US20140218875A1 - Aqueous polyimide precursor solution composition and method for producing aqueous polyimide precursor solution composition - Google Patents

Aqueous polyimide precursor solution composition and method for producing aqueous polyimide precursor solution composition Download PDF

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US20140218875A1
US20140218875A1 US14/343,745 US201214343745A US2014218875A1 US 20140218875 A1 US20140218875 A1 US 20140218875A1 US 201214343745 A US201214343745 A US 201214343745A US 2014218875 A1 US2014218875 A1 US 2014218875A1
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mol
polyimide precursor
tetracarboxylic acid
aromatic
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Takeshige Nakayama
Susumu Takasaki
Tomonori Nakayama
Kensuke Hiroshige
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C/O UBE INDUSTRIES Ltd
Ube Corp
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Assigned to UBE INDUSTRIES, LTD. reassignment UBE INDUSTRIES, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TAKASAKI, SUSUMU, HIROSHIGE, KENSUKE, NAKAYAMA, TAKESHIGE, NAKAYAMA, TOMONORI
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1021—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • 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
    • 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
    • C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C08G73/128—Unsaturated polyimide precursors the unsaturated precursors containing heterocyclic moieties in the main chain
    • 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
    • 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
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • H05K1/0277—Bendability or stretchability details
    • H05K1/028—Bending or folding regions of flexible printed circuits
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/007—Manufacture or processing of a substrate for a printed circuit board supported by a temporary or sacrificial carrier
    • 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
    • C09D179/085—Unsaturated polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133305—Flexible substrates, e.g. plastics, organic film

Definitions

  • the present invention relates to an aqueous polyimide precursor solution composition and a method for easily producing an aqueous polyimide precursor solution composition.
  • the aqueous polyimide precursor solution composition is preferred because of having high environmental acceptability as compared with a polyimide precursor solution composition comprising an organic solvent.
  • the production method of the present invention does not require any solvent other than water, and therefore it may provide an aqueous polyimide precursor solution composition having a lower content of organic solvent than the conventional compositions, and may provide an aqueous polyimide precursor solution composition containing an aqueous solvent and containing no organic solvent, which has higher environmental acceptability.
  • a polyimide may be suitably obtained from the aqueous polyimide precursor solution composition.
  • a polyimide obtained from a specific aqueous polyimide precursor solution composition of the present invention in particular, has excellent properties such as heat resistance, mechanical strength, electrical properties, and solvent resistance, and further has excellent flexibility.
  • the present invention also relates to a method for producing a polyimide seamless belt using the aqueous polyimide precursor solution composition.
  • the present invention also relates to a binder resin composition (aqueous polyimide precursor solution composition for a binder resin) for an electrode of an electrochemical device such as a lithium ion secondary battery and an electric double layer capacitor.
  • the present invention also relates to an aqueous polyimide precursor solution composition for a flexible device substrate, for example, an aqueous polyimide precursor solution composition for a substrate of a display device such as a liquid crystal display, an organic EL display and an electronic paper, and a light-receiving device such as a light-receiving element of a thin-film solar cell.
  • a polyimide obtained from a tetracarboxylic dianhydride and a diamine particularly an aromatic polyimide obtained from an aromatic tetracarboxylic dianhydride and an aromatic diamine has excellent properties such as heat resistance, mechanical strength, electrical properties, and solvent resistance, and therefore is widely used in the electrical/electronics industrial field and the like.
  • polyimides have poor solubility in organic solvents, however, polyimides are generally prepared by applying a solution composition in which a polyamic acid as a polyimide precursor is dissolved in an organic solvent, for example, onto a substrate surface, and then heating the solution composition at a high temperature to effect dehydration/ring closure (imidization).
  • the polyamic acid solution composition to produce a polyimide contains an organic solvent and must be subjected to heat treatment at a high temperature, and therefore the polyamic acid solution composition is not necessarily environmentally friendly and in some cases, its application is limited.
  • an aromatic polyimide obtained from an aromatic tetracarboxylic dianhydride and an aromatic diamine has excellent heat resistance, mechanical strength and the like, and therefore is widely used in the electrical/electronics industrial field and the like.
  • a polyimide further having excellent flexibility, for example, in the binder application, flexible-device application and the like.
  • Patent Literature 1 proposes a process for producing an aqueous polyamide acid salt solution composition, comprising
  • polyimide precursor composition reacting the polyamide acid in water with a certain amine compound such as 2-methylamino diethanol to form a water-soluble polyamide acid salt.
  • a certain amine compound such as 2-methylamino diethanol
  • Patent Literature 2 proposes a water-soluble polyimide precursor prepared by reacting a polyamic acid (polyimide precursor), which is prepared by reacting a tetracarboxylic acid component with an aromatic diamine component in an organic solvent, with 1,2-dimethylimidazole and/or 1-methyl-2-ethylimidazole, and then separating the water-soluble polyimide precursor from the reaction mixture.
  • the water-soluble polyimide precursors prepared in Examples of Patent Literature 2 were ones from which only amorphous aromatic polyimides could be obtained.
  • a polyimide which is obtained from the water-soluble polyimide precursor prepared in Patent Literature 2 is amorphous and thermal-fusion bondable, and is suitably used as a binder for a woven or nonwoven fabric made of organic or inorganic fibers, there is room for improvement in the properties of the polyimide in some applications.
  • the aqueous polyimide precursor solution composition is prepared by a process, comprising
  • Non Patent Literature 1 shows that a binder resin for electrodes having a lower degree of swelling in a liquid electrolyte is preferred, because the retention of discharge capacity in charge-discharge cycles increases with the decrease in the degree of swelling of the binder resin.
  • Non Patent Literature 2 a reductive decomposition reaction of a liquid electrolyte in a lithium battery is analyzed, and it is confirmed that lithium methoxide and the like are formed on a surface of an electrode. That is, in a battery environment, a liquid electrolyte will contain lithium methoxide, which is strongly alkaline and may adversely affect a binder resin.
  • Patent Literature 3 proposes a method for producing a flexible device substrate, using a polyimide precursor resin composition which comprises an organic solvent, specifically, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, or the like as a solvent.
  • an organic solvent specifically, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, or the like.
  • the first objective of the present invention is to provide an aqueous polyimide precursor solution composition which comprises an aqueous solvent and has good environmental acceptability, and may provide a polyimide having excellent properties such as flexibility, heat resistance, mechanical strength, electrical properties, and solvent resistance, and preferably comprises a polyimide precursor (polyamic acid) having a high molecular weight and a solvent containing no organic solvent other than water.
  • Another objective of the present invention is to provide a method for easily producing the aqueous polyimide precursor solution composition without the need for a solvent other than water.
  • the second objective of the present invention is to provide a method for producing a polyimide seamless belt which have excellent properties such as flexibility, heat resistance, mechanical strength, electrical properties, and solvent resistance, and therefore may be suitably used as an intermediate transfer seamless belt or a fixing seamless belt of an electrophotographic device, using an aqueous polyimide precursor solution composition which comprises an aqueous solvent and has good environmental acceptability.
  • the third objective of the present invention is to provide a binder resin composition for electrodes which comprises an aqueous solvent and has good environmental acceptability, and may provide a polyimide having excellent properties such as flexibility, heat resistance, mechanical strength, electrical properties, and solvent resistance, and furthermore having a low degree of swelling in a battery environment, and having excellent toughness, and preferably comprises a polyimide precursor (polyamic acid) having a high molecular weight and a solvent containing no organic solvent other than water.
  • a polyimide precursor polyamic acid
  • the fourth objective of the present invention is to provide a polyimide precursor resin composition for flexible device substrates which comprises an aqueous solvent and has good environmental acceptability, and may provide a polyimide substrate for flexible device having excellent properties such as flexibility, heat resistance, mechanical strength, electrical properties, and solvent resistance, and being suitably usable as a substrate for flexible device as a display device such as substrates for a liquid crystal display, an organic EL display and an electronic paper, a substrate for flexible device as a light-receiving device such as a substrate for a thin-film solar cell, and the like, and preferably comprises a polyimide precursor (polyamic acid) having a high molecular weight and a solvent containing no organic solvent other than water.
  • a polyimide precursor polyamic acid
  • the present invention relates to the following items.
  • a polyamic acid which is formed by the reaction of a tetracarboxylic acid component and a diamine component, and consists of a repeating unit represented by the following formula (1), is dissolved in an aqueous solvent together with an imidazole in an amount of 1.6 mole or more per mole of the tetracarboxylic acid component of the polyamic acid.
  • A represents at least one selected from the group consisting of a tetravalent group of an aromatic tetracarboxylic acid containing no fluorine group, from which carboxyl groups have been removed, a tetravalent group of an aliphatic tetracarboxylic acid, from which carboxyl groups have been removed, and a tetravalent group of an aromatic tetracarboxylic acid containing a fluorine group, from which carboxyl groups have been removed, and
  • B represents at least one selected from the group consisting of a divalent group of an aromatic diamine containing no fluorine group and having a solubility in water at 25° C. of 0.1 g/L or more, from which amino groups have been removed, a divalent group of an aliphatic diamine having a molecular weight of 500 or less, from which amino groups have been removed, and a divalent group of an aromatic diamine containing a fluorine group, from which amino groups have been removed, with the proviso that
  • A more than 50 mol % of A is a tetravalent group of an aromatic tetracarboxylic acid containing no fluorine group, from which carboxyl groups have been removed, and less than 50 mol %, including 0 mol %, of A is a tetravalent group of an aliphatic tetracarboxylic acid, from which carboxyl groups have been removed, and/or a tetravalent group of an aromatic tetracarboxylic acid containing a fluorine group, from which carboxyl groups have been removed, and
  • B is a divalent group of an aromatic diamine containing no fluorine group and having a solubility in water at 25° C. of 0.1 g/L or more, from which amino groups have been removed, and less than 50 mol %, including 0 mol %, of B is a divalent group of an aliphatic diamine having a molecular weight of 500 or less, from which amino groups have been removed, and/or a divalent group of an aromatic diamine containing a fluorine group, from which amino groups have been removed, and
  • aqueous polyimide precursor solution composition as described in [1], wherein the imidazole is selected from the group consisting of 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, and 1-methyl-4-ethylimidazole.
  • a method for producing a polyimide seamless belt comprising a step of:
  • an aqueous polyimide precursor solution composition in which a polyamic acid, which is formed by the reaction of a tetracarboxylic acid component and a diamine component, and consists of a repeating unit represented by the following formula (1), is dissolved in an aqueous solvent together with an imidazole in an amount of 1.6 mole or more per mole of the tetracarboxylic acid component of the polyamic acid.
  • A represents at least one selected from the group consisting of a tetravalent group of an aromatic tetracarboxylic acid containing no fluorine group, from which carboxyl groups have been removed, a tetravalent group of an aliphatic tetracarboxylic acid, from which carboxyl groups have been removed, and a tetravalent group of an aromatic tetracarboxylic acid containing a fluorine group, from which carboxyl groups have been removed, and
  • B represents at least one selected from the group consisting of a divalent group of an aromatic diamine containing no fluorine group and having a solubility in water at 25° C. of 0.1 g/L or more, from which amino groups have been removed, a divalent group of an aliphatic diamine having a molecular weight of 500 or less, from which amino groups have been removed, and a divalent group of an aromatic diamine containing a fluorine group, from which amino groups have been removed, with the proviso that
  • A more than 50 mol % of A is a tetravalent group of an aromatic tetracarboxylic acid containing no fluorine group, from which carboxyl groups have been removed, and less than 50 mol %, including 0 mol %, of A is a tetravalent group of an aliphatic tetracarboxylic acid, from which carboxyl groups have been removed, and/or a tetravalent group of an aromatic tetracarboxylic acid containing a fluorine group, from which carboxyl groups have been removed, and
  • B is a divalent group of an aromatic diamine containing no fluorine group and having a solubility in water at 25° C. of 0.1 g/L or more, from which amino groups have been removed, and less than 50 mol %, including 0 mol %, of B is a divalent group of an aliphatic diamine having a molecular weight of 500 or less, from which amino groups have been removed, and/or a divalent group of an aromatic diamine containing a fluorine group, from which amino groups have been removed, and
  • a polyamic acid which is formed by the reaction of a tetracarboxylic acid component and a diamine component, and consists of a repeating unit represented by the following formula (1), is dissolved in an aqueous solvent together with an imidazole in an amount of 1.6 mole or more per mole of the tetracarboxylic acid component of the polyamic acid.
  • A represents at least one selected from the group consisting of a tetravalent group of an aromatic tetracarboxylic acid containing no fluorine group, from which carboxyl groups have been removed, a tetravalent group of an aliphatic tetracarboxylic acid, from which carboxyl groups have been removed, and a tetravalent group of an aromatic tetracarboxylic acid containing a fluorine group, from which carboxyl groups have been removed, and
  • B represents at least one selected from the group consisting of a divalent group of an aromatic diamine containing no fluorine group and having a solubility in water at 25° C. of 0.1 g/L or more, from which amino groups have been removed, a divalent group of an aliphatic diamine having a molecular weight of 500 or less, from which amino groups have been removed, and a divalent group of an aromatic diamine containing a fluorine group, from which amino groups have been removed, with the proviso that
  • A more than 50 mol % of A is a tetravalent group of an aromatic tetracarboxylic acid containing no fluorine group, from which carboxyl groups have been removed, and less than 50 mol %, including 0 mol %, of A is a tetravalent group of an aliphatic tetracarboxylic acid, from which carboxyl groups have been removed, and/or a tetravalent group of an aromatic tetracarboxylic acid containing a fluorine group, from which carboxyl groups have been removed, and
  • B is a divalent group of an aromatic diamine containing no fluorine group and having a solubility in water at 25° C. of 0.1 g/L or more, from which amino groups have been removed, and less than 50 mol %, including 0 mol %, of B is a divalent group of an aliphatic diamine having a molecular weight of 500 or less, from which amino groups have been removed, and/or a divalent group of an aromatic diamine containing a fluorine group, from which amino groups have been removed, and
  • a polyamic acid which is formed by the reaction of a tetracarboxylic acid component and a diamine component, and consists of a repeating unit represented by the following formula (1), is dissolved in an aqueous solvent together with an imidazole in an amount of 1.6 mole or more per mole of the tetracarboxylic acid component of the polyamic acid.
  • A represents at least one selected from the group consisting of a tetravalent group of an aromatic tetracarboxylic acid containing no fluorine group, from which carboxyl groups have been removed, a tetravalent group of an aliphatic tetracarboxylic acid, from which carboxyl groups have been removed, and a tetravalent group of an aromatic tetracarboxylic acid containing a fluorine group, from which carboxyl groups have been removed, and
  • B represents at least one selected from the group consisting of a divalent group of an aromatic diamine containing no fluorine group and having a solubility in water at 25° C. of 0.1 g/L or more, from which amino groups have been removed, a divalent group of an aliphatic diamine having a molecular weight of 500 or less, from which amino groups have been removed, and a divalent group of an aromatic diamine containing a fluorine group, from which amino groups have been removed, with the proviso that
  • A more than 50 mol % of A is a tetravalent group of an aromatic tetracarboxylic acid containing no fluorine group, from which carboxyl groups have been removed, and less than 50 mol %, including 0 mol %, of A is a tetravalent group of an aliphatic tetracarboxylic acid, from which carboxyl groups have been removed, and/or a tetravalent group of an aromatic tetracarboxylic acid containing a fluorine group, from which carboxyl groups have been removed, and
  • B is a divalent group of an aromatic diamine containing no fluorine group and having a solubility in water at 25° C. of 0.1 g/L or more, from which amino groups have been removed, and less than 50 mol %, including 0 mol %, of B is a divalent group of an aliphatic diamine having a molecular weight of 500 or less, from which amino groups have been removed, and/or a divalent group of an aromatic diamine containing a fluorine group, from which amino groups have been removed, and
  • a method for producing a flexible device which is a display device or a light-receiving device comprising steps of:
  • a method for producing an aqueous polyimide precursor solution composition comprising
  • a tetracarboxylic acid component which comprises an aromatic tetracarboxylic dianhydride containing no fluorine group in an amount of more than 50 mol % and comprises an aliphatic tetracarboxylic dianhydride and/or an aromatic tetracarboxylic dianhydride containing a fluorine group in an amount of less than 50 mol %, or alternatively, does not comprise an aliphatic tetracarboxylic dianhydride and an aromatic tetracarboxylic dianhydride containing a fluorine group, and a diamine component, which comprises an aromatic diamine containing no fluorine group and having a solubility in water at 25° C.
  • an aqueous polyimide precursor solution composition which comprises an aqueous solvent and has good environmental acceptability, and may provide a polyimide having excellent properties such as flexibility, heat resistance, mechanical strength, electrical properties, and solvent resistance, and preferably comprises a polyimide precursor (polyamic acid) having a high molecular weight and a solvent containing no organic solvent other than water.
  • a polyimide having excellent properties may be obtained from the aqueous polyimide precursor solution composition, which preferably comprises a polyimide precursor (polyamic acid) having a high molecular weight.
  • the flexibility of the polyimide obtained may be improved when using an aliphatic tetracarboxylic dianhydride and/or an aliphatic diamine having a molecular weight of 500 or less in addition to an aromatic tetracarboxylic dianhydride and an aromatic diamine.
  • the flexibility of the polyimide obtained may be also improved when using an aromatic tetracarboxylic dianhydride containing a fluorine group (fluorine atom) and/or an aromatic diamine containing a fluorine group (fluorine atom).
  • the polyimide which is obtained from the aqueous solution composition of the polyimide precursor having a specific composition and prepared according to the present invention has excellent properties such as flexibility, heat resistance, mechanical strength, electrical properties, and solvent resistance. Accordingly, the polyimide may be suitably used as parts for various precision machines such as electrical/electronic equipments and a copying machine, and may be suitably used, for example, as various materials for a flexible printed wiring board and the like, and as a seamless belt for intermediate transfer, fixing, or transport in a copying machine. Meanwhile, the polyimide has a low degree of swelling in a battery environment, and has excellent toughness. Accordingly, the polyimide may also be suitably used as a binder for an electrode of a battery, and the like.
  • the polyimide may also be suitably used as a substrate of a flexible device, for example, a display device such as a liquid crystal display, an organic EL display and an electronic paper, and a light-receiving device such as a light-receiving element of a thin-film solar cell.
  • a display device such as a liquid crystal display, an organic EL display and an electronic paper
  • a light-receiving device such as a light-receiving element of a thin-film solar cell.
  • a method for producing a polyimide seamless belt which have excellent properties such as flexibility, heat resistance, mechanical strength, electrical properties, and solvent resistance, and therefore may be suitably used as an intermediate transfer seamless belt or a fixing seamless belt of an electrophotographic device, using an aqueous polyimide precursor solution composition which comprises an aqueous solvent and has good environmental acceptability.
  • the aqueous polyimide precursor solution composition to be used preferably comprises a polyimide precursor (polyamic acid) having a high molecular weight and a solvent containing no organic solvent other than water.
  • the method for producing a polyimide seamless belt using an aqueous polyimide precursor solution composition is preferred because of having high environmental acceptability as compared with a method wherein a polyimide precursor solution composition in which a polyamic acid as a polyimide precursor is dissolved in an organic solvent is used.
  • the seamless belt of the polyimide having a specific composition which is obtained according to the production method may have excellent properties such as flexibility, heat resistance, mechanical strength, electrical properties, and solvent resistance, and therefore may be suitably used as an intermediate transfer seamless belt or a fixing seamless belt of an electrophotographic device, in particular, which requires high stability of electrical resistance, and high toughness.
  • a binder resin composition for electrodes which comprises an aqueous solvent and has good environmental acceptability, and may provide a polyimide having excellent properties such as flexibility, heat resistance, mechanical strength, electrical properties, and solvent resistance, and furthermore having a low degree of swelling in a battery environment, and having excellent toughness, and preferably comprises a polyimide precursor (polyamic acid) having a high molecular weight and a solvent containing no organic solvent other than water.
  • the binder resin composition for electrodes is preferred because of having high environmental acceptability as compared with a polyimide precursor solution composition comprising an organic solvent.
  • the polyimide obtained from the binder resin composition for electrodes and having a specific composition may have excellent properties such as flexibility, heat resistance, mechanical strength, electrical properties, and solvent resistance, and have a low degree of swelling in a battery environment, and have excellent toughness, and therefore may be suitably used as a binder resin composition for electrodes of electrochemical devices such as a lithium ion secondary battery and an electric double layer capacitor.
  • a polyimide precursor resin composition for flexible device substrates which comprises an aqueous solvent and has good environmental acceptability, and may provide a polyimide substrate for flexible device having excellent properties such as flexibility, heat resistance, mechanical strength, electrical properties, and solvent resistance, and being suitably usable as a substrate for flexible device as a display device such as substrates for a liquid crystal display, an organic EL display and an electronic paper, a substrate for flexible device as a light-receiving device such as a substrate for a thin-film solar cell, and the like, and preferably comprises a polyimide precursor (polyamic acid) having a high molecular weight and a solvent containing no organic solvent other than water.
  • a polyimide precursor polyamic acid
  • the polyimide precursor resin composition for flexible device substrates is preferred because of having high environmental acceptability as compared with a polyimide precursor solution composition comprising an organic solvent.
  • the polyimide substrate for flexible device which is obtained from the polyimide precursor resin composition and has a specific composition may have excellent properties such as flexibility, heat resistance, mechanical strength, electrical properties, and solvent resistance, and therefore may be suitably used, for example, as a substrate for flexible device which is a display device such as substrates for a liquid crystal display, an organic EL display and an electronic paper, and as a substrate for flexible device which is a light-receiving device such as a substrate for a thin-film solar cell, in particular, which requires flexibility, and high toughness, and may be particularly suitably used as a substrate for a flexible display.
  • an aqueous polyimide precursor solution composition which has higher environmental acceptability, without the need for a solvent other than water.
  • an aqueous polyimide precursor solution composition particularly an aqueous polyimide precursor solution composition comprising an aqueous solvent which has an organic solvent content of less than 5 wt %, further preferably contains no organic solvent, may be very easily (directly) produced.
  • aqueous polyimide precursor solution composition may be produced by the production method of the present invention, which allows the reaction of a tetracarboxylic acid component and a diamine component in an aqueous solvent to form a polyimide precursor (polyamic acid).
  • an aqueous polyimide precursor solution composition is produced by reacting a tetracarboxylic dianhydride and a diamine in the presence of an imidazole, using water as a reaction solvent, provided that
  • more than 50 mol % of the tetracarboxylic dianhydride to be reacted is an aromatic tetracarboxylic dianhydride containing no fluorine group, preferably an aromatic tetracarboxylic dianhydride having two to three aromatic rings and containing no fluorine group, and less than 50 mol %, including 0 mol %, of the tetracarboxylic dianhydride to be reacted is an aliphatic tetracarboxylic dianhydride and/or an aromatic tetracarboxylic dianhydride containing a fluorine group, and
  • more than 50 mol % of the diamine to be reacted is an aromatic diamine having a solubility in water at 25° C. of 0.1 g/L or more and containing no fluorine group, preferably an aromatic diamine having one to two aromatic rings, and having a solubility in water at 25° C. of 0.1 g/L or more and containing no fluorine group, and less than 50 mol %, including 0 mol %, of the diamine to be reacted is an aliphatic diamine having a molecular weight of 500 or less and/or an aromatic diamine containing a fluorine group, preferably an aromatic diamine having one to two aromatic rings, and containing a fluorine group,
  • the term “using water as a reaction solvent” means that water is used as the main component of the solvent. Therefore, an organic solvent other than water may be used in a ratio of 50 wt % or less, preferably 30 wt % or less, more preferably 10 wt % or less, relative to the whole solvent.
  • the “organic solvent” as used herein does not include a tetracarboxylic acid component such as tetracarboxylic dianhydride, a diamine component, a polyimide precursor such as polyamic acid, and an imidazole.
  • organic solvent examples include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, hexamethylphosphoric triamide, 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, tetrahydrofuran, bis[2-(2-methoxyethoxy)ethyl]ether, 1,4-dioxane, dimethyl sulfoxide, dimethyl sulfone, diphenyl ether, sulfolane, diphenyl sulfone, tetramethylurea, anisole, m-cresol, phenol, and ⁇ -butyrolactone.
  • the reaction solvent is preferably a solvent having an organic solvent content of less than 5 wt %, particularly preferably an aqueous solvent containing no organic solvent other than water, in view of high environmental acceptability.
  • the composition of the reaction solvent may be appropriately selected depending on the intended solvent composition of the aqueous polyimide precursor solution composition to be produced, and it may be preferably the same as the intended solvent composition of the aqueous polyimide precursor solution composition.
  • imidazole (compound) used in the present invention include a compound represented by the following formula (10).
  • X 1 to X 4 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • the imidazole used in the present invention preferably has a solubility in water at 25° C. of 0.1 g/L or more, particularly preferably 1 g/L or more.
  • X 1 to X 4 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • An imidazole in which at least two of X 1 to X 4 are alkyl groups having 1 to 5 carbon atoms, or an imidazole having two or more alkyl groups as substituents is more preferred.
  • An imidazole having two or more alkyl groups as substituents has high solubility in water, and therefore, when using such an imidazole, an aqueous polyimide precursor solution composition may be easily produced.
  • the imidazole include 1,2-dimethylimidazole (solubility in water at 25° C.: 239 g/L; the same shall apply hereinafter), 2-ethyl-4-methylimidazole (1000 g/L), 4-ethyl-2-methylimidazole (1000 g/L), and 1-methyl-4-ethylimidazole (54 g/L).
  • the “solubility in water at 25° C.” means the maximum amount (g) of the substance soluble in 1 L (liter) of water at 25° C. This value may be easily searched using SciFinder®, which is known as a search service based on the data bases such as Chemical Abstracts.
  • SciFinder® which is known as a search service based on the data bases such as Chemical Abstracts.
  • the imidazole to be used may be a single imidazole, or may be a mixture of two or more imidazoles.
  • the amount of the imidazole used in the present invention is preferably 0.8 equivalents or more, more preferably 1.0 equivalent or more, further preferably 1.2 equivalents or more per equivalent of the carboxyl group of the polyamic acid, which is formed by the reaction of a tetracarboxylic dianhydride and a diamine as starting materials.
  • the amount of the imidazole used is less than 0.8 equivalents per equivalent of the carboxyl group of the polyamic acid, it may not be easy to provide an aqueous polyimide precursor solution composition in which the polyamic acid is homogeneously dissolved.
  • the upper limit of the amount of the imidazole used may be generally, but not limited to, less than 10 equivalents, preferably less than 5 equivalents, more preferably less than 3 equivalents per equivalent of the carboxyl group of the polyamic acid. If the amount of the imidazole used is too great, it will be uneconomical, and the storage stability of the aqueous polyimide precursor solution composition may be reduced.
  • the “equivalents per equivalent of the carboxyl group of the polyamic acid”, which defines the amount of the imidazole means the number (number of molecules) of imidazole used per one carboxyl group to form an amic acid group in the polyamic acid.
  • the number of carboxyl groups to form amic acid groups in the polyamic acids may be calculated on the assumption that two carboxyl groups would be formed per one molecule of the tetracarboxylic acid component as a starting material.
  • the amount of the imidazole used in the present invention is preferably 1.6 mole or more, more preferably 2.0 mole or more, further preferably 2.4 mole or more per mole of the tetracarboxylic dianhydride as a starting material (per mole of the tetracarboxylic acid component of the polyamic acid).
  • the characteristics of the imidazole used in the present invention are that the imidazole forms a salt with a carboxyl group of a polyamic acid (polyimide precursor), which is formed by the reaction of a tetracarboxylic dianhydride and a diamine as starting materials, thereby increasing the solubility of the polyamic acid in water, and also that the imidazole exhibits a very high catalytic activity during the imidization (dehydration/ring closure) of the polyimide precursor to form a polyimide.
  • polyimide precursor polyamic acid
  • the imidazole exhibits a very high catalytic activity during the imidization (dehydration/ring closure) of the polyimide precursor to form a polyimide.
  • a polyimide, a polyimide seamless belt, a binder resin for electrodes, and a substrate for flexible devices which have very high properties, may be easily produced even though the aqueous polyimide precursor solution composition is heated at a lower temperature for a shorter period of time, for example.
  • an aqueous polyimide precursor solution composition may be very easily (directly) produced preferably by reacting a tetracarboxylic acid component and a diamine component in the presence of an imidazole, preferably in the presence of an imidazole having two or more alkyl groups as substituents, using water as a reaction solvent.
  • the reaction is performed at a relatively low temperature of 100° C. or lower, preferably 80° C. or lower, so as to suppress the imidization reaction, using substantially equimolar amounts of a tetracarboxylic acid component (tetracarboxylic dianhydride) and a diamine component.
  • the reaction temperature may be generally, but not limited to, from 25° C. to 100° C., preferably from 40° C. to 80° C., more preferably from 50° C. to 80° C.
  • the reaction time may be preferably, but not limited to, from about 0.1 hours to about 24 hours, preferably from about 2 hours to about 12 hours.
  • an aqueous polyimide precursor solution composition which comprises a polyimide precursor having a high molecular weight may be easily produced with good production efficiency.
  • the reaction may be preferably performed in an inert gas atmosphere, preferably in a nitrogen gas atmosphere, although the reaction may be performed in an air atmosphere.
  • substantially equimolar amounts of a tetracarboxylic acid component (tetracarboxylic dianhydride) and a diamine component specifically means that a molar ratio [tetracarboxylic acid component/diamine component] is from about 0.90 to about 1.10, preferably from about 0.95 to about 1.05.
  • the tetracarboxylic dianhydride used in the present invention is an aromatic tetracarboxylic dianhydride containing no fluorine group and preferably having two to three aromatic rings, or alternatively, an aromatic tetracarboxylic dianhydride containing no fluorine group and preferably having two to three aromatic rings, and an aliphatic tetracarboxylic dianhydride and/or an aromatic tetracarboxylic dianhydride containing a fluorine group, and may be more preferably, but not limited to, a combination of an aromatic tetracarboxylic dianhydride containing no fluorine group and an alicyclic tetracarboxylic dianhydride, in terms of the properties of the polyimide obtained.
  • the diamine component to be reacted is only an aromatic diamine containing no fluorine group, however, both an aromatic tetracarboxylic dianhydride containing no fluorine group, and an aliphatic tetracarboxylic dianhydride and/or an aromatic tetracarboxylic dianhydride containing a fluorine group are used.
  • aromatic tetracarboxylic dianhydride containing no fluorine group used in the present invention include 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 2,2′,3,3′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, diphenylsulfone tetracarboxylic dianhydride, p-terphenyl tetracarboxylic dianhydride, and m-terphenyl tetracarboxylic dianhydride.
  • aliphatic tetracarboxylic dianhydride used in the present invention include cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, dicyclohexyl-3,3′,4,4′-tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic acid-1,2:4,5-dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, and bicyclo[2.2.2]octo-7-ene-2,3; 5,6-tetracarboxylic dianhydride.
  • aromatic tetracarboxylic dianhydride containing a fluorine group used in the present invention include 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, 3,3′-(hexafluoroisopropylidene)diphthalic anhydride, 5,5′-[2,2,2-trifluoro-1-[3-(trifluoromethyl)phenyl]ethylidene]diphthalic anhydride, 5,5′[2,2,3,3,3-pentafluoro-1-(trifluoromethyl)propylidene]diphthalic anhydride, 1H-diflo[3,4-b:3′,4′-i]xanthene-1,3,7,9(11H)-tetron, 5,5′-oxybis[4,6,7-trifluoro-pyromellitic anhydride], 3,6-bis(trifluoromethyl)pyromellitic dianhydride, 4-(
  • the aromatic tetracarboxylic dianhydride containing no fluorine group, the aliphatic tetracarboxylic dianhydride, and the aromatic tetracarboxylic dianhydride containing a fluorine group each may not be a single component, and may be a mixture of two or more types thereof.
  • the diamine used in the present invention is an aromatic diamine having a solubility in water at 25° C. of 0.1 g/L or more and containing no fluorine group and preferably having one to two aromatic rings, or alternatively, an aromatic diamine having a solubility in water at 25° C. of 0.1 g/L or more and containing no fluorine group and preferably having one to two aromatic rings, and an aliphatic diamine having a molecular weight of 500 or less and/or an aromatic diamine containing a fluorine group.
  • the tetracarboxylic acid component to be reacted is only an aromatic tetracarboxylic dianhydride containing no fluorine group, however, both an aromatic diamine containing no fluorine group, and an aliphatic diamine and/or an aromatic diamine containing a fluorine group are used.
  • the aromatic diamine containing no fluorine group used in the present invention is not limited as long as the solubility in water at 25° C. is 0.1 g/L or more, but may be preferably an aromatic diamine having one to two aromatic rings.
  • an aromatic diamine having a solubility in water at 25° C. of less than 0.1 g/L is used, it may be difficult to provide an aqueous polyimide precursor solution composition in which the polyimide precursor is homogeneously dissolved.
  • the aromatic diamine has more than two aromatic rings, the aromatic diamine may have a solubility in water at 25° C. of less than 0.1 g/L, and therefore it may be difficult to provide an aqueous polyimide precursor solution composition in which the polyimide precursor is homogeneously dissolved.
  • the aliphatic diamine used in the present invention is not limited as long as the molecular weight (which means “molecular weight” in the case of monomer, and “weight average molecular weight” in the case of polymer) is 500 or less, but may be preferably an aliphatic diamine having a solubility in water at 25° C. of 0.1 g/L or more, or an alicyclic diamine having one to two alicyclic rings.
  • an aliphatic diamine having a molecular weight of more than 500 it may be difficult to provide an aqueous polyimide precursor solution composition in which the polyimide precursor is homogeneously dissolved.
  • the aromatic diamine containing a fluorine group used in the present invention may be preferably, but not limited to, an aromatic diamine having one to two aromatic rings and containing a fluorine group.
  • an aromatic diamine containing a fluorine group has more than two aromatic rings, it may be difficult to provide an aqueous polyimide precursor solution composition in which the polyimide precursor is homogeneously dissolved.
  • aromatic diamine containing no fluorine group used in the present invention include p-phenylenediamine (solubility in water at 25° C.: 120 g/L; the same shall apply hereinafter), m-phenylenediamine (77 g/L), 4,4′-diaminodiphenyl ether (0.19 g/L), 3,4′-diaminodiphenyl ether (0.24 g/L), 4,4′-diaminodiphenylmethane (0.54 g/L), 2,4-toluenediamine (62 g/L), 3,3′-dihydroxy-4,4′-diaminobiphenyl (1.3 g/L), bis(4-amino-3-carboxyphenyl)methane (200 g/L), and 2,4-diaminotoluene (62 g/L).
  • p-phenylenediamine solubility in water at 25° C.: 120 g/L
  • p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and a mixture thereof are preferred, and p-phenylenediamine, 4,4′-diaminodiphenyl ether, and a mixture thereof are more preferred.
  • Preferable examples of the aliphatic diamine used in the present invention include trans-1,4-diaminocyclohexane (1000 g/L, molecular weight: 114), cis-1,4-diaminocyclohexane (1000 g/L, molecular weight: 114), 1,6-hexamethylene diamine (1000 g/L, molecular weight: 116), 1,10-decamethylene diamine (1000 g/L, molecular weight: 172), 1,3-bis(aminomethyl)cyclohexane (1000 g/L, molecular weight: 142), 1,4-bis(aminomethyl)cyclohexane (999 g/L, molecular weight: 142), and polyoxypropylene diamine having a weight average molecular weight of 500 or less.
  • aromatic diamine containing a fluorine group used in the present invention include 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,3,5,6-tetrafluoro-1,4-diaminobenzene, 2,4,5,6-tetrafluoro-1,3-diaminobenzene, 2,3,5,6-tetrafluoro-1,4-benzene(dimethaneamine), 2,2′-difluoro-(1,1′-biphenyl)-4,4′-diamine, 2,2′,6,6′-tetrafluoro-(1,1′-biphenyl)-4,4′-diamine, 4,4′-diamino octafluorobiphenyl, 2,2-bis(4-aminophenyl) hexafluoropropane, and 4,4′-oxybis(2,3,5,6-tetrafluoroaniline).
  • the aromatic diamine containing no fluorine group, the aliphatic diamine, and the aromatic diamine containing a fluorine group each may not be a single component, and may be a mixture of two or more types thereof.
  • the aromatic diamine containing no fluorine group it is also possible to use a diamine which has a high solubility in water in combination with other diamines such that the diamine component has a solubility in water at 25° C. of 0.1 g/L or more as a whole.
  • the “diamine having a solubility in water at 25° C. of 0.1 g/L or more” means that 0.1 g or more of the diamine is dissolved in 1 L (1000 ml) of water at 25° C.
  • the “solubility in water at 25° C.” means the maximum amount (g) of the substance soluble in 1 L (liter) of water at 25° C. This value may be easily searched using SciFinder®, which is known as a search service based on the data bases such as Chemical Abstracts.
  • SciFinder® which is known as a search service based on the data bases such as Chemical Abstracts.
  • a tetracarboxylic acid component consisting of one or more aromatic tetracarboxylic dianhydrides containing no fluorine group, and one or more aliphatic tetracarboxylic dianhydrides and/or one or more aromatic tetracarboxylic dianhydrides containing a fluorine group, and a diamine component consisting of one or more aromatic diamines containing no fluorine group are reacted, or (II) a tetracarboxylic acid component consisting of one or more aromatic tetracarboxylic dianhydrides containing no fluorine group, and a diamine component consisting of one or more aromatic diamines containing no fluorine group, and one or more aliphatic diamines and/or one or more aromatic diamines containing a fluorine group are reacted.
  • the amount of the aromatic tetracarboxylic dianhydride containing no fluorine group in the tetracarboxylic acid component is not limited as long as the amount is more than 50 mol %, but may be preferably more than 50 mol % and not more than 80 mol % in terms of the properties of the polyimide obtained.
  • 0.1 g/L or more and containing no fluorine group in the diamine component is not limited as long as the amount is more than 50 mol %, but may be preferably not less than 60 mol % and not more than 90 mol % in terms of the properties of the polyimide obtained.
  • the polyamic acid which constitutes the aqueous polyimide precursor solution composition of the present invention consists of a repeating unit represented by the formula (1).
  • the “A” group is a chemical structure derived from the tetracarboxylic acid component of a polyamic acid, and is a tetravalent group of an aromatic tetracarboxylic acid containing no fluorine group and preferably having two to three aromatic rings, from which carboxyl groups have been removed, and/or a tetravalent group of an aliphatic tetracarboxylic acid, from which carboxyl groups have been removed, and/or a tetravalent group of an aromatic tetracarboxylic acid containing a fluorine group, from which carboxyl groups have been removed.
  • more than 50 mol % of A is preferably a tetravalent group of an aromatic tetracarboxylic acid containing no fluorine group and preferably having two to three aromatic rings, from which carboxyl groups have been removed, and less than 50 mol % of A is preferably a tetravalent group of an aliphatic tetracarboxylic acid, from which carboxyl groups have been removed, and/or a tetravalent group of an aromatic tetracarboxylic acid containing a fluorine group, from which carboxyl groups have been removed, so as to provide a polyamic acid having an adequate solubility in water, and to provide a polyimide having excellent flexibility, heat resistance, mechanical strength, electrical properties and solvent resistance, thereby easily producing a polyimide seamless belt, a binder resin for electrodes, and a polyimide substrate for flexible devices, which have high properties.
  • the “A” group in the formula (1) which is a constituent unit derived from the aromatic tetracarboxylic dianhydride containing no fluorine group is preferably any one or more of the groups represented by the following formulas (2) to (7), particularly preferably any one or more of the groups represented by the following formulas (2), (3) and (5) in the main, further preferably any one or more of the groups represented by the following formulas (2) to (3).
  • the “13” group is a chemical structure derived from the diamine component of a polyamic acid, and is a divalent group of an aromatic diamine having a solubility in water at 25° C. of 0.1 g/L or more and containing no fluorine group and preferably having one to two aromatic rings, from which amino groups have been removed, and/or a divalent group of an aliphatic diamine having a molecular weight of 500 or less, preferably an aliphatic diamine having a solubility in water of 0.1 g/L or more, or an aliphatic diamine having one to two alicyclic rings, from which amino groups have been removed, and/or a divalent group of an aromatic diamine containing a fluorine group, preferably an aromatic diamine containing a fluorine group and having one to two aromatic rings, from which amino groups have been removed.
  • more than 50 mol % of B is preferably a divalent group of an aromatic diamine having a solubility in water at 25° C. of 0.1 g/L or more and containing no fluorine group and preferably having one to two aromatic rings, from which amino groups have been removed, and less than 50 mol % of B is preferably a divalent group of an aliphatic diamine having a molecular weight of 500 or less, from which amino groups have been removed, and/or a divalent group of an aromatic diamine containing a fluorine group, from which amino groups have been removed, so as to provide a polyamic acid having an adequate solubility in water, and to provide a polyimide having excellent flexibility, heat resistance, mechanical strength, electrical properties and solvent resistance, thereby easily producing a polyimide seamless belt, a binder resin for electrodes, and a polyimide substrate for flexible devices, which have high properties.
  • the “B” group in the formula (1) which is a constituent unit derived from the aromatic diamine containing no fluorine group is preferably any one or more of the groups represented by the following formulas (8) to (9).
  • the polyimide precursor (which is substantially a polyamic acid) preferably has a high molecular weight, and more specifically, has an inherent viscosity of 0.2 or more, preferably 0.4 or more, more preferably 0.6 or more, further preferably 0.8 or more, particularly preferably 1.0 or more, or more than 1.0, wherein the inherent viscosity is measured at a temperature of 30° C. and a concentration of 0.5 g/100 mL (dissolved in water) which is based on the solid content of the polyimide precursor.
  • the polyimide precursor When the inherent viscosity is lower than the range as described above, the polyimide precursor has a low molecular weight, and therefore it may be difficult to provide a polyimide, a polyimide seamless belt, a binder resin for electrodes, and a polyimide substrate for flexible devices, which have high properties, even if the aqueous polyimide precursor solution composition of the present invention is used.
  • the solid content based on the polyimide precursor (which is substantially a polyamic acid) of the aqueous polyimide precursor solution composition of the present invention may be preferably, but not limited to, from 5 wt % to 45 wt %, more preferably from 7 wt % to 40 wt %, further preferably from 9 wt % to 30 wt %, relative to the total amount of the polyimide precursor and the solvent.
  • the solid content is lower than 5 wt %, the productivity and the handling in use may be reduced.
  • the solid content is higher than 45 wt %, the solution may lose the fluidity.
  • the solution viscosity at 30° C. of the aqueous polyimide precursor solution composition of the present invention may be preferably, but not limited to, 1000 Pa ⁇ sec or lower, more preferably from 0.5 Pa ⁇ sec to 500 Pa ⁇ sec, further preferably from 1 Pa ⁇ sec to 300 Pa ⁇ sec, particularly preferably from 3 Pa ⁇ sec to 200 Pa ⁇ sec.
  • the composition may lose the fluidity, and therefore it may be difficult to uniformly apply the composition onto a metal (such as a current collecting foil), a glass, and the like.
  • the solution viscosity is lower than 0.5 Pa ⁇ sec, dripping, cissing, and the like may occur when applying the composition onto a metal (such as a current collecting foil), a glass, and the like, and it may be difficult to provide a polyimide, a polyimide seamless belt, a binder resin for electrodes, and a polyimide substrate for flexible devices, which have high properties.
  • the aqueous polyimide precursor solution composition of the present invention comprises an aqueous solvent
  • an organic solvent other than water for example, a known organic solvent to be used in the preparation of a polyamic acid may be used in a ratio of 50 wt % or less, preferably 30 wt % or less, more preferably 10 wt % or less, relative to the whole solvent.
  • the aqueous polyimide precursor solution composition of the present invention is a composition in which a polyamic acid as a polyimide precursor is dissolved, together with an imidazole, in an aqueous solvent (water-based solvent), wherein the aqueous solvent is only water, or a mixture of water and an organic solvent having a water content of 50 wt % or more, preferably 70 wt % or more, more preferably 90 wt % or more.
  • organic solvent examples include N,N-dimethylformamide, N,N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, hexamethylphosphoric triamide, 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, tetrahydrofuran, bis[2-(2-methoxyethoxy)ethyl]ether, 1,4-dioxane, dimethyl sulfoxide, dimethyl sulfone, diphenyl ether, sulfolane, diphenyl sulfone, tetramethylurea, anisole, m-cresol, phenol, and ⁇ -butyrolactone.
  • the solvent is particularly preferably a solvent having an organic solvent content of less than 5 wt %, more preferably an aqueous solvent containing no organic solvent other than water, i.e. only water, in view of environmental acceptability.
  • aqueous polyimide precursor solution composition of the present invention may also be prepared according to the following methods, for example, as described in Patent Literatures 1 and 2:
  • a polyimide may be suitably prepared by heating the aqueous polyimide precursor solution composition of the present invention to remove an aqueous solvent and effect imidization (dehydration/ring closure).
  • the heat treatment conditions are not limited, but, in general, the aqueous polyimide precursor solution composition may be preferably heated at a temperature of 100° C. or higher, preferably from 120° C. to 600° C., more preferably from 150° C. to 500° C., further preferably from 150° C. to 350° C., for from 0.01 hours to 30 hours, preferably from 0.01 hours to 10 hours, preferably while increasing the temperature stepwise.
  • the heat treatment may be suitably performed under atmospheric pressure, and may be performed under reduced pressure so as to efficiently remove the aqueous solvent.
  • the aqueous polyimide precursor solution composition may be heated at a relatively low temperature under reduced pressure at the early stage for deaeration. When the heating temperature is rapidly increased, a problem such as foaming may occur.
  • the aqueous polyimide precursor solution composition of the present invention may be heated at a relatively low temperature (for example, 150° C. to 300° C., preferably 180° C. to 250° C.) to readily provide a polyimide, which has excellent properties, for example, high adhesiveness to a metal and the like, and is in no way inferior to a polyimide obtained from a commonly-used polyimide precursor (polyamic acid) solution composition comprising an organic solvent. Accordingly, a polyimide seamless belt and the like, as well as a polyimide film, may be suitably obtained from the aqueous polyimide precursor solution composition of the present invention.
  • a relatively low temperature for example, 150° C. to 300° C., preferably 180° C. to 250° C.
  • a coating film of an aqueous polyimide precursor solution composition layer is formed on a substrate by applying or spraying an aqueous polyimide precursor solution composition (specifically, an aqueous polyimide precursor solution composition in which a polyamic acid consisting of a repeating unit represented by the formula (1) is homogeneously dissolved in an aqueous solvent together with an imidazole in an amount of 1.6 mole or more per mole of the tetracarboxylic acid component of the polyamic acid) onto the substrate surface, and then the aqueous polyimide precursor solution composition is heated.
  • an aqueous polyimide precursor solution composition specifically, an aqueous polyimide precursor solution composition in which a polyamic acid consisting of a repeating unit represented by the formula (1) is homogeneously dissolved in an aqueous solvent together with an imidazole in an amount of 1.6 mole or more per mole of the tetracarboxylic acid component of the polyamic acid
  • a polyimide seamless belt may be suitably prepared by heating the aqueous polyimide precursor solution composition to remove an aqueous solvent and effect imidization (dehydration/ring closure).
  • the heat treatment conditions are not limited, but, in general, the aqueous polyimide precursor solution composition may be preferably heated at a temperature of 100° C. or higher, preferably from 120° C. to 600° C., more preferably from 150° C. to 500° C., further preferably from 150° C. to 350° C., for from 0.01 hours to 30 hours, preferably from 0.01 hours to 10 hours, preferably while increasing the temperature stepwise.
  • the heat treatment may be suitably performed under atmospheric pressure, and may be performed under reduced pressure so as to efficiently remove the aqueous solvent.
  • the aqueous polyimide precursor solution composition may be heated at a relatively low temperature under reduced pressure at the early stage for deaeration. When the heating temperature is rapidly increased, a problem such as foaming may occur, and therefore a polyimide seamless belt having excellent properties may not be obtained.
  • the aqueous polyimide precursor solution composition may be heated at a relatively low temperature (for example, 150° C. to 300° C., preferably 180° C. to 250° C.) to readily provide a polyimide seamless belt, which has excellent properties, and is in no way inferior to a polyimide seamless belt obtained from a commonly-used polyimide precursor (polyamic acid) solution composition comprising an organic solvent.
  • a relatively low temperature for example, 150° C. to 300° C., preferably 180° C. to 250° C.
  • a seamless belt may be suitably produced by rotational molding, i.e. a method comprising
  • a coating film of an aqueous polyimide precursor solution composition by application (coating) or spraying, for example, on a surface (inner surface or outer surface) of a cylindrical mold, which functions as a substrate, while rotating the mold;
  • the aqueous polyimide precursor solution composition of the present invention may contain other additive component(s) depending on the intended application of the polyimide seamless belt obtained. Additionally, another resin layer and/or a metal layer may be laminated on the polyimide seamless belt obtained.
  • the thickness of the polyimide seamless belt of the present invention may be appropriately selected depending on the intended use, and it may be generally from about 20 ⁇ m to about 200 ⁇ m.
  • the polyimide seamless belt obtained according to the present invention preferably has excellent properties such as flexibility, heat resistance, mechanical strength, electrical properties, and solvent resistance, and therefore it may be suitably used as an intermediate transfer seamless belt or a fixing seamless belt of an electrophotographic device.
  • a conductive filler may be preferably added to the seamless belt so that semiconductivity is imparted to the seamless belt, specifically, the seamless belt has a surface resistivity of 10 8 ⁇ / ⁇ to 10 16 ⁇ / ⁇ and a volume resistivity of 10 8 ⁇ cm to 10 16 ⁇ cm.
  • a conductive or semiconductive particle which is used for a conventional intermediate transfer seamless belt may be used as the conductive filler.
  • Examples thereof include, but not limited to, carbon blacks such as ketjen black and acetylene black, metals such as aluminum and nickel, metal oxide compounds such as tin oxide, and potassium titanate.
  • the conductive filler may be used alone or in combination of two or more.
  • a carbon black may be preferably used as the conductive filler, and, among them, a carbon black having an average primary particle size of from 5 nm to 100 nm, particularly preferably from 10 nm to 50 nm, is particularly preferred. When the average primary particle size is more than 100 nm, the uniformity of mechanical properties and electric resistance may be liable to be inadequate.
  • the amount of the conductive filler may vary depending on the type, particle size, and a dispersion state of the filler. In general, the amount of the conductive filler is preferably from 1 to 50 parts by weight, more preferably from 2 to 30 parts by weight, relative to 100 parts by weight of the polyimide (solid content). In the present invention, the surface resistivity and the volume resistivity may be controlled to within the range (10 8 ⁇ / ⁇ to 10 16 ⁇ / ⁇ , and 10 8 ⁇ cm to 10 16 ⁇ cm) suitable for an intermediate transfer belt by a combination of the selection of the conductive filler and its appropriate amount.
  • a filler such as silica, boron nitride, aluminum nitride, silicon nitride, and alumina may be preferably added to the seamless belt so that thermal conductivity is imparted to the seamless belt, and a fluororesin powder, for example, may be preferably added to the seamless belt so that rubber elasticity is imparted to the seamless belt, and a metal foil as a heating element may be preferably laminated on the seamless belt.
  • the amount of the filler is preferably from 1 to 50 parts by weight, more preferably from 2 to 30 parts by weight, relative to 100 parts by weight of the polyimide (solid content).
  • the seamless belt When the polyimide seamless belt is used as a fixing belt of an electrophotographic device, the seamless belt may preferably have a thermal conductivity of 0.15 W/mK or more, preferably 0.20 W/mK or more.
  • the seamless belt may preferably have a rubber elastic layer or a release layer laminated on the surface.
  • the release layer is not limited as long as the layer improves the releasability of the surface of the seamless belt, and a known material including polytetrafluoroethylene (PTFE), and a modified material thereof such as tetrafluoroethylene-perfluoroalkylvinylether copolymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-vinylidene fluoride copolymer (TFE/VdF), tetrafluoroethylene-hexafluoropropylene-perfluoroalkylvinylether copolymer (EPA), polychlorotrifluoroethylene (PC), polytetrafluoroethylene-perfluoroalkylvinylether copolymer (
  • the aqueous polyimide precursor solution composition of the present invention may also be suitably used as a binder resin composition for electrodes.
  • a polyimide may be suitably prepared by heating the aqueous polyimide precursor solution composition of the present invention (binder resin composition for electrodes of the present invention) to remove an aqueous solvent and effect imidization (dehydration/ring closure) in this case, as well.
  • the heat treatment conditions are not limited, but, in general, the aqueous polyimide precursor solution composition may be preferably heated at a temperature of 100° C. or higher, preferably from 120° C. to 600° C., more preferably from 150° C. to 500° C., for from 0.01 hours to 30 hours, preferably from 0.01 hours to 10 hours.
  • the binder resin composition for electrodes may be heated at a relatively low temperature (for example, 150° C. to 300° C., preferably 180° C. to 250° C.) to provide a polyimide, which has excellent properties, for example, high adhesiveness to a metal, and is in no way inferior to a polyimide obtained from a commonly-used binder resin composition for electrodes comprising an organic solvent.
  • a relatively low temperature for example, 150° C. to 300° C., preferably 180° C. to 250° C.
  • the binder resin composition for electrodes of the present invention may be suitably used as a binder resin composition for batteries, because the polyimide resin, which is obtained by the heat treatment as described above, preferably has a weight increase of 3 wt % or less, more preferably 2 wt % or less, further preferably 1 wt % or less, when immersed in dimethyl carbonate for 24 hours at a temperature of 25° C.
  • dimethyl carbonate is a compound commonly used as an electrolyte component of a battery, and when the weight increase in a liquid electrolyte (rate of swelling when immersed in the liquid electrolyte for 24 hours at a temperature of 25° C.) of the binder resin, which is caused by swelling by the liquid electrolyte, is 5 wt % or less, more preferably 3 wt % or less, particularly preferably 2 wt % or less, the influence of the volume change of the electrode may be suitably reduced.
  • the polyimide resin obtained from the binder resin composition for electrodes of the present invention preferably has a weight increase in a liquid electrolyte containing lithium methoxide (rate of swelling when immersed in the liquid electrolyte for 24 hours at a temperature of 25° C.) of 5 wt % or less, more preferably 3 wt % or less, particularly preferably 2 wt % or less.
  • An electrode mixture paste may be suitably prepared by mixing the binder resin composition for electrodes of the present invention with at least an electrode active material, preferably, but not limited to, at a temperature of from 10° C. to 60° C. Any known electrode active material may be suitably used, and a lithium-containing metal composite oxide, a carbon powder, a silicon powder, a tin powder, and a silicon-containing or tin-containing alloy powder may be more preferred.
  • the amount of the electrode active material in the electrode mixture paste may be generally, but not limited to, from 0.1 to 1000 times, preferably from 1 to 1000 times, more preferably from 5 to 1000 times, further preferably from 10 to 1000 times, the weight of the solid content based on the polyamic acid on a weight basis.
  • the electrode mixture paste may contain an additive such as a surfactant, a viscosity modifier, and a conductive auxiliary agent, as necessary.
  • the solid content of the polyamic acid may be preferably from 1 wt % to 15 wt %, relative to the whole solid content in the electrode mixture paste. When the solid content of the polyamic acid is outside the above-mentioned range, the performance of the electrode may be degraded.
  • An electrode may be produced by
  • the electrode mixture paste comprises the binder resin composition for electrodes of the present invention, and an electrode active material which is capable of reversibly incorporating and releasing lithium ion on charge and discharge, for example, a lithium-containing metal composite oxide;
  • the heating temperature is outside the above-mentioned range, the imidization reaction may not sufficiently proceed, and the properties of the formed electrode may be degraded.
  • the heat treatment may be performed in multiple steps so as to prevent foaming and powdering. Additionally, the heating time is preferably from 3 minutes to 48 hours. The heating time longer than 48 hours is not preferred in terms of productivity. The heating time shorter than 3 minutes is not preferred because the imidization reaction, and the removal of the solvent may not sufficiently proceed.
  • the electrode thus obtained may be particularly suitably used as a positive electrode of a lithium ion secondary battery.
  • An electrode may be produced by
  • the electrode mixture paste comprises the binder resin composition for electrodes of the present invention, and an electrode active material which is capable of reversibly incorporating and releasing lithium ion on charge and discharge, for example, a carbon powder, a silicon powder, a tin powder, or a silicon-containing or tin-containing alloy powder; and then
  • the electrode mixture paste at a temperature of from 80° C. to 300° C., more preferably from 120° C. to 280° C., particularly preferably from 150° C. to 250° C., to remove a solvent and effect imidization.
  • the heating temperature is lower than 80° C.
  • the imidization reaction may not sufficiently proceed, and the properties of the formed electrode may be degraded.
  • the electrode mixture paste is heated at a temperature higher than 300° C.
  • copper may deform, and therefore the product may not be used as an electrode.
  • the heat treatment may be performed in multiple steps so as to prevent foaming and powdering, in this case, as well.
  • the heating time is preferably from 3 minutes to 48 hours. The heating time longer than 48 hours is not preferred in terms of productivity. The heating time shorter than 3 minutes is not preferred because the imidization reaction, and the removal of the solvent may not sufficiently proceed.
  • the electrode thus obtained may be particularly suitably used as a negative electrode of a lithium ion secondary battery.
  • aqueous polyimide precursor solution composition of the present invention may also be suitably used as a polyimide precursor resin composition for flexible device substrates.
  • a coating film of an aqueous polyimide precursor solution composition layer is formed on a substrate by applying or spraying an aqueous polyimide precursor solution composition (specifically, an aqueous polyimide precursor solution composition in which a polyamic acid consisting of a repeating unit represented by the formula (1) is homogeneously dissolved in an aqueous solvent together with an imidazole in an amount of 1.6 mole or more per mole of the tetracarboxylic acid component of the polyamic acid) onto the substrate surface, and then the aqueous polyimide precursor solution composition is heated to provide a polyimide substrate for flexible devices.
  • an aqueous polyimide precursor solution composition specifically, an aqueous polyimide precursor solution composition in which a polyamic acid consisting of a repeating unit represented by the formula (1) is homogeneously dissolved in an aqueous solvent together with an imidazole in an amount of 1.6 mole or more per mole of the tetracarboxylic acid component of
  • a polyimide substrate for flexible devices may be suitably prepared by heating the aqueous polyimide precursor solution composition to remove an aqueous solvent and effect imidization (dehydration/ring closure).
  • the heat treatment conditions are not limited, but, in general, the aqueous polyimide precursor solution composition may be preferably heated at a temperature of 100° C. or higher, preferably from 120° C. to 600° C., more preferably from 150° C. to 500° C., further preferably from 150° C. to 350° C., for from 0.01 hours to 30 hours, preferably from 0.01 hours to 10 hours, preferably while increasing the temperature stepwise.
  • the heat treatment may be suitably performed under atmospheric pressure, and may be performed under reduced pressure so as to efficiently remove the aqueous solvent.
  • the aqueous polyimide precursor solution composition may be heated at a relatively low temperature under reduced pressure at the early stage for deaeration. When the heating temperature is rapidly increased, a problem such as foaming may occur, and therefore a good flexible device substrate may not be obtained.
  • the aqueous polyimide precursor solution composition may be heated at a relatively low temperature (for example, 150° C. to 300° C., preferably 180° C. to 250° C.) to readily provide a polyimide substrate for flexible devices, which has excellent properties, and is in no way inferior to a polyimide substrate obtained from a commonly-used polyimide precursor (polyamic acid) solution composition comprising an organic solvent.
  • a relatively low temperature for example, 150° C. to 300° C., preferably 180° C. to 250° C.
  • a solid polyimide resin film is formed on a carrier substrate as a support by applying a polyimide precursor resin composition (aqueous polyimide precursor solution composition) onto the carrier substrate, and heating the composition; a circuit is formed on the polyimide resin film; and then the polyimide resin film on which the circuit is formed is separated from the carrier substrate.
  • a polyimide precursor resin composition aqueous polyimide precursor solution composition
  • Any method for applying an aqueous polyimide precursor solution composition may be applied, as long as a coating film having a uniform thickness is formed on a carrier substrate (support).
  • a coating film having a uniform thickness is formed on a carrier substrate (support).
  • die coating, spin coating, and screen printing may be employed for the application.
  • a substrate for flexible devices may be suitably produced by a method, comprising
  • the aqueous polyimide precursor solution composition of the present invention may contain other additive component(s) depending on the intended application of the polyimide substrate for flexible devices obtained. Additionally, another resin layer may be laminated on the polyimide substrate for flexible devices obtained.
  • the thickness of the polyimide resin film is desirably from 1 ⁇ m to 20 ⁇ m.
  • the thickness is less than 1 ⁇ m, the polyimide resin film may not remain adequately resistant, and therefore the polyimide resin film may not withstand stress and may be broken when used as a flexible device substrate.
  • the thickness of the polyimide resin film is more than 20 ⁇ m and greater, it may be difficult to achieve the thinning of the flexible device.
  • the thickness of the polyimide resin film is more desirably from 2 ⁇ m to 10 ⁇ m so as to achieve the further thinning, while maintaining an adequate resistance for the flexible device.
  • a circuit needed for a display device or a light-receiving device is formed on the polyimide resin film formed as described above.
  • This step differs from device to device.
  • a TFT liquid crystal display device a TFT of amorphous silicon, for example, is formed on the polyimide resin film.
  • the TFT comprises a gate metal layer, a silicon nitride gate dielectric layer, and an ITI pixel electrode.
  • a structure needed for a liquid crystal display may be formed thereon by a known method.
  • the method for forming a circuit, and the like is not limited because the polyimide resin film obtained according to the present invention has excellent properties such as heat resistance, and toughness.
  • the polyimide resin film on which the circuit etc. is formed as described above is separated from the carrier substrate.
  • the method for the separation is not limited.
  • the polyimide resin film on which the circuit is formed may be separated from the carrier substrate by irradiation with laser or the like from the carrier substrate side. Because the polyimide resin film obtained according to the present invention has high flexibility and toughness, it may be physically separated from the carrier substrate (support) simply.
  • Examples of the flexible device in the present invention include display devices such as a liquid crystal display, an organic EL display and an electronic paper, and light-receiving devices such as a solar cell and CMOS.
  • the present invention may be particularly suitably applied to devices to be thinner and flexible.
  • a sample solution (the weight is referred to as “w1”) was heated at 120° C. for 10 minutes, 250° C. for 10 minutes, and then 350° C. for 30 minutes in a hot air dryer, and the weight of the sample after the heat treatment (the weight is referred to as “w2”) was measured.
  • the solid content [wt %] was calculated by the following formula.
  • a sample solution was diluted to a concentration of 0.5 g/dl based on the solid content (the solvent: water).
  • the flowing time (T 1 ) of the diluted solution was measured at 30° C. using a Cannon-Fenske viscometer No. 100.
  • the inherent viscosity was calculated by the following formula using the flowing time (T 0 ) of the blank water.
  • the solution viscosity was measured at 30° C. using an E type viscometer manufactured by Tokimec, Inc.
  • An aqueous polyimide precursor solution composition obtained was applied on a glass plate as a substrate with a bar coater.
  • the resulting coating film was deaerated and predried at 25° C. for 30 minutes under reduced pressure. Subsequently, the predried coating film was placed into a hot air dryer and heated at 80° C. for 30 minutes, and then 200° C. for 1 hour under atmospheric pressure, to provide a polyimide film having a thickness of 25 ⁇ m.
  • the properties of the polyimide film were evaluated.
  • the tensile test was performed in accordance with ASTM D882 using a tensile tester (RTC-1225A, manufactured by Orientec Co., Ltd.) to determine the tensile elastic modulus, tensile elongation at break, and tensile strength at break.
  • RTC-1225A tensile tester
  • the 180° folding test was performed, and an article in which no crack appeared in the polyimide film was evaluated as ⁇ , and an article in which a crack appeared in the polyimide film was evaluated as x.
  • aqueous polyimide precursor solution composition was uniformly applied on the inner surface of a cylindrical mold having an inside diameter of 150 mm and a length of 300 mm, while rotating the mold at 100 rpm. Subsequently, the resulting coating film was heated at 80° C. for 30 minutes, and then 200° C. for 1 hour, while rotating the mold at 200 rpm, to provide a polyimide seamless belt having a thickness of 50 ⁇ m.
  • the state of the seamless belt obtained was visually observed. Additionally, the properties of the polyimide seamless belt were evaluated.
  • the polyimide seamless belt sample obtained from the aqueous polyimide precursor solution composition and having a thickness of 50 ⁇ m was cut into a 10 mm ⁇ 50 mm rectangle. The 180° folding test was repeated, and the number of times the 180° folding test was repeated until a crack appeared was determined.
  • a binder resin composition for electrodes obtained was applied on a glass plate as a substrate with a bar coater.
  • the resulting coating film was deaerated and predried at 25° C. for 30 minutes under reduced pressure. Subsequently, the predried coating film was placed into a hot air dryer and heated at 80° C. for 30 minutes, and then 200° C. for 1 hour under atmospheric pressure, to provide a polyimide film having a thickness of 25 ⁇ m.
  • the properties of the polyimide film were evaluated.
  • the polyimide film obtained from the binder resin composition for electrodes was cut into a 5 cm square (thickness: 25 ⁇ m), which was used as a sample.
  • the sample was dried at 60° C. for 24 hours under vacuum, and the weight of the sample was defined as “dry weight (Wd)”.
  • the sample was immersed in a dimethyl carbonate (DMC) solution or a 10 wt % lithium methoxide methanol solution at 25° C. for 24 hours, and the weight of the sample was defined as “wet weight (Ww)”.
  • DMC dimethyl carbonate
  • Ww dry weight
  • the “swelling rate (S)” was calculated by the following formula.
  • s-BPDA 3,3′,4,4′-biphenyltetracarboxylic dianhydride
  • ODPA 4,4′-oxydiphthalic dianhydride
  • t-DCDA trans-dicyclohexyl-3,3′,4,4′-tetracarboxylic dianhydride
  • H-PMDA 1,2,4,5-cyclohexane tetracarboxylic-1,2:4,5-dianhydride
  • 6FDA 4,4′-(hexafluoroisopropylidene)diphthalic anhydride
  • ODA 4,4′-diaminodiphenyl ether (solubility in water at 25° C.: 0.19 g/L)
  • PPD p-phenylenediamine (solubility in water at 25° C.: 120 g/L)
  • t-CHDA trans-1,4-diaminocyclohexane (solubility in water at 25° C.: 1000
  • aqueous polyimide precursor solution having a solid content of 13.0 wt %, a solution viscosity of 20.1 Pa ⁇ s, and an inherent viscosity of 0.42.
  • Example A1 Example A2 Example A1 Example A2 acid s-BPDA (mol %) 100 100 100 100 100 component diamine ODA (mol %) 20 90 90 component PPD (mol %) 20 HMD (mol %) 80 80 D2000 (mol %) 10 1074 (mol %) 10 imidazole 1,2-DMZ (equivalents) 1.25 1.25 1.25 1.25 Aqueous polymerization temperature 70 70 70 polyimide polymerization time 6 6 6 6 precursor inherent viscosity 0.72 0.86 Aqueous polyimide precursor solution solid content (wt %) 16.0 15.7 solution could not be obtained.
  • a polyimide seamless belt was prepared from the aqueous polyimide precursor solution composition obtained in Example A1, as described in ⁇ Production of Polyimide Seamless Belt> section.
  • a polyimide seamless belt was prepared from the aqueous polyimide precursor solution composition obtained in Example A4, as described in ⁇ Production of Polyimide Seamless Belt> section.
  • a polyimide seamless belt was prepared from the aqueous polyimide precursor solution composition obtained in Example AG, as described in ⁇ Production of Polyimide Seamless Belt> section.
  • a polyimide seamless belt was prepared from the aqueous polyimide precursor solution composition obtained in Example A7, as described in ⁇ Production of Polyimide Seamless Belt> section.
  • An aromatic polyimide seamless belt was prepared from the aqueous polyimide precursor solution composition, as described in ⁇ Production of Aromatic Polyimide Seamless Belt> section.
  • An aromatic polyimide seamless belt was prepared from the aqueous polyimide precursor solution composition, as described in ⁇ Production of Aromatic Polyimide Seamless Belt> section.
  • Example B1 Example B2 Example B3 Example B4 Example B1 Example B2 acid s-BPDA (mol %) 100 100 70 50 100 70 component ODPA (mol %) 30 50 30 diamine ODA (mol %) 50 60 60 100 70 component PPD (mol %) 60 20 20 20 30 t-CHDA (mol %) 40 HMD (mol %) 30 20 20 imidazole 1,2-DMZ (equivalents) 1.25 1.25 1.25 1.25 1.25 1.25 Aqueous polymerization temperature 70 70 70 70 70 70 polyimide polymerization time 6 6 6 6 4 4 precursor inherent viscosity 1.04 0.38 0.46 0.42 0.42 0.46 solution solid content (wt %) 16.7 16.7 13.1 13.0 8.7 9.0 solution viscosity (Pa ⁇ s) 27.2 20.7 54.8 20.1 32.0 5.2 Polyimide state observation ⁇ ⁇ ⁇ ⁇ ⁇ seamless flexibility test (number of times) 70 75 85 82 35 50 belt
  • aqueous polyimide precursor solution composition binder resin composition for electrodes obtained in Example A2 (solid content after imidization: 0.8 g) and 9.2 g of 300 mesh silicon powder were ground and kneaded to provide an electrode mixture paste.
  • the obtained paste was capable of being spread on a copper foil with a glass rod.
  • the copper foil on which the paste was applied was fixed on a substrate, and heated at 120° C. for 1 hour, 200° C. for 10 minutes, 220° C. for 10 minutes, and then 250° C. for 10 minutes in a nitrogen atmosphere, to suitably provide an electrode having an active material layer thickness of 100 ⁇ m.
  • An electrode was suitably prepared from the aqueous polyimide precursor solution composition (binder resin composition for electrodes) obtained in Example A4 in the same way as in Example C1.
  • An electrode was suitably prepared from the aqueous polyimide precursor solution composition (binder resin composition for electrodes) obtained in Example A5 in the same way as in Example C1.
  • An electrode was suitably prepared from the aqueous polyimide precursor solution composition (binder resin composition for electrodes) obtained in Example A6 in the same way as in Example C1.
  • An electrode was suitably prepared from the aqueous polyimide precursor solution composition (binder resin composition for electrodes) obtained in Example A7 in the same way as in Example C1.
  • the aqueous polyimide precursor solution composition obtained in Example A1 was applied on a glass plate as a substrate with a bar coater.
  • the resulting coating film was deaerated and predried at 25° C. for 30 minutes under reduced pressure. Subsequently, the predried coating film was placed into a hot air dryer and heated at 80° C. for 30 minutes, 120° C. for 30 minutes, 200° C. for 10 minutes, and then 250° C. for 10 minutes under atmospheric pressure, to provide a polyimide film having a thickness of 10 ⁇ m.
  • the aqueous polyimide precursor solution composition obtained in Example A5 was applied on a glass plate as a substrate with a bar coater.
  • the resulting coating film was deaerated and predried at 25° C. for 30 minutes under reduced pressure. Subsequently, the predried coating film was placed into a hot air dryer and heated at 80° C. for 30 minutes, 120° C. for 30 minutes, 200° C. for 10 minutes, and then 250° C. for 10 minutes under atmospheric pressure, to provide a polyimide film having a thickness of 10 ⁇ m.
  • the aqueous polyimide precursor solution composition obtained in Example A9 was applied on a glass plate as a substrate with a bar coater.
  • the resulting coating film was deaerated and predried at 25° C. for 30 minutes under reduced pressure. Subsequently, the predried coating film was placed into a hot air dryer and heated at 80° C. for 30 minutes, 120° C. for 30 minutes, 200° C. for 10 minutes, and then 250° C. for 10 minutes under atmospheric pressure, to provide a polyimide film having a thickness of 10 ⁇ m.
  • the aqueous polyimide precursor solution composition obtained in Example A10 was applied on a glass plate as a substrate with a bar coater.
  • the resulting coating film was deaerated and predried at 25° C. for 30 minutes under reduced pressure. Subsequently, the predried coating film was placed into a hot air dryer and heated at 80° C. for 30 minutes, 120° C. for 30 minutes, 200° C. for 10 minutes, and then 250° C. for 10 minutes under atmospheric pressure, to provide a polyimide film having a thickness of 10 ⁇ m.
  • an aqueous polyimide precursor solution composition having an extremely low organic solvent content particularly an aqueous polyimide precursor solution composition comprising an aqueous solvent which contains no organic solvent, may be very easily (directly) produced.
  • an aqueous polyimide precursor solution composition which comprises an aqueous solvent and has good environmental acceptability, and may provide a polyimide having excellent properties such as flexibility, heat resistance, mechanical strength, electrical properties, and solvent resistance, and preferably comprises a polyimide precursor having a high molecular weight and a solvent containing no organic solvent other than water.
  • the seamless belt of the polyimide which is obtained according to the production method of the present invention may have excellent properties such as flexibility, heat resistance, mechanical strength, electrical properties, and solvent resistance, and therefore may be suitably used as an intermediate transfer seamless belt or a fixing seamless belt of an electrophotographic device.
  • a binder resin composition for electrodes which comprises an aqueous solvent and has good environmental acceptability.
  • the polyimide obtained from the binder resin composition for electrodes may have excellent properties such as flexibility, heat resistance, mechanical strength, electrical properties, and solvent resistance, and have a low degree of swelling in a battery environment, and have excellent toughness.
  • a polyimide precursor resin composition for flexible device substrates which comprises an aqueous solvent and has good environmental acceptability.
  • the polyimide substrate for flexible device which is obtained according to the present invention may have excellent properties such as flexibility, heat resistance, mechanical strength, electrical properties, and solvent resistance, and therefore may be suitably used, for example, as a substrate for flexible device which is a display device such as substrates for a liquid crystal display, an organic EL display and an electronic paper, and as a substrate for flexible device which is a light-receiving device such as a substrate for a thin-film solar cell.
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015101710A (ja) * 2013-11-27 2015-06-04 宇部興産株式会社 ポリイミド前駆体組成物、ポリイミドの製造方法、ポリイミド、ポリイミドフィルム、及び基板
US20150291715A1 (en) * 2014-04-12 2015-10-15 Xerox Corporation Vinyl acetate crotonic acid intermediate transfer members
EP3051613A1 (en) * 2013-09-26 2016-08-03 UBE Industries, Ltd. Polyimide binder for power storage device, electrode sheet using same, and power storage device
US9505886B2 (en) 2014-07-25 2016-11-29 Fuji Xerox Co., Ltd. Polyimide precursor composition, method for preparing polyimide precursor, polyimide molded article, and method for preparing polyimide molded article
US9550862B2 (en) 2014-07-25 2017-01-24 Fuji Xerox Co., Ltd. Polyimide precursor composition, method for preparing polyimide precursor, polyimide molded article, and method for preparing polyimide molded article
US9685654B2 (en) * 2014-04-18 2017-06-20 Ube Industries, Ltd. Method for producing electrode
US20180022873A1 (en) * 2015-02-20 2018-01-25 Sabic Global Technologies B.V. Poly(amic acid) synthesis and conversion to high molecular weight polyimide
US20180037700A1 (en) * 2016-08-04 2018-02-08 Tetramer Technologies, Llc Copolymers Exhibiting Improved Thermo-Oxidative Stability
US10511025B2 (en) 2014-06-05 2019-12-17 Ube Industries, Ltd. Electrode manufacturing method
US10739513B2 (en) 2018-08-31 2020-08-11 RAB Lighting Inc. Apparatuses and methods for efficiently directing light toward and away from a mounting surface
US10801679B2 (en) 2018-10-08 2020-10-13 RAB Lighting Inc. Apparatuses and methods for assembling luminaires
US10903497B2 (en) * 2016-03-31 2021-01-26 Lg Chem, Ltd. Cathode having improved safety and lithium secondary battery including the same
US11407868B2 (en) 2012-01-13 2022-08-09 Ube Industries, Ltd. Method for producing aqueous polyimide precursor solution composition
US11407857B2 (en) * 2011-09-09 2022-08-09 Ube Industries, Ltd. Method for producing aqueous polyimide precursor solution composition

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5879971B2 (ja) * 2011-11-28 2016-03-08 宇部興産株式会社 ポリイミド溶液組成物
JP5978842B2 (ja) * 2012-08-03 2016-08-24 宇部興産株式会社 ポリイミド被膜の製造方法
WO2014148440A1 (ja) * 2013-03-19 2014-09-25 日産化学工業株式会社 横電界駆動用の液晶配向処理剤
JP2015109254A (ja) * 2013-10-25 2015-06-11 三井化学株式会社 リチウムイオン二次電池用バインダー樹脂組成物およびそれを含む負極合材ペースト、リチウムイオン二次電池用負極およびそれを含む二次電池
KR102281153B1 (ko) * 2013-11-27 2021-07-22 우베 고산 가부시키가이샤 폴리이미드 전구체 조성물, 폴리이미드의 제조 방법, 폴리이미드, 폴리이미드 필름, 및 기판
JP6314707B2 (ja) * 2014-07-09 2018-04-25 宇部興産株式会社 ポリイミド前駆体組成物、及びそれを用いた絶縁被覆層の製造方法
JP2016076481A (ja) * 2014-10-02 2016-05-12 セントラル硝子株式会社 有機エレクトロルミネッセンス用基板およびそれを用いた有機エレクトロルミネッセンスディスプレイ
JP6635403B2 (ja) * 2014-12-26 2020-01-22 荒川化学工業株式会社 樹脂付銅箔、銅張積層板、プリント配線板及び多層配線板
KR101692133B1 (ko) * 2015-01-13 2017-01-02 연세대학교 원주산학협력단 폴리이미드 수용액을 이용한 폴리이미드 성형방법
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KR101578545B1 (ko) * 2015-03-12 2015-12-17 (주)상아프론테크 2차 전지용 수용성 바인더, 이의 제조방법, 이를 이용한 2차 전지용 전극활물질 코팅제 및 2차 전지용 전극
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JP6939017B2 (ja) * 2016-03-30 2021-09-22 荒川化学工業株式会社 ポリイミド、ポリイミド系接着剤、フィルム状接着材、接着層、接着シート、樹脂付銅箔、銅張積層板及びプリント配線板、並びに多層配線板及びその製造方法
TWI641654B (zh) * 2016-04-08 2018-11-21 Taiwan Textile Research Institute 聚醯亞胺組成物以及分離膜的製備方法
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EP3534431A4 (en) * 2016-10-28 2020-03-11 Toray Industries, Inc. SEPARATOR FOR NONAQUEOUS ELECTROLYTE CELL, AND NONAQUEOUS ELECTROLYTE CELL
JP6897690B2 (ja) * 2016-12-08 2021-07-07 日産化学株式会社 剥離層の製造方法
KR101842447B1 (ko) * 2017-04-06 2018-05-14 주식회사 피엔에스테크놀로지 저온경화형 폴리이미드 전구체 조성물
JP2019172970A (ja) * 2018-03-26 2019-10-10 東レ株式会社 表示デバイスまたは受光デバイスの基板用樹脂組成物、並びに、それを用いた表示デバイスまたは受光デバイスの基板、表示デバイス、受光デバイス、表示デバイスまたは受光デバイスの製造方法。
US20210115279A1 (en) * 2018-03-30 2021-04-22 Virginia Tech Intellectual Properties, Inc. Additive manufacturing of aromatic thermoplastics from photocurable precursor salts
TW202041642A (zh) * 2019-03-27 2020-11-16 日商宇部興產股份有限公司 蓄電裝置用聚醯亞胺系黏結劑、電極合劑膏、負極活性物質層、蓄電裝置用負極片及蓄電裝置
CN114747043A (zh) * 2019-10-02 2022-07-12 宇部兴产株式会社 负极活性材料层及其制造方法、蓄电装置负极用电极混合物糊剂、蓄电装置用负极和蓄电装置
EP4040533A1 (en) * 2019-10-02 2022-08-10 Ube Industries, Ltd. Active material layer for negative electrode, method for producing same, electrode mix paste for power storage device negative electrode, negative electrode for power storage device, and power storage device
WO2023144709A1 (en) * 2022-01-25 2023-08-03 Tata Steel Limited Preparation and application of polyimide intermediates for anti-corrosion coating on metal surfaces
WO2023218512A1 (ja) * 2022-05-09 2023-11-16 株式会社レゾナック ポリアミド酸含有液及びポリアミド酸含有液の製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3703493A (en) * 1966-05-05 1972-11-21 Fred Holub Preparation of polyamide-acid solution in aqueous tertiary amine
WO2012008543A1 (ja) * 2010-07-14 2012-01-19 宇部興産株式会社 ポリイミド前駆体水溶液組成物、及びポリイミド前駆体水溶液組成物の製造方法

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1162203A (en) 1966-04-06 1969-08-20 Nat Res Dev Production of Polyamic Acids and Polyimides
US3507765A (en) * 1966-05-05 1970-04-21 Gen Electric Method for electrocoating a polyamide acid
US3440197A (en) * 1966-05-05 1969-04-22 Gen Electric Coating solutions and methods for preparing and using the same
US3575923A (en) * 1968-10-11 1971-04-20 Monsanto Co Aqueous process for the preparation of polyimide resins
US4221897A (en) * 1979-05-09 1980-09-09 General Electric Company Method for making polyetheramide acid
JPS58145419A (ja) 1982-02-23 1983-08-30 Toray Ind Inc 芳香族ポリイミドフイルムの製造方法
US4480088A (en) 1983-10-20 1984-10-30 United Technologies Corporation Water soluble polyimide resin system
US5393864A (en) * 1993-04-26 1995-02-28 E. I. Du Pont De Nemours And Company Wet-etchable random polyimide copolymer for multichip module applications
JPH0859832A (ja) 1993-10-29 1996-03-05 Hitachi Ltd 水溶性ポリアミド酸塩とポリイミド前駆体ワニス及びポリイミドとその用途
JPH07302969A (ja) * 1994-04-28 1995-11-14 Ube Ind Ltd 基板上金属配線の被覆方法
JP2000297152A (ja) * 1999-04-15 2000-10-24 Unitika Ltd ポリイミド前駆体水溶液及びその製造方法、それから得られるポリイミド塗膜及びその製造方法
US20020151234A1 (en) * 2001-02-05 2002-10-17 Ube Industries, Ltd. Water-soluble polyimide precursor, aqueous polyimide precursor solution, polyimide, impregnated material with polyimide binder, and laminate
JP4497732B2 (ja) * 2001-02-05 2010-07-07 宇部興産株式会社 水溶性ポリイミド前駆体、ポリイミド前駆体水溶液、その製法およびポリイミド
JP4039011B2 (ja) * 2001-07-02 2008-01-30 宇部興産株式会社 耐熱性不織布及びバインダ−樹脂
CN1311039C (zh) * 2003-01-31 2007-04-18 帝人株式会社 粘合片材和层合体
JP2006232911A (ja) * 2005-02-23 2006-09-07 Toray Ind Inc 熱可塑性ポリイミド前駆体組成物およびこれを用いた積層ポリイミドフィルムの製造方法
JP5370631B2 (ja) * 2007-02-05 2013-12-18 Ｊｓｒ株式会社 液晶配向剤、液晶配向膜および液晶表示素子
JP5186855B2 (ja) * 2007-09-25 2013-04-24 宇部興産株式会社 バインダー樹脂
JP2010202729A (ja) 2009-03-02 2010-09-16 Hitachi Chemical Dupont Microsystems Ltd フレキシブルデバイス基板用ポリイミド前駆体樹脂組成物及びそれを用いたフレキシブルデバイスの製造方法、フレキシブルデバイス
EP2580264A1 (en) * 2010-06-08 2013-04-17 Tata Steel Nederland Technology B.V. A method of preparing a polyetherimide coated substrate
JP5834930B2 (ja) * 2011-09-09 2015-12-24 宇部興産株式会社 ポリイミド前駆体水溶液組成物、及びポリイミド前駆体水溶液組成物の製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3703493A (en) * 1966-05-05 1972-11-21 Fred Holub Preparation of polyamide-acid solution in aqueous tertiary amine
WO2012008543A1 (ja) * 2010-07-14 2012-01-19 宇部興産株式会社 ポリイミド前駆体水溶液組成物、及びポリイミド前駆体水溶液組成物の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Chemical Abstracts (solubility data for Benzenamine, 4,4'-[1,3-phenylenebis(oxy)]bis-, 2479-46-1, downloaded 8/24/15). *

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11407857B2 (en) * 2011-09-09 2022-08-09 Ube Industries, Ltd. Method for producing aqueous polyimide precursor solution composition
US11407868B2 (en) 2012-01-13 2022-08-09 Ube Industries, Ltd. Method for producing aqueous polyimide precursor solution composition
EP3051613A1 (en) * 2013-09-26 2016-08-03 UBE Industries, Ltd. Polyimide binder for power storage device, electrode sheet using same, and power storage device
EP3051613A4 (en) * 2013-09-26 2017-04-26 UBE Industries, Ltd. Polyimide binder for power storage device, electrode sheet using same, and power storage device
US10056614B2 (en) 2013-09-26 2018-08-21 Ube Industries, Ltd. Polyimide binder for power storage device, electrode sheet using same, and power storage device
JP2015101710A (ja) * 2013-11-27 2015-06-04 宇部興産株式会社 ポリイミド前駆体組成物、ポリイミドの製造方法、ポリイミド、ポリイミドフィルム、及び基板
US20150291715A1 (en) * 2014-04-12 2015-10-15 Xerox Corporation Vinyl acetate crotonic acid intermediate transfer members
US9493596B2 (en) * 2014-04-12 2016-11-15 Xerox Corporation Vinyl acetate crotonic acid intermediate transfer members
US9685654B2 (en) * 2014-04-18 2017-06-20 Ube Industries, Ltd. Method for producing electrode
US10511025B2 (en) 2014-06-05 2019-12-17 Ube Industries, Ltd. Electrode manufacturing method
US9505886B2 (en) 2014-07-25 2016-11-29 Fuji Xerox Co., Ltd. Polyimide precursor composition, method for preparing polyimide precursor, polyimide molded article, and method for preparing polyimide molded article
US9550862B2 (en) 2014-07-25 2017-01-24 Fuji Xerox Co., Ltd. Polyimide precursor composition, method for preparing polyimide precursor, polyimide molded article, and method for preparing polyimide molded article
US20180022873A1 (en) * 2015-02-20 2018-01-25 Sabic Global Technologies B.V. Poly(amic acid) synthesis and conversion to high molecular weight polyimide
US10501579B2 (en) * 2015-02-20 2019-12-10 Sabic Global Technologies B.V. Poly(amic acid) synthesis and conversion to high molecular weight polyimide
US10903497B2 (en) * 2016-03-31 2021-01-26 Lg Chem, Ltd. Cathode having improved safety and lithium secondary battery including the same
US10487177B2 (en) * 2016-08-04 2019-11-26 Tetramer Technologies, Inc. Copolymers exhibiting improved thermo-oxidative stability
US20180037700A1 (en) * 2016-08-04 2018-02-08 Tetramer Technologies, Llc Copolymers Exhibiting Improved Thermo-Oxidative Stability
US10739513B2 (en) 2018-08-31 2020-08-11 RAB Lighting Inc. Apparatuses and methods for efficiently directing light toward and away from a mounting surface
US10801679B2 (en) 2018-10-08 2020-10-13 RAB Lighting Inc. Apparatuses and methods for assembling luminaires

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US20200224054A1 (en) 2020-07-16
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US11407857B2 (en) 2022-08-09
EP2754683B1 (en) 2018-05-30
US20170073545A1 (en) 2017-03-16
WO2013035806A1 (ja) 2013-03-14
EP2754683A1 (en) 2014-07-16
EP2754683A4 (en) 2015-06-24
TWI570157B (zh) 2017-02-11
KR20140059283A (ko) 2014-05-15
CN103930470B (zh) 2016-11-23
JP2013067769A (ja) 2013-04-18
JP5834930B2 (ja) 2015-12-24

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