the mass ratio of the use amount thereof is regarded as the light transmittance, namely, for example, when a tetracarboxylic acid component having a light transmittance of 100% is used in an amount of 70 parts by mass and a tetracarboxylic acid component having a light transmittance of 90% is used in an amount of 30 parts by mass, the light transmittance of the tetracarboxylic acid component to be used is calculated
• the light transmittance herein is a transmittance at a wavelength of 400 nm and an optical path length of 1 cm as a 10% by mass solution obtained by dissolving a tetracarboxylic acid component in a 2N sodium hydroxide solution.
• the light transmittance of a tetracarboxylic acid component is preferably 70% or more, because degree of coloration of the resultant polyimide is reduced.
• the diamine component to be used in the polyimide precursor (A) of the present invention is a diamine component having at least one amide bond and an aromatic ring in the chemical structure.
• an amide bond is introduced by a diamine component into the chemical structure of the polyimide precursor (A) of the present invention.
• the diamine component preferably has one or more amide bonds, preferably a plurality of amide bonds, in the chemical structure. Note that, if the number of amide bonds in a diamine component is excessively large, the solubility of the resultant polyimide precursor may sometimes decrease.
• divalent group derived from the diamine component represented by B in the above chemical formula (1) for example, groups represented by the above chemical formulae (4-1) to (4-3) are preferable.
• Ar 1 to Ar 13 in the above chemical formula (4-1) to (4.3) are each independently a divalent group having an aromatic ring having 6 to 18 carbon atoms.
• the aromatic ring herein refers to a divalent aromatic compound such as benzene, biphenyl, terphenyl, naphthalene and anthracene.
• a part of hydrogen atoms of the aromatic ring may be substituted with C 1-3 alkyl group, halogen group, nitro group, hydroxyl group, carboxylic group and the like.
• the divalent aromatic compound benzene and biphenyl are preferable since the light transmittance of the resultant polyimide is excellent.
• the bonding position of a divalent aromatic compound is preferably the para position in the case of benzene, biphenylene and terphenyl, and the 2- or 6-position in the case of naphthalene and anthracene, because the coefficient of linear thermal expansion of the resultant polyimide can be reduced.
• the examples of the diamine components to introduce the chemical structure of the above chemical formulae (4.1) to (4-3) include 4,4′-diaminobenzanilide, 3′-chloro-4,4′-diaminobenzanilide, 2′-chloro-4,4-diaminobenzanilide, 2′,6′-dichloro-4,4′-diaminobenzanilide, 3′-methyl-4,4′-diaminobenzanilide, 2′-methyl-4,4′-diaminobenzanilide, 2′,6′-dimethyl-4,4′-diaminobenzanilide, 3′-trifluoromethyl-4,4′-diaminobenzanilide, 2′-trifluoromethyl-4,4′-diaminobenzanilide, 3-chloro-4,4′-diaminobenzanilide, 3-bromo-4,4′-diaminobenzanilide, 3-methyl
• 4,4′-diaminobenzanilide, N,N′-bis(4-aminophenyl)terephthalamid and N,N′-p-phenylenebis (p-aminobenzamide) are preferred, and N,N′-bis(4-aminophenyl)terephthalamid and N,N′-p-phenylenebis (p-aminobenzamide) are more preferred because they provides polyimide having low coefficient of thermal expansion.
• the abovementioned diamine components may be used alone or in combination of two or more.
• diamine components generally employed for polyimides may be used together in a small amount within the range that the properties of the polyimide of the present invention can be achieved (preferably 30% by mole or less, more preferably 10% by mole or less, further preferably less than 10% by mole).
• diamine components used in the present invention include oxydianiline, p-phenylenediamine, m-phenylenediamine, benzidine, 3,3′-dimethylbenzidine, 2,2′-dimethylbenzidine, p-methylene bis(phenylenediamine), bis(aminophenoxy)benzene, bis[(aminophenoxy)phenyl]hexafluoropropane, bis(aminophenyl)hexafluoropropane, bis(aminophenyl)sulfone, bis(trifluoromethyl)benzidine, cyclohexane diamine, bis[(aminophenoxy)phenyl]propane, bis(aminohydroxyphenyl)hexafluoropropane, bis[(aminophenoxy)diphenyl]sulfone and the like.
• the diamine component to be used in the present invention is not particularly limited; however, it preferably has a purity of 99% or more, and more preferably 99.5% or more (in the case of using a plurality of types of diamine components, it is the value of a diamine component having the highest purity, or it is an average purity value obtained by individually obtaining the purities of all diamine components to be used and weighing them each by the mass ratio of the use amount thereof is regarded as the purity, namely, for example, when a diamine component having a purity of 100% is used in an amount of 70 parts by mass and a diamine component having a purity of 90% is used in an amount of 30 parts by mass, the purity of the diamine component to be used is calculated as 97%). If the purity is less than 98%, the molecular weight of the resultant polyimide precursor is not sufficiently increased and the heat resistance of the resultant polyimide is sometimes inferior.
• the purity is a value obtained by gas chromatographic analysis or liquid chromatographic analysis.
• the diamine component to be used in the present invention is not particularly limited; however, it preferably has a light transmittance of 30% or more (in the case of using a plurality of types of diamine components, it is the value of a diamine component having the most excellent light transmittance, or it is an average light transmittance value obtained by individually obtaining the purities of all diamine components to be used and weighing them each by the mass ratio of the use amount thereof is regarded as the light transmittance, namely for example, when a diamine component having a light transmittance of 100% is used in an amount of 70 parts by mass and a diamine component having a light transmittance of 90% is used in an amount of 30 parts by mass, the light transmittance of the diamine component to be used is calculated as 97%).
• the light transmittance herein is a transmittance at a wavelength of 400 nm and an optical path length of 1 cm as an 8% by mass solution obtained by dissolving a diamine component in methanol, water, N,N-dimethylacetamide or acetic acid or hydrochloric acid solutions thereof.
• the light transmittance of a diamine component is preferably 30% or more, because degree of coloration of the resultant polyimide is reduced.
• the tetracarboxylic acid component to be used in the polyimide precursor (B) of the present invention is not particularly limited as long as it is an aliphatic tetracarboxylic acid component; however, it is preferably an alicyclic tetracarboxylic acid component having at least one aliphatic six-membered ring and no aromatic ring in the chemical structure.
• the six-membered ring contained in the tetracarboxylic acid component may also be plural and a plurality of six-membered rings may have two or more common carbon atoms as constituents.
• carbon atoms (within the six-membered ring) constituting a six-membered ring may chemically bind to each other to form another ring.
• the six-membered ring may have a crosslinked cyclic form.
• the tetracarboxylic acid component not have an asymmetric but a highly symmetric six-membered ring structure, because a polymer chain can be densely packed and the resultant polyimide has excellent solvent resistance, heat resistance and mechanical strength.
• tetracarboxylic acid component have polyalicyclic type of six-membered rings having two or more common carbon atoms as constituents, or the tetracarboxylic acid component is a crosslinked cyclic type of six-membered ring, in which carbon atoms constituting the ring chemically bind to each other to form another ring, because satisfactory heat resistance, solvent resistance and a low coefficient of linear thermal expansion of the resultant polyimide can be easily attained.
• the tetravalent group derived from the tetracarboxylic acid component represented by A in the above chemical formula (1) for example, groups represented by the above chemical formulae (3-1) to (3-4) are preferable; a group represented by the above chemical formula (3-3) or (3-4) is more preferable; and a group represented by the above chemical formula (3-4) is particularly preferable.
• the groups represented by the above chemical formulae (3-3) and (3-4) are more preferable because they are a crosslinked cyclic type and thus the heat resistance of the polyimide is excellent and the coefficient of linear thermal expansion thereof is low.
• the group represented by the above chemical formula (3-4) is particularly preferable because it is a polyalicyclic/crosslinked cyclic type and thus the heat resistance of the polyimide is more excellent.
• tetracarboxylic acid components to introduce the chemical structure of the above chemical formulae (3-1) and (3-2) include the same examples as those listed for the polyimide precursor (A), and preferable examples are the same.
• tetracarboxylic acid components to introduce the chemical structure of the above chemical formulae (3-3) or (3-4) include the same examples as those listed for the polyimide precursor (A), and preferable examples are the same.
• the tetracarboxylic acid component as mentioned above can be used alone or in combination of a plurality of types.
• aromatic or aliphatic tetracarboxylic acid components generally employed for polyimides may be used together in a small amount within the range that the properties of the polyimide of the present invention can be achieved, (preferably 30 mole % or less, more preferably 10 mole % or less, further preferably less than 10 mole %).
• the tetracarboxylic acid component to be used in the present invention is not particularly limited; however, it preferably has a purity of 99% or more, and preferably 99.5% or more (in the case that plural stereoisomers are contained, the purity is determined by regarding the stereoisomers as a single component without distinguishing them; in the case of using a plurality of types of tetracarboxylic acid components, it is the value of a tetracarboxylic acid component having the highest purity, or it is an average purity value obtained by individually obtaining the purities of all tetracarboxylic acid components to be used and weighing them each by the mass ratio of the use amount thereof is regarded as the purity, namely, for example, when a tetracarboxylic acid component having a purity of 100% is used in an amount of 70 parts by mass and a tetracarboxylic acid component having a purity of 90% is used in an amount of 30 parts by mass, the purity of the tetracarboxylic acid
• the purity is less than 98%, the molecular weight of the resultant polyimide precursor is not sufficiently increased and the heat resistance of the resultant polyimide is sometimes inferior.
• the purity is a value obtained by gas chromatographic analysis or 1 H-NMR analysis.
• the purity thereof can be obtained in terms of tetracarboxylic acid obtained by hydrolyzing the tetracarboxylic dianhydride.
• the tetracarboxylic acid component to be used in the present invention is not particularly limited; however, it preferably has a light transmittance of 70% or more, preferably 80% or more and more preferably 90% or more (in the case of using a plurality of types of tetracarboxylic acid components, it is the value of a tetracarboxylic acid component having the most excellent light transmittance, or it is an average light transmittance value obtained by individually obtaining the purities of all tetracarboxylic acid components to be used and weighing them each by the mass ratio of the use amount thereof is regarded as the light transmittance, namely, for example, when a tetracarboxylic acid component having a light transmittance of 100% is used in an amount of 70 parts by mass and a tetracarboxylic acid component having a light transmittance of 90% is used in an amount of 30 parts by mass, the light transmittance of the tetracarboxylic acid component to be used is calculated
• the light transmittance herein is a transmittance at a wavelength of 400 nm and an optical path length of 1 cm as a 10% by mass solution obtained by dissolving a tetracarboxylic acid component in a 2N sodium hydroxide solution.
• the light transmittance of a tetracarboxylic acid component is preferably 70% or more, because degree of coloration of the resultant polyimide is reduced.
• the diamine component to be used in the polyimide precursor (B) of the present invention is a diamine component having at least one chemical structure represented by the above chemical formula (2) in the chemical structure.
• the chemical structure represented by the above chemical formula (2) is introduced into the chemical structure of the polyimide precursor (B) of the present invention by a diamine component.
• a coefficient of linear thermal expansion, solvent resistance or the like are improved presumably because intermolecular interaction is augmented by the introduced chemical structure represented by the above chemical formula (2).
• flame resistance (as an indicator thereof, the oxygen index is used) or adhesion are improved presumably because the chemical structure represented by the above chemical formula (2) has two nitrogen atoms, and thus, the nitrogen atoms can be efficiently introduced into the resultant polyimide. Therefore, the diamine component preferably contains one or more chemical structures represented by the above chemical formula (2), preferably a plurality of chemical structures represented by the above chemical formula (2) in the chemical structure.
• diamine component represented by B in the above chemical formula (1) for example, groups represented by the above chemical formula (4-4) is preferable. That is, the diamine components preferably used are diamines represented by the following chemical formula (4-5):
• Ar 14 and Ar 15 are each independently a divalent aromatic group having 6 to 18 carbon atoms; and R5 is a hydrogen atom or a monovalent organic group.
• diamines represented by the aforementioned chemical formula (4-5) include 2,4-bis(4-aminoanilino)-1,3,5-triazine, 2,4-bis(4-aminoanilino)-6-methyl-1,3,5-triazine, 2,4-bis(4-aminoanilino)-6-ethyl-1,3,5-triazine, 2,4-bis(4-aminoanilino)-6-phenyl-1,3,5-triazine, 2,4-bis(4-aminoanilino)-6-amino-1,3,5-triazine, 2,4-bis(4-aminoanilino)-6-methylamino-1,3,5-triazine, 2,4-bis(4-aminoanilino)-6-dimethylamino-1,3,5-triazine, 2,4-bis(4-aminoanilino)-6-ethylamino-1,3,5-triazin
• 2,4-bis(4-aminoanilino)-6-amino-1,3,5-triazine 2,4-bis(4-aminoanilino)-6-methylamino-1,3,5-triazine, 2,4-bis(4-aminoanilino)-6-ethylamino-1,3,5-triazine, 2,4-bis(4-aminoanilino)-6-anilino-1,3,5-triazine and more preferred are 2,4-bis(4-aminoanilino)-6-anilino-1,3,5-triazine.
• the abovementioned diamine components may be used alone or in combination of two or more.
• diamine components generally employed for polyimides may be used together in a small amount within the range that the properties of the polyimide of the present invention can be achieved (preferably 30% by mole or less, more preferably 10% by mole or less, further preferably less than 10% by mole).
• the diamine component to be used in the present invention is not particularly limited; however, it preferably has a purity of 99% or more, and more preferably 99.5% or more (in the case of using a plurality of types of diamine components, it is the value of a diamine component having the highest purity, or it is an average purity value obtained by individually obtaining the purities of all diamine components to be used and weighing them each by the mass ratio of the use amount thereof is regarded as the purity, namely, for example, when a diamine component having a purity of 100% is used in an amount of 70 parts by mass and a diamine component having a purity of 90% is used in an amount of 30 parts by mass, the purity of the diamine component to be used is calculated as 97%). If the purity is less than 98%, the molecular weight of the resultant polyimide precursor is not sufficiently increased and the heat resistance of the resultant polyimide is sometimes inferior.
• the purity is a value obtained by gas chromatographic analysis.
• the diamine component to be used in the present invention is not particularly limited; however, it preferably has a light transmittance of 30% or more (in the case of using a plurality of types of diamine components, it is the value of a diamine component having the most excellent light transmittance, or it is an average light transmittance value obtained by individually obtaining the purities of all diamine components to be used and weighing them each by the mass ratio of the use amount thereof is regarded as the light transmittance, namely, for example, when a diamine component having a light transmittance of 100% is used in an amount of 70 parts by mass and a diamine component having a light transmittance of 90% is used in an amount of 30 parts by mass, the light transmittance of the diamine component to be used is calculated as 97%).
• the light transmittance herein is a transmittance at a wavelength of 400 nm and an optical path length of 1 cm as an 8% by mass solution obtained by dissolving a diamine component in methanol, water, N,N-dimethylacetamide or acetic acid or hydrochloric acid solutions thereof.
• the light transmittance of a diamine component is preferably 30% or more, because degree of coloration of the resultant polyimide is reduced.
• X 1 and X 2 in the above chemical formula (1) are each independently hydrogen or a C 1-6 alkyl group, preferably a C 1-3 alkyl group, or a C 3-9 alkylsilyl group.
• the types and introduction ratio of functional groups represented by X 1 and X 2 can be changed by the production method described later.
• X 1 and X 2 are each a C 1-6 alkyl group, preferably a C 1-3 alkyl group, the storage stability of the polyimide precursor tends to be excellent.
• X 1 and X 2 are each more preferably a methyl group or an ethyl group.
• X 1 and X 2 are each a C 3-9 alkylsilyl group, the solubility of the polyimide precursor tends to be excellent. Furthermore, if X 1 and X 2 are each a C 3-9 alkylsilyl group (more specifically, the case of using a sililating agent), usually, a coefficient of linear thermal expansion tends to further decrease although situation varies depending upon the tetracarboxylic acid component and the diamine component (more specifically, depending upon components A and B in chemical formula (1)). In this case, it is preferable that X 1 and X 2 each be a trimethylsilyl group or a t-butyldimethylsilyl group.
• the introduction ratio of a functional group is not particularly limited.
• an alkyl group or an alkylsilyl group can be introduced as X 1 and X 2 , in a ratio of 25% or more, preferably 50% or more, and more preferably 75% or more.
• the polyimide precursors of the present invention can be classified depending upon the chemical structure taken by X 1 and X 2 to 1) polyamic acids (X 1 and X 2 are hydrogen), 2) polyamic acid esters (at least part of X 1 and X 2 is an alkyl group) and 3) polyamic silyl esters (at least part of X 1 and X 2 is an alkylsilyl group).
• the polyimide precursors of the present invention can be easily produced by the following production methods, respectively according to these classes.
• the production method for the polyimide precursor of the present invention is not limited to the following production methods.
• a plurality of structures of the classes mentioned above can be introduced in a same molecule chain of a polyimide precursor and a plurality of types of polyimide precursors of the classes mentioned above can be used as a mixture.
• the polyimide precursor of the present invention can be suitably obtained as a polyimide precursor solution composition by reacting a tetracarboxylic acid component (preferably a tetracarboxylic dianhydride) and a diamine component in almost equal moles, preferably in a molar ratio of the diamine component to the tetracarboxylic acid component [diamine component mole number to tetracarboxylic acid component mole number] of preferably 0.90 to 1.10, and more preferably 0.95 to 1.05, in a solvent at a relatively low temperature such as 120° C. or less to suppress the imidization.
• a tetracarboxylic acid component preferably a tetracarboxylic dianhydride
• diamine component in almost equal moles, preferably in a molar ratio of the diamine component to the tetracarboxylic acid component [diamine component mole number to tetracarboxylic acid component mole number] of preferably 0.
• a polyimide precursor solution composition can be obtained by dissolving a diamine in a solvent, gradually adding a tetracarboxylic dianhydride to the solution while stirring, and stirring the solution at a temperature in the range of 0 to 120° C., preferably 5 to 80° C. for 1 to 72 hours.
• the reaction is performed at 80° C. or more, the molecular weight varies depending upon temperature history during polymerization.
• imidization proceeds with heat, there is a possibility that a polyimide precursor is not stably produced.
• the addition order of a diamine and a tetracarboxylic dianhydride in the above production method is preferable since the molecular weight of the polyimide precursor is easily increased. Furthermore, it is also possible and preferable to invert the addition order of a diamine and a tetracarboxylic dianhydride in the above production method since the amount of precipitate is reduced.
• a carboxylic acid derivative may be added in an amount substantially corresponding to the excessive mole number of the diamine component. In this manner, the molar ratio of the tetracarboxylic acid component and the diamine component can be brought closer to almost an equivalent.
• a tetracarboxylic acid which does not substantially increase the viscosity of a polyimide precursor solution, in other words, is not substantially involved in molecular chain extension, or a tricarboxylic acid serving as an end terminating agent and an anhydride thereof, and a dicarboxylic acid and an anhydride thereof are suitable.
• a tetracarboxylic dianhydride is reacted with an arbitral alcohol to obtain a diester dicarboxylic acid, which is then reacted with a chlorinating reagent (e.g., thionyl chloride, oxalyl chloride) to obtain a diester dicarboxylic acid chloride.
• a chlorinating reagent e.g., thionyl chloride, oxalyl chloride
• the diesterdicarboxylic acid chloride and a diamine are stirred in the range of ⁇ 20 to 120° C., preferably ⁇ 5 to 80° C., for 1 to 72 hours to obtain a polyimide precursor.
• the reaction is performed at 80° C. or more, the molecular weight varies depending upon temperature history during polymerization and, in addition, imidization proceeds with heat.
• a polyimide precursor is not stably produced. Furthermore, a polyimide precursor can be easily obtained by dehydration condensation between a diester dicarboxylic acid and a diamine by use of a phosphorous-based condensing agent or a carbodiimide condensing agent.
• the polyimide precursor obtained by this method is stable, the polyimide precursor can be purified through e.g., reprecipitation performed by adding a solvent such as water or alcohols.
• a diamine and a sililating agent are reacted to obtain a sililated diamine in advance.
• the sililated diamine is purified by e.g., distillation.
• the sililated diamine is dissolved in a dehydrated solvent.
• a tetracarboxylic dianhydride is gradually added while stirring.
• the mixture is stirred in the range of 0 to 120° C., and preferably 5 to 80° C. for 1 to 72 hours to obtain a polyimide precursor.
• the reaction is performed at 80° C. or more, the molecular weight varies depending upon temperature history during polymerization and, in addition, imidization proceeds with heat. As a result, there is a possibility that a polyimide precursor is not stably produced.
• a sililating agent is added and stirred in the range of 0 to 180° C., and preferably 5 to 150° C., for 1 to 72 hours to obtain a polyimide precursor.
• the reaction is performed at 150° C. or less is preferable, because a polyimide precursor can be obtained stably while suppressing an imidization reaction.
• the sililating agent used herein is not particularly limited as long as it is a C 3-9 alkylsilyl compound.
• halogenated trialkylsilyl and a sililating agent containing no halogen can be used.
• the halogenated trialkylsilyl preference is given to trimethylsilyl chloride, triethylsilyl chloride, isopropyldimethylsilyl chloride, t-butyldimethylsilyl chloride, and triisopropylsilyl chloride, and particularly preferably to trimethylsilyl chloride and t-butyldimethylsilyl chloride because they have high reactivity and are inexpensive.
• the examples thereof include N,O-bis(trimethylsilyl)trifluoroacetamide, N,O-bis(trimethylsilyl)acetamide, and hexamethyldisilazane.
• the sililating agent containing no halogen such as a chlorine atom is preferable since it is not necessary to purify the sililated diamine.
• N,O-bis(trimethylsilyl)acetamido and hexamethyldisilazane are particularly preferable since they contain no fluorine atoms and are inexpensive.
• an amine catalyst such as pyridine, piperidine and triethylamine can be used to facilitate the reaction.
• the catalyst can be used as it is as a catalyst for polymerizing a polyimide precursor.
• aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide, and water; and particularly N,N-dimethylacetamide is preferable.
• the structure of the solvent is not particularly limited and any solvents may be used as long as the starting monomer components and the produced polyimide precursors are dissolved in the solvents.
• solvents preferably employed include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; cyclic ester solvents such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, and ⁇ -methyl- ⁇ -butyrolactone; carbonate solvents such as ethylene carbonate and propylene carbonate; glycol-based solvents such as triethylene glycol; phenol-based solvents such as m-cresol, p-cresol, 3-chlorophenol and 4-chlorophenol; acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethylsulfoxide and water.
• amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone
• cyclic ester solvents such
• the solvent for use in preparing a polyimide precursor and the solvent for use in a polyimide precursor solution composition as described later preferably satisfy at least one of the following conditions (specified below) of properties involved in purity: (a) light transmittance, (b) light transmittance after heating to reflux, (c) purity by gas chromatographic analysis, (d) ratio of peaks of impurities by gas chromatographic analysis, (e) amount of nonvolatile components, and (f) the content of metal components; and, in general, more preferably satisfy the conditions as many as possible.
• a solvent has a light transmittance of 89% or more, more preferably 90% or more, and particularly preferably 91% or more at a wavelength of 400 nm and an optical path length of 1 cm.
• a solvent has a light transmittance of 20% or more, more preferably 40% or more, and particularly preferably 80% or more at a wavelength of 400 nm and an optical path length of 1 cm after heating to reflux in nitrogen for 3 hours.
• a solvent has a purity of 99.8% or more, more preferably 99.9% or more, and further preferably 99.99% or more, as measured by gas chromatographic analysis.
• a solvent satisfies that amount of impurities of which peak appears on the longer time side with respect to the main component peak retention time in gas chromatography is less than 0.2%, more preferably 0.1% or less, particularly preferably 0.05% or less.
• the amount of components nonvolatile at 250° C. in the solvent to be used is 0.1% or less, more preferably 0.05% or less, and particularly preferably 0.01% or less.
• the content of metal components (for example, Li, Na, Mg, Ca, Al, K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Cd) in the solvent to be used is 10 ppm or less, more preferably 1 ppm or less, particularly preferably 500 ppb or less, and further particularly preferably 300 ppb or less.
• the organic solvents to be used may be one type or two or more types.
• the use of two or more types of organic solvents means a case of using a solvent mixture in a specific step and a case of using different solvents in different steps such that the polymerization solvent and the solvent for diluting an additive are different from each other.
• a solvent mixture each requirement for characteristics relating to the purity is applied to the solvent mixture as a whole.
• each requirement for characteristics relating to the purity is applied to the mixture of all organic solvents finally contained in a varnish.
• the characteristics may be each measured for a mixture prepared actually mixing organic solvents. Alternatively, the characteristics may be each measured for each organic solvent, and the characteristic of a mixture as a whole may be determined by calculation. For example, when 70 parts of solvent A having a purity of 100% and 30 parts of solvent B having a purity of 90% are used, the organic solvent used has a purity of 97%.
• the logarithmic viscosity of a polyimide precursor is not particularly limited; however, it is preferable that the logarithmic viscosity of a polyimide precursor in N,N-dimethylacetamide solution of 0.5 g/dL in concentration at 30° C. is 0.2 dL/g or more, and preferably 0.5 dL/g or more. If the logarithmic viscosity is 0.2 dL/g or more, the molecular weight of a polyimide precursor is high and thus the mechanical strength and heat resistance of the resultant polyimide are excellent.
• the polyimide precursor of the present invention is not particularly limited; however, when a polyimide precursor is dissolved in a solvent selected from N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide and water in a concentration of 10 mass % to obtain a solution, a light transmittance at a wavelength of 400 nm and an optical path length of 1 cm through the solution is preferably 30% or more, and more preferably 40% or more. If the transmittance of light at a wavelength of 400 nm is 30% or more, the resultant polyimide is excellent in light transmittance.
• a solvent selected from N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imi
• a polyimide precursor solution composition contain at least the polyimide precursor of the present invention and a solvent, and the sum of tetracarboxylic acid component and diamine component is 5 mass % or more, preferably 10 mass % or more, and more preferably 15 mass % or more based on the total amount of solvent, tetracarboxylic acid component and diamine component.
• the ratio be usually 60 mass % or less, and preferably 50 mass % or less.
• the concentration is close to the concentration of a solid substance ascribed to a polyimide precursor. If the concentration is extremely low, it becomes difficult to control the thickness of a polyimide film obtained for example when a polyimide film is produced.
• amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone
• cyclic ester solvents such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, and ⁇ -methyl- ⁇ -butyrolactone
• carbonate solvents such as ethylene carbonate and propylene carbonate
• glycol-based solvents such as triethylene glycol
• phenol-based solvents such as m-cresol, p-cresol, 3-chlorophenol and 4-chlorophenol
• acetophenone 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethylsulfoxide and water.
• the viscosity of a polyimide precursor solution composition is not particularly limited; however, the rotatory viscosity, which is measured by an E-type rotatory viscometer at a temperature of 25° C. and at a shearing rate of 20 sec ⁇ 1 , is preferably 0.01 to 1000 Pa ⁇ sec, and more preferably 0.1 to 100 Pa ⁇ sec. Furthermore, if necessary, thixotropy can be imparted. In the above viscosity range, the composition is easily handled in coating and forming a film. In addition, since repulsion is suppressed and leveling property is excellent, a satisfactory film can be obtained.
• a chemical imidizing agent an acid anhydride such as acetic anhydride, an amine compound such as pyridine and isoquinoline
• an antioxidant an antioxidant
• a filler a dye, a pigment, a coupling agent such as a silane coupling agent, a primer, a flame retardant, a defoaming agent, a leveling agent, a rheology control agent (auxiliary flowability control agent), a remover and the like
• an acid anhydride such as acetic anhydride, an amine compound such as pyridine and isoquinoline
• an antioxidant a filler
• a dye such as a silane coupling agent
• primer a primer
• a flame retardant such as a defoaming agent
• leveling agent such as a leveling agent
• a rheology control agent auxiliary flowability control agent
• the polyimide of the present invention is characterized in that a repeating unit represented by the above chemical formula (5) is contained as a constituent.
• the polyimide of the present invention can be suitably produced by a ring closure reaction (imidization reaction) of the polyimide precursor of the present invention as mentioned above.
• the imidization method is not particularly limited. A heat imidization or chemical imidization method known in the art can be suitably applied.
• the preferred form of the polyimide obtained may be, for example, a film, a laminate of a polyimide film and a substrate, a coating film, a powder, beads, a compact, a foam product and vanish.
• the polyimide of the present invention has excellent light transmittance, and although it is not particularly limited, the total light transmittance (average transmittance of light having a wavelength 380 nm to 780 nm) of a film formed of the polyimide having a thickness of 10 ⁇ m, is preferably 70% or more, more preferably 80% or more, and particularly preferably 85% or more.
• the polyimide of the present invention has excellent transparency, and although it is not particularly limited, the transmittance of light at a wavelength of 400 nm when formed into a film with a thickness of 10 ⁇ m is preferably 50% or more, more preferably 60% or more, more preferably 70% or more, particularly preferably 75% or more.
• the polyimide of the present invention has an extremely low coefficient of linear thermal expansion, and although it is not particularly limited, the average coefficient of linear thermal expansion of a film formed thereof is preferably 50 ppm/K or less, more preferably 40 ppm/K or less, and particularly preferably 20 ppm/K or less at 50° C. to 200° C.
• the polyimide of the present invention has excellent flame resistance.
• the oxygen index of a film formed of the polyimide and obtained in accordance with JIS K 7201 is 22% (volume fraction) or more and more preferably 24% (volume fraction) or more.
• the polyimide of the present invention having high flame resistance is obtained from a polyimide precursor (B).
• A” in the above chemical formula (5) represents an aliphatic tetravalent group and “B” is preferably a divalent group having at least one chemical structure represented by the above chemical formula (2) in the chemical structure.
• the film thickness of a film formed of the polyimide of the present invention is preferably about 1 ⁇ m to 250 ⁇ m, and further preferably about 1 ⁇ m to 150 ⁇ m.
• the polyimide of the present invention has excellent properties such as transparency, bending resistance and high heat resistance, and furthermore has an extremely low coefficient of linear thermal expansion and excellent solvent resistance, or excellent solvent resistance and flame resistance together.
• the polyimide of the present invention can be suitably used as transparent substrates for displays, touch panels or as substrates for solar batteries.
• the polyimide precursor solution composition of the present invention is cast onto a base material such as a ceramic (glass, silicon, alumina), a metal (copper, aluminum, stainless steel), or a thermally stable plastic film (polyimide) and is dried in a temperature range of 20 to 180° C., preferably 20 to 150° C., with hot air or infrared radiation in vacuum, in an inert gas such as nitrogen, or in the air.
• a base material such as a ceramic (glass, silicon, alumina), a metal (copper, aluminum, stainless steel), or a thermally stable plastic film (polyimide)
• the resulting polyimide precursor film is heated for imidization on the base material or in a state peeled from the base material and fixed at the ends at 200 to 500° C., more preferably about 250 to 450° C., with hot air or infrared radiation in vacuum, in an inert gas such as nitrogen, or in the air.
• a polyimide film/base material laminate or a polyimide film can be produced.
• the thermal imidization in vacuum or in an inert gas is desirable for preventing oxidative degradation of the resulting polyimide film. If the temperature for the thermal imidization is not too high, thermal imidization in the air is allowable.
• the thickness of the polyimide film (in the case of the polyimide film/base material laminate, the polyimide film layer) is preferably 1 to 250 ⁇ m, more preferably 1 to 150 ⁇ m, for the transportability in the subsequent steps.
• the imidization of the polyimide precursor may be also performed by chemical treatment by, for example, immersing the polyimide precursor in a solution containing a cyclodehydrating agent such as acetic anhydride in the presence of a tertiary amine such as pyridine or triethylamine, instead of the thermal imidization by heat treatment as described above.
• a partially imidized polyimide precursor may be produced by stirring a polyimide precursor solution composition containing a cyclodehydrating agent in advance, casting the mixture onto a base material, and drying it.
• the partially imidized polyimide precursor can be formed into a polyimide film/base material laminate or a polyimide film by the heat treatment described above.
• the thus-prepared polyimide film/base material laminate or polyimide film can be formed into a flexible conductive substrate by forming a conductive layer on one surface or both surfaces of the laminate or the film.
• the flexible conductive substrate can be prepared by, for example, the following methods. That is, in a first method, a conductive laminate of (conductive layer)/(polyimide film)/(base material) is produced by forming a conductive layer of a conductive material (e.g., a metal, a metal oxide, a conductive organic material, or conductive carbon) on the polyimide film surface of the (polyimide film)/(base material) laminate without peeling the polyimide film from the substrate by, for example, sputtering deposition or printing. Subsequently, the (electrically conductive layer)/(polyimide film) laminate is peeled from the base material as necessary to provide a transparent and flexible conductive substrate composed of conductive layer/polyimide film laminate.
• a conductive laminate of (conductive layer)/(polyimide film)/(base material) is produced by forming a conductive layer of a conductive material (e.g., a metal, a metal oxide, a
• the polyimide film is peeled off from the base material of a (polyimide film)/(base material) laminate to provide a polyimide film, and a conductive layer of a conductive material (e.g., a metal, a metal oxide, a conductive organic material, or conductive carbon) is formed on the polyimide film surface as in the first method to provide a transparent and flexible conductive substrate composed of (conductive layer)/(polyimide film) laminate.
• a conductive layer of a conductive material e.g., a metal, a metal oxide, a conductive organic material, or conductive carbon
• a gas-barrier layer against water vapor, oxygen, etc. or an inorganic layer such as a light controlling layer may be optionally formed by, for example, sputtering deposition or a gel-sol method before the formation of the conductive layer on the polyimide film surface.
• a circuit is suitably formed on the conductive layer by a method such as photolithography, various printing methods, or ink-jetting.
• the substrate of the present invention includes the circuit of the conductive layer on the surface of a polyimide film formed from the polyimide of the present invention, if necessary via a gas-barrier layer or an inorganic layer.
• the substrate is flexible and has excellent transparency, bending resistance, and heat resistance and also has a considerably low coefficient of linear thermal expansion and high solvent resistance. Therefore, a fine circuit can be readily formed. Accordingly, the substrate can be suitably used as a substrate for a display, touch panel, or solar cell.
• a flexible thin-film transistor is produced by further forming a transistor (inorganic transistor or organic transistor) on the substrate by a method such as deposition, various printing methods, or ink-jet method and is suitably used as a liquid crystal device for a display device, EL device, or photoelectric device.
• tetracarboxylic components a predetermined amount of tetracarboxylic components was dissolved in a solvent (2 N aqueous solution of sodium hydroxide) to obtain a 10 mass % solution.
• diamine components a predetermined amount of diamine components was dissolved in a solvent (methanol) to obtain an 8 mass % solution.
• a MCPD-300 manufactured by Otsuka Electronics Co., Ltd., and a standard cell having a light path length of 1 cm the light transmittance at 400 nm of the prepared solutions of the diamine components and the tetracarboxylic components was measured using the measurement solvent as a blank.
• the solvent purity was measured under the following conditions using a GC-2010 manufactured by Shimadzu Corporation.
• the purity (GC) was determined from the peak surface area fraction.
• the light transmittance of a solvent at 400 nm was measured using water as a blank.
• light transmittance after heating with refluxing As for light transmittance after heating with refluxing, light transmittance at 400 nm was measured for a solvent that had been heated to reflux for 3 hours under nitrogen atmosphere having oxygen concentration of 200 ppm or less.
• the metal content contained in the solvent was quantified based on inductively coupled plasma mass spectrometry (ICP-MS) using an Elan DRC II manufactured by PerkinElmer Inc.
• ICP-MS inductively coupled plasma mass spectrometry
• the viscosity of the polyimide precursor solution at a temperature of 25° C. and a shear rate of 20 sec ⁇ 1 was determined using a TV-22 E-type rotary viscometer manufactured by Toki Sangyo Co., Ltd.
• the logarithmic viscosity was determined by measuring a 0.5 g/dL solution of the polyimide precursor in N,N-dimethylacetamide at 30° C. using an Ubbelohde viscometer.
• the polyimide precursor was diluted with N,N-dimethylacetamide so as to form a 10 mass % polyimide precursor solution. Then, using the prepared solutions and using a MCPD-300 manufactured by Otsuka Electronics Co., Ltd., and a standard cell having a light path length of 1 cm, the light transmittance at 400 nm of the 10 mass % polyimide precursor solution was measured using N,N-dimethylacetamide as a blank.
• the light transmittance at 400 nm and total light transmittance (average light transmittance from 380 nm to 780 nm) of a polyimide film with a thickness of 10 ⁇ m were measured using a MCPD-300 manufactured by Otsuka Electronics Co., Ltd.
• the initial elastic modulus and elongation at break for a chuck interval of 30 mm and a tension rate of 2 mm/min were measured using a Tensilon manufactured by Orientec Co., Ltd., on a test piece produced by punching a polyimide film with a thickness of 10 ⁇ m into an IEC450 standard dumbbell shape.
• a test piece was produced by cutting a polyimide film with a thickness of 10 ⁇ m into a strip with a width of 4 mm. Then, using a TMA-50 manufactured by Shimadzu Corporation, the temperature of the test piece was increased to 300° C. at a rate of temperature increase of 20° C./min with a chuck interval of 15 mm and a load of 2 g. The average coefficient of thermal expansion from 50° C. to 200° C. was determined from the obtained TMA curve.
• a test piece was produced by cutting a polyimide film with a thickness of 10 ⁇ m into a strip with a width of 4 mm. The test piece was bent with a curvature radius of 1 mm under the conditions of a temperature of 25° C. and a humidity of 50% RH. The resultant test pieces were visually observed. A test piece having no abnormality was indicated by ⁇ (good) and a test piece having a crack was indicated by x (bad).
• a polyimide film having a thickness of about 10 ⁇ m was soaked in N,N-dimethylacetamide under the conditions of a temperature of 25° C. for one hour and thereafter, the state of the film was visually observed.
• a test piece having no abnormality was indicated by ⁇ (good); a test piece having wrinkle or partly having a change of shape was indicated by ⁇ (mdedium), and a test piece dissolved or having a significant change of shape was indicated by x (bad).
• a polyimide film having a thickness of about 10 ⁇ m was used as a test piece.
• the temperature of the test piece was increased from 25° C. to 600° C. by use of a differential thermogravity/thermogravity simultaneous measuring apparatus (TG/DTA6300) manufactured by SII Nano Technology Inc., under a nitrogen flow at a temperature raising rate of 10° C./min. From the obtained weight curve, 5% weight loss temperature was obtained.
• TG/DTA6300 differential thermogravity/thermogravity simultaneous measuring apparatus manufactured by SII Nano Technology Inc.
• a polyimide film having a thickness of about 30 ⁇ m was used as a test piece.
• Oxygen index of the test piece was obtained by a method (test piece shape: V type, 140 mm ⁇ 52 mm ⁇ about 30 ⁇ m) in accordance with JIS K 7201 using a candle combustion tester D-type manufactured by Toyo Seiki Seisaku-sho, Ltd.
• DABAN 4,4′-diaminobenzanilide; purity 99.90% (GC analysis).
• PPD p-phenylene diamine purity 99.9% (GC analysis).
• TFMB 2,2′-his (trifluoromethyl)benzidine; purity 99.83% (GC analysis).
• BABA N,N′-p-phenylene bis(p-aminobenzamide); purity 99% (GC analysis).
• AZDA 2,4-bis(4-aminoanilino)-6-anilino-1,3,5-triazine; purity 99.9% (GC analysis).
• BABB 1,4-Bis(4-aminobenzoyloxy)benzene; purity 99.8% (GC analysis).
• PMDA-HS 1R,2S,4S,5R-Cyclohexane tetracarboxylic dianhydride; purity (as PMDA-HS) 92.7% (GC analysis); purity (as hydrogenated pyromellitic dianhydride) 99.9% (GC analysis).
• BPDA-H 3,3′,4,4′-bicyclohexyltetracarboxylic dianhydride; purity (as mixture of stereoisomers) 99.9% (GC analysis).
• DNDAxx (4arH,8acH)-decahydro-1t, 4t:5c,8c-dimethano naphthalene-2t,3t,6c,7c-tetracarboxylic dianhydride; purity (as DNDAxx) 99.2% (GC analysis).
• DNDAdx (4arH,8acH)-decahydro-1t,4t:5c,8c-dimethano naphthalene-2c,3c,6c,7c-tetracarboxylic dianhydride; purity (as DNDAdx) 99.7% (GC analysis).
• Table 3 shows the structural formulae of the tetracarboxylic acid components and diamine components used in Examples and Comparative examples.
• Tetracarboxylic acid component DABAN PMDA-HS 4-APTP BPDA-H BABA cis/cis-BTA-H AZDA DNDAxx TFMB DNDAdx PPD ODA
• the polyimide precursor solution that was filtered using a PTFE membrane filter was applied on a glass substrate, and thermally imidized by heating at 120° C. for 1 hour, at 150° C. for 30 minutes, at 200° C. for 30 minutes, then heating up and at 350° C. for 5 minutes while holding it on the substrate under nitrogen atmosphere (oxygen concentration is 200 ppm or less) to obtain a colorless transparent polyimide/glass laminate.
• oxygen concentration is 200 ppm or less
• Polyimide precursor solutions and polyimide films were obtained in the same manner as Example 1 except that diamine component and carboxylic acid component were selected as indicated in Table 4-1, and N,N-dimethylacetamide is used in such an amount that the feeding amount of monomers (total amount of diamine component and carboxylic acid component) is 15% by mass.
• Polyimide precursor solutions and polyimide films were obtained in the same manner as Example 1 except that diamine components and carboxylic acid components were selected as indicated in Table 4-2, and N,N-dimethylacetamide is used in such an amount that the feeding amount of monomers (total amount of diamine component and carboxylic acid component) is 15% by mass for Comparative examples 1 and 2 and 20% by mass for Comparative examples 3 and 4.
• Examples 1 to 18 according to the present invention in which diamines having amide bonds) are used have smaller coefficient of linear thermal expansion and excellent solvent resistance compared with Comparative Examples 1 to 4.
• the produced polyimides have higher 5% weight loss temperature and are therefore excellent in heat resistance compared with the case in which a tetracarboxylic acid component having one six-membered ring structure is used (Examples 1 and 2).
• the produced polyimides have further higher 5% weight loss temperature and are therefore excellent in heat resistance, compared with the cases in which a tetracarboxylic acid component having two six-membered ring structure is used (Example 3) or that a crosslinked cyclic type tetracarboxylic acid component in which carbon atoms constituting six-membered ring are chemically bonded to form another ring is used (Examples 4 and 5).
• silylating agent results in the increase in elongation at break or smaller coefficient of linear thermal expansion (Examples 8, 12, 13 and 17).
• the polyimides obtained from the polyimide precursors of the present invention have excellent light transmittance and bending resistance, and furthermore low coefficient of linear thermal expansion and excellent solvent resistance in combination. Therefore, they are suitably used as a transparent substrate that is colorless and transparent and capable of forming a fine circuit for use in displays and the like.
• the polyimide precursor solution that was filtered using a PTFE membrane filter was applied on a glass substrate, and thermally imidized by heating at 120° C. for 1 hour, at 150° C. for 30 minutes, at 200° C. for 30 minutes, then heating up and at 350° C. for 5 minutes while holding it on the substrate under nitrogen atmosphere (oxygen concentration is 200 ppm or less) to obtain a colorless transparent polyimide/glass laminate.
• oxygen concentration is 200 ppm or less
• Examples 19 to 21 according to the present invention in which diamines having a chemical structure represented by formula (2) are used have smaller coefficient of linear thermal expansion and are excellent in solvent resistance, heat resistance and flame resistance (high oxygen index), compared with Comparative Examples 5 to 7.
• the polyimides obtained from the polyimide precursors of the present invention have excellent light transmittance and bending resistance, and furthermore low coefficient of linear thermal expansion, excellent solvent resistance and flame resistance in combination. Therefore, they are suitably used as a transparent substrate that is colorless and transparent and capable of forming a fine circuit for use in displays and the like.
• a polyimide having excellent properties such as transparency, bending resistance and high heat resistance in combination with an extremely low coefficient of linear thermal expansion and excellent solvent resistance, and a precursor thereof. Furthermore, according to the present invention, there is provided a polyimide having excellent properties such as transparency, bending resistance and high heat resistance in combination with an extremely low coefficient of linear thermal expansion, excellent solvent resistance and flame resistance, and a precursor thereof.
• the polyimide obtained from the polyimide precursor and the polyimide have high transparency and a low coefficient of linear thermal expansion allowing a fine circuit to be easily formed, and solvent resistance in combination.

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