WO2013133168A1 - Polyamic acid and polyimide - Google Patents

Polyamic acid and polyimide Download PDF

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Publication number
WO2013133168A1
WO2013133168A1 PCT/JP2013/055690 JP2013055690W WO2013133168A1 WO 2013133168 A1 WO2013133168 A1 WO 2013133168A1 JP 2013055690 W JP2013055690 W JP 2013055690W WO 2013133168 A1 WO2013133168 A1 WO 2013133168A1
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group
formula
resin composition
carbon atoms
structural unit
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PCT/JP2013/055690
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French (fr)
Japanese (ja)
Inventor
隆行 田村
江原　和也
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日産化学工業株式会社
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Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to KR20147026144A priority Critical patent/KR20140133585A/en
Priority to CN201380009835.7A priority patent/CN104114606A/en
Publication of WO2013133168A1 publication Critical patent/WO2013133168A1/en

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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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • 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
    • 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
    • C08G73/16—Polyester-imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide

Definitions

  • the present invention relates to a resin composition for a display substrate, and more particularly to a resin composition for a display substrate capable of forming a useful polyimide film having an appropriate linear expansion coefficient and an appropriate flexibility.
  • Polyimide resins are widely used in the field of electrical and electronic materials because of their high heat resistance, flame retardancy, and excellent electrical insulation. Specifically, it is used as a film for flexible printed wiring boards and heat-resistant adhesive tapes as a film, and as a resin varnish for semiconductor insulating films, protective films, and the like.
  • display devices such as an organic EL (Electroluminescence) display and a liquid crystal display have been demanded only for high definition, but their applications are rapidly expanding to information devices and the like.
  • a flexible display using a plastic film as a substrate is attracting attention in order to satisfy the demand for ultra-thin and light weight.
  • an active matrix driving panel is used for a high-definition display.
  • an active matrix layer including a thin film active element in addition to a matrix-like pixel electrode In order to form an active matrix layer including a thin film active element in addition to a matrix-like pixel electrode, a high temperature treatment of 200 ° C. or higher is required in the manufacturing process, and extremely accurate alignment is required. However, since it is inferior in heat resistance and dimensional stability by changing from a glass substrate to a plastic material for flexibility, it is very difficult to directly form an active element thereon.
  • a polyimide film is formed on a glass substrate, the manufacturing conditions are not limited, and an amorphous silicon TFT element, a color filter, etc. are formed with high-definition alignment to form a transfer layer.
  • Patent Documents 1 and 2 a method of manufacturing a display element by transferring and forming the transfer layer on a plastic film.
  • a linear expansion coefficient is mentioned as a characteristic of the polyimide required at the said process.
  • the linear expansion coefficient of the film is in the range of 60 to 80 ppm / K and does not have low linear expansion characteristics. Under such circumstances, a polyimide film having a low linear expansion coefficient has been developed.
  • an acid dianhydride having poor versatility is used as a raw material, the resulting product becomes expensive (Patent Document 3).
  • the present invention has been made in view of such circumstances, and has heat resistance that can withstand the manufacturing process without using acid dianhydride having poor versatility as a raw material, and has an appropriate linear expansion coefficient and It aims at providing the resin composition for display substrates which can form the useful cured film which has moderate softness
  • flexibility here means self-supporting property and the high softness
  • the present inventor combined an acid anhydride having a biphenyl skeleton as an acid dianhydride component with pyromellitic anhydride and a diamine having a fluorene skeleton as a diamine component. It is useful to have high heat resistance, moderate linear expansion coefficient, and moderate flexibility from the resin composition for display substrates containing the polyamic acid or polyimide derived from the acid dianhydride component and the diamine component.
  • the present invention was completed by finding that a cured film can be obtained.
  • the present invention provides a polyamic acid containing a structural unit represented by the following formula (1) and a structural unit represented by the formula (3), or a structural unit represented by the following formula (2) and It is related with the resin composition for display substrates containing the polyimide containing the structural unit represented by Formula (4).
  • X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups
  • Y 1 represents a divalent aromatic group or aliphatic group
  • Y 2 represents a divalent aromatic group having a fluorene skeleton
  • n and m represent natural numbers.
  • Y 2 is represented by the following formula (5) relates to a display substrate resin composition according to the first aspect.
  • R 0 to R 7 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom.
  • W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group.
  • (circle) represents a bond.
  • the Y 2 is to a display substrate for resin composition according to the second aspect represented by the following formula (5a).
  • ⁇ represents a bond.
  • the Y 1 is represented by the following formula (6), a display substrate resin composition according to any one of the first aspect to the third aspect.
  • R 8 to R 11 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom.
  • W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group.
  • q represents an integer of 1 or 2.
  • the present invention relates to the display substrate resin composition according to the third aspect, in which the divalent aromatic group represented by the formula (6) is derived from phenylenediamine.
  • the present invention relates to the resin composition for display substrates according to the fifth aspect, in which R 8 to R 11 represent hydrogen atoms.
  • the X 1 represents a group represented by the following formula (7), a group represented by the formula (8), or both groups, and any one of the first to sixth aspects. It relates to the resin composition for display substrates as described in above.
  • R 12 to R 23 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, hydroxy group, a halogen atom , nitro group, formyl group, cyano group, carboxyl group, W 1 with an optionally substituted phenyl group, W 1 with an optionally substituted naphthyl group, W 1 with an optionally substituted thienyl group or W Represents a furyl group optionally substituted by 1 , W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group.
  • the present invention relates to the resin composition for display substrates according to the seventh aspect, wherein p represents an integer of 2.
  • the present invention relates to the resin composition for a display substrate according to the eighth aspect, in which R 12 to R 23 represent a hydrogen atom.
  • the present invention relates to the resin composition for a display substrate according to any one of the first aspect to the ninth aspect, wherein the polyamic acid further includes a structural unit represented by the formula (9).
  • X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups
  • Y 3 represents a divalent group having an ether bond
  • l represents a natural number.
  • the resin composition for display substrates as described in any one of the 1st viewpoint thru
  • X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups
  • Y 3 represents a divalent group having an ether bond
  • l represents a natural number.
  • n in the formula (1) and m in the formula (3) have a relationship of n / (n + m) ⁇ 60%. It is related with the resin composition for display substrates of description.
  • n in the formula (2) and m in the formula (4) have a relationship of n / (n + m) ⁇ 60%. It is related with the resin composition for display substrates of description.
  • the present invention relates to the resin composition for display substrates according to the fourteenth aspect, in which the crosslinking agent is a compound having two or more epoxy groups.
  • the present invention relates to the display substrate resin composition according to the fifteenth aspect, in which the crosslinking agent is a compound having an aromatic group.
  • the crosslinking agent has a compound having 6 or less epoxy groups, and the compound has an alkyl group having 1 to 10 carbon atoms that bonds the epoxy group and the aromatic group.
  • the resin composition for display substrates as described in a viewpoint.
  • the resin composition for a display substrate according to any one of the 14th aspect to the 17th aspect wherein the crosslinking agent is 20 parts by mass or less with respect to 100 parts by mass of the polyamic acid or polyimide.
  • the present invention relates to a varnish, wherein the display substrate resin composition according to any one of the first to eighteenth aspects is dissolved in at least one solvent.
  • a 20th viewpoint it is related with the cured film obtained by baking at 230 degreeC or more using the varnish as described in a 19th viewpoint.
  • a 21st viewpoint it is related with a structure provided with at least one layer which consists of a cured film as described in a 20th viewpoint on a board
  • a 22nd viewpoint it is related with the polyamic acid containing the structural unit represented by the structural unit represented by following formula (1), and Formula (3).
  • X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups
  • Y 1 represents a divalent aromatic group or aliphatic group
  • Y 2 represents a divalent aromatic group having a fluorene skeleton
  • n and m represent natural numbers.
  • X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups
  • Y 1 represents a divalent aromatic group or aliphatic group
  • Y 2 represents a divalent aromatic group having a fluorene skeleton
  • n and m represent natural numbers.
  • the present invention relates to the polyimide according to the twenty-fourth aspect, which further includes a structural unit represented by the formula (10).
  • X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups
  • Y 3 represents a divalent group having an ether bond
  • l represents a natural number.
  • the present invention relates to a varnish characterized in that the composition according to the twenty-sixth aspect or the twenty-seventh aspect is dissolved in at least one solvent.
  • a 29th viewpoint it is related with the cured film obtained by baking at 230 degreeC or more using the varnish as described in a 28th viewpoint.
  • the resin composition for display substrates of the present invention includes a specific structure in which the polyamic acid or polyimide is derived from an aromatic diamine containing an dianhydride having an aromatic group and two or more carbonyl groups and a fluorene skeleton.
  • a useful cured film having high heat resistance, an appropriate linear expansion coefficient, and an appropriate flexibility can be formed. Therefore, the cured film can be used as a base film for flexible displays.
  • the present invention is represented by a polyamic acid containing a structural unit represented by the following formula (1) and a structural unit represented by the formula (3), or a structural unit represented by the following formula (2) and the formula (4).
  • the present invention relates to a resin composition for a display substrate containing polyimide containing a structural unit.
  • X 1 represents a tetravalent organic group having an aromatic group and two carbonyl groups
  • Y 1 represents a divalent aromatic group or aliphatic group
  • Y 2 represents a divalent aromatic group having a fluorene skeleton
  • n and m represent natural numbers.
  • the ratio of the solid content in the resin composition for display substrates of the present invention is 1 to 100% by mass, or 5 to 100% by mass, or 50 to 100% by mass, or 80 to 100% by mass.
  • solid content is the remaining component which removed the solvent from all the components of the resin composition for display substrates.
  • the content of the polyamic acid or polyimide in the resin composition for display substrates of the present invention is 8 to 99.9 mass%, preferably 40 to 99 mass%, based on the solid content of the resin composition. More preferably, it is 70 to 99% by mass.
  • the resin composition for display substrate of the present invention contains polyamic acid or polyimide.
  • the polyamic acid contained in the display substrate resin composition of the present invention is obtained by polymerizing an acid anhydride component and a diamine component in a solvent.
  • the polyamic acid is represented by the following formula (11) in a known method, for example, in an inert gas atmosphere such as nitrogen: (Wherein X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups), and the following formula (12): H 2 N—Y 1 —NH 2 (12) (Wherein Y 1 represents a divalent aromatic group or aliphatic group) and at least one diamine represented by the following formula (13): H 2 N—Y 2 —NH 2 (13) (Wherein, Y 2 is represented.
  • the divalent aromatic group having a fluorene skeleton) and at least one diamine represented by dissolving in a solvent is obtained by reacting.
  • the reaction temperature at this time is ⁇ 20 to 100 ° C., preferably 20 to 60 ° C.
  • the reaction time is 1 to 72 hours.
  • the polyamic acid reaction solution can be used as it is or after dilution, or the polyamic acid precipitated and recovered from the reaction solution can be used by re-dissolving in a suitable solvent.
  • the solvent used for the dilution and re-dissolution is not particularly limited as long as it can dissolve the obtained polyamic acid.
  • 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N- Vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropylamide, 3-propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethylpropylamide, 3-tert-butoxy -N, N-dimethylpropylamide, ⁇ -butyrolactone and the like can be mentioned.
  • These solvents may be used alone or in combination of two or more.
  • an acid dianhydride and X 1 where X 1 is represented by the following formula (7) is an acid dianhydride represented by the following formula (8)
  • these acid dianhydrides may be used in combination.
  • R 12 to R 23 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom.
  • W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group.
  • Z 1 and Z 2 each independently represent —NH—, —NZ 3 — or an oxygen atom
  • Z 3 represents an alkyl group having 1 to 10 carbon atoms
  • p represents an integer of 1 or 2.
  • (circle) represents a bond.
  • Formula (8) represents a group derived from pyromellitic anhydride.
  • the p is an integer of 2.
  • Examples of such acid dianhydrides in which X 1 is represented by the formula (7) include p-phenylenebis (trimellitic acid monoester anhydride), 2-methyl-1,4-phenylenebis (trimellitic). Acid monoester anhydride), 2,5-dimethyl-1,4-phenylenebis (trimellitic acid monoester anhydride), 2,3,5,6-tetramethyl-1,4-phenylenebis (trimellitic acid) Monoester anhydride), 2-trifluoromethyl-1,4-phenylenebis (trimellitic acid monoester anhydride), 2,5-ditrifluoromethyl-1,4-phenylenebis (trimellitic acid monoester anhydride) ), 2-chloro-1,4-phenylenebis (trimellitic acid monoester anhydride), 2,5-dichloro-1,4-phenylenebis (trimellitic acid monoe) Steal anhydride), 2-fluoro-1,4-phenylenebis (trimelli
  • R 12 to R in the formula (7) from the viewpoint that the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient and a sufficiently high strength.
  • 4,4-biphenylbis (trimellitic acid monoester acid anhydride) (a compound represented by the following formula ( 21) , wherein 21 represents a hydrogen atom, Z 1 and Z 2 represent an oxygen atom, and m represents an integer of 2. 15)) is preferred.
  • Examples of the acid dianhydride in which X 1 is represented by the formula (8) include pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3-chloropyromellitic dianhydride, 3-bromo Pyromellitic dianhydride, 3-hydroxypyromellitic dianhydride, 3-methylpyromellitic dianhydride, 3-trifluoromethylpyromellitic dianhydride, 3-trichloromethylpyromellitic dianhydride, 3-tribromomethylpyromellitic dianhydride, 3,6-difluoropyromellitic dianhydride, 3,6-dichloropyromellitic dianhydride, 3,6-dibromopyromellitic dianhydride, 3, 6-dihydroxypyromellitic dianhydride, 3,6-dimethylpyromellitic dianhydride, 3,6-bistrifluoromethylpyromellitic dianhydride, 3,6-bistrichloro
  • the aromatic diamine represented by the formula (12) is a diamine having a rigid and linear molecular structure from the viewpoint that the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient. It is preferable to use it.
  • a diamine having a structure in which Y 1 is represented by the following formula (6) is particularly preferable.
  • R 8 to R 11 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom.
  • W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group.
  • q represents an integer of 1 or 2.
  • (circle) represents a bond.
  • the divalent aromatic group represented by the formula (6) is preferably derived from phenylenediamine. Further, from the viewpoint that the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient and a sufficiently high strength, in the formula (6), R 8 to R 11 are hydrogen atoms. Preferably there is.
  • Examples of the aromatic diamine represented by the formula (12) include p-phenylenediamine, o-phenylenediamine, methyl-1,4-phenylenediamine, 2-trifluoromethyl-1,4-phenylenediamine, 2 -Methoxy-1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,5-bis (trifluoromethyl) -1,4-phenylenediamine, 4,4'-diaminobenzanilide, 4-aminophenyl-4′-aminobenzoate, benzidine, 3,3′-dimethoxybenzidine, 3,3′-dichlorobenzidine, o-tolidine, m-tolidine, 2,2′-bis (trifluoromethyl) benzidine, 3,3′-bis (trifluoromethyl) benzidine, octafluorobenzidine, 3,3 ′, 5,5 -Tetramethylbenzidine, 2,2 '
  • Examples of the aliphatic diamine represented by the formula (12) include 4,4′-methylenebis (cyclohexylamine), 4,4′-methylenebis (3-methylcyclohexylamine), isophoronediamine, trans-1,4- Cyclohexanediamine, cis-1,4-cyclohexanediamine, 1,4-cyclohexanebis (methylamine), 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,6-bis (aminomethyl) ) Bicyclo [2.2.1] heptane, 3,8-bis (aminomethyl) tricyclo [5.2.1.0] decane, 1,3-diaminoadamantane, 2,2-bis (4-aminocyclohexyl) Propane, 2,2-bis (4-aminocyclohexyl) hexafluoropropane, 1,3-propanediamine, 1,4 Tetramethylenediamine, 1,5-pentamethylenediamine
  • aliphatic diamines from the viewpoint that the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient, it is preferable to use a diamine having a rigid and linear molecular structure, For example, trans-1,4-cyclohexanediamine is preferably used.
  • the diamine represented by the formula (13) is also a diamine having a rigid and linear molecular structure from the viewpoint that the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient. Is preferably used.
  • the diamine represented by the formula (13) a diamine in which Y 2 is an aromatic group having a fluorene skeleton is preferable, and a group in which Y 2 is a structure represented by the following formula (5) is particularly preferable. preferable.
  • R 0 to R 7 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom.
  • W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group.
  • W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group.
  • (circle) represents a bond. )
  • Examples of the diamine represented by the formula (13) include 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-fluorophenyl) fluorene, and 9,9-bis.
  • (4-amino-3-chlorophenyl) fluorene, 9,9-bis (4-amino-3-bromophenyl) fluorene, 9,9-bis (4-amino-3-hydroxyphenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl) fluorene and the like can be mentioned, and 9,9-bis (4-aminophenyl) fluorene in which Y 2 is a group represented by the following formula (5a) is particularly preferable.
  • the resin anhydride and the diamine represented by the formula (12) and the formula (13) are further added.
  • diamines represented by formula (14) are 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoro.
  • the solvent used in the polyamic acid production reaction is not particularly limited.
  • N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone 3-methoxy-N , N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropylamide, 3-propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethylpropylamide, 3-tert-butoxy-N, N-dimethylpropylamide, hexamethylphosphoramide, dimethylsulfoxide, ⁇ -butyrolactone, 1, 3-Dimethyl-2-imidazolidinone, 1,2-dimethoxy Aprotic solvents such as ethane-bis (2-methoxyethyl) ether, te
  • the ratio of the diamine component is such that the molar ratio of the diamine represented by the above formula (12) and the diamine represented by the above formula (13) is 60/40 to 99/1, From the viewpoint that the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient and a sufficiently high strength, 70/30 to 90/10 is more preferable.
  • the weight average molecular weight of the produced polyamic acid is preferably 3,000 to 300,000 in terms of polystyrene in order to maintain the strength of the cured film obtained from the resin composition for display substrate containing polyamic acid. If the weight average molecular weight is less than 3,000, the resulting film may become brittle. On the other hand, if the weight average molecular weight exceeds 300,000, the viscosity of the polyamic acid varnish may be too high. This is because handling becomes difficult.
  • n and m in the above formulas (1) and (3) are n + m, usually 6 to 180, preferably 10 to 100, more preferably 10 to 50.
  • the number of repeating structural units in the polyamic acid composed of the structural unit represented by the above formula (1) and the structural unit represented by the formula (3) is represented by the formula (1). It is preferable that n and m in the above formula (3) have a relationship of n / (n + m) ⁇ 60%.
  • the polyimide contained in the resin composition for display substrates of the present invention can be obtained by subjecting the polyamic acid synthesized as described above to dehydration ring closure (thermal imidization) by heating. At this time, polyamic acid can be converted to imide in a solvent and used as a solvent-soluble polyimide.
  • the method of chemically ring-closing using a well-known dehydration ring-closing catalyst is also employable.
  • the method by heating can be performed at an arbitrary temperature of 100 to 500 ° C., preferably 120 to 400 ° C.
  • the method of chemically cyclizing can be performed, for example, in the presence of pyridine, triethylamine or the like and acetic anhydride, and the temperature at this time can be selected from -20 to 200 ° C. .
  • the polyimide reaction solution can be used as it is or after dilution, or a poor solvent such as methanol or ethanol is added to the reaction solution and the recovered polyimide is redissolved in an appropriate solvent. can do.
  • the solvent used for dilution and re-dissolution is not particularly limited as long as it can dissolve the obtained polyimide.
  • N-cresol 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropylamide, 3-propoxy -N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethylpropylamide, 3- and tert-butoxy-N, N-dimethylpropylamide, ⁇ -butyrolactone, and the like.
  • solvents may be used alone or in combination of two or more.
  • the weight average molecular weight of the polyimide produced is preferably 3,000 to 300,000 in terms of polystyrene in order to maintain the strength of the cured film obtained from the resin composition for display substrate containing polyimide. If the weight average molecular weight is less than 3,000, the resulting film may be brittle, while if the weight average molecular weight exceeds 300,000, the viscosity of the polyimide varnish may be too high, and as a result, This is because handling becomes difficult.
  • n and m in the above formulas (2) and (4) are usually n + m and are usually 6 to 180, preferably 10 to 100, more preferably 10 Thirty to fifty.
  • the number of repeating structural units in the polyimide composed of the structural unit represented by the above formula (2) and the structural unit represented by the formula (4) is n in the above formula (2).
  • m in the above formula (4) preferably have a relationship of n / (n + m) ⁇ 60%.
  • the polyimide in addition to the structural unit represented by the above formula (10), the polyimide has a structure.
  • n: m: l 60: 20: 20 to 90: 5: 5, and more preferably 70:15:15 to 90: 5: 5.
  • the resin composition for a display substrate of the present invention can contain a solvent.
  • solvents include the solvents described in paragraph [0014].
  • the resin composition for display substrates of the present invention can contain a crosslinking agent (hereinafter also referred to as a crosslinkable compound).
  • a crosslinkable compound is a group capable of reacting with an organic group contained in at least one of polyamic acid or polyimide in the step of converting a coating film obtained by using the positive photosensitive resin composition into a cured film. If it is a compound which has this, it will not specifically limit. Examples of such a compound include a compound containing two or more epoxy groups, a melamine derivative, a benzoguanamine derivative, or a group in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group, or both.
  • the melamine derivative and benzoguanamine derivative may be a dimer or a trimer, or may be a mixture arbitrarily selected from a monomer, a dimer and a trimer. These melamine derivatives and benzoguanamine derivatives preferably have an average of 3 or more and less than 6 methylol groups or alkoxymethyl groups per one triazine ring. Moreover, you may use the crosslinking agent used for this invention individually or in combination of 2 or more types.
  • crosslinkable compound examples include Epolide GT-401, Epolide GT-403, Epolide GT-301, Epolide GT-302, Celoxide 2021, and Celoxide 3000 (manufactured by Daicel Chemical Industries, Ltd.).
  • Epoxy compounds having a cyclohexene structure bisphenol A type epoxy compounds such as Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010, Epicoat 828 (above, manufactured by Japan Epoxy Resins Co., Ltd.); Bisphenol F type epoxy compound such as 807 (manufactured by Japan Epoxy Resin Co., Ltd.); Epicoat 152, Epicoat 154 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPP 201, EPPN202 (above, Nippon Kayaku Co., Ltd.) and other phenol novolac epoxy compounds; ECON-102, ECON-103S, ECON-104S, ECON-1020, ECON-1025, ECON-1027 (above, Nippon Kayaku) Yakuhin Co., Ltd.), Crecoat novolak type epoxy compounds such as Epicote 180S75 (Japan Epoxy Resin Co., Ltd.); Naphthalene type epoxy compounds such as V8000-
  • benzoguanamine derivative or glycoluril having a group in which the hydrogen atom of the amino group is substituted with a methylol group, an alkoxymethyl group, or both, an average of 3.7 methoxymethyl groups are substituted per triazine ring.
  • MX-750 MW-30 substituted with an average of 5.8 methoxymethyl groups per triazine ring (above, manufactured by Sanwa Chemical Co., Ltd.); Cymel 300, Cymel 301, Cymel 303, Cymel 350 Methoxymethylated melamine such as Cymel 370, Cymel 771, Cymel 325, Cymel 327, Cymel 703, Cymel 712, etc .; Mela Butoxymethylated melamines such as Cymel 506 and Cymel 508; carboxyl group-containing methoxymethylated isobutoxymethylated melamines such as Cymel 1141; methoxymethylated ethoxymethylated benzoguanamines such as Cymel 1123; Methoxymethylated butoxymethylated benzoguanamine; butoxymethylated benzoguanamine such as Cymel 1128; methoxymethylated ethoxymethylated benzoguanamine containing carboxyl groups such as Cymel 1125-80; butoxymethylated glycoluril such as Cymel 1170;
  • the content of the crosslinking agent in the resin composition for display substrates of the present invention is not particularly limited, but from the viewpoint of further improving the storage stability of the resin composition, 20 masses with respect to 100 mass parts of polyamic acid or polyimide. From the viewpoint that the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient, 15 parts by mass or less is more preferable.
  • a cured film comprising the resin composition for a display substrate of the present invention
  • the resin composition is dissolved or dispersed in a solvent to form a varnish (film forming material), and the varnish is used as a substrate.
  • a coating film is obtained.
  • the cured film is formed by baking the obtained coating film with a hotplate, oven, etc.
  • the firing temperature is usually 100 to 500 ° C, preferably 100 to 400 ° C.
  • the substrate examples include plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, slate, and the like. Can be mentioned.
  • the solvent used in the form of the varnish is not particularly limited as long as it dissolves the resin composition for a display substrate, and examples thereof include a solvent used in the reaction for producing the polyamic acid. These solvents may be used alone or in combination of two or more. Further, the concentration at which the resin composition is dissolved or dispersed in the solvent is arbitrary, but the concentration of the resin composition for display substrate is 5 to 40 with respect to the total mass (total mass) of the resin composition for display substrate and the solvent. It is preferably 10 to 20% by mass from the viewpoint of further improving the storage stability of the resin composition, and more preferably 10 to 15% by mass from the viewpoint of more uniformly applying the resin composition. Although the thickness of the cured film formed from the resin composition for display substrates is not specifically limited, Usually, 1-50 micrometers, Preferably it is 5-40 micrometers.
  • this invention provides the polyamic acid containing the structural unit represented by following formula (1) and the structural unit represented by Formula (3), and the structural unit and formula (4) represented by Formula (2)
  • the polyimide containing the structural unit represented by this is provided.
  • preferred specific examples of X 1 , Y 1 , Y 2 , n and m are X 1 , Y 1 , Y 2 and the like described in the resin composition for display substrates. The same as the specific examples of n and m.
  • the present invention further provides a polyamic acid containing a structural unit represented by formula (9) or a polyimide containing a structural unit represented by formula (10).
  • this invention provides the composition containing the said polyamic acid and a crosslinking agent, and provides the composition containing the said polyimide and a crosslinking agent.
  • the preferable specific example of a crosslinking agent is the same as the specific example of the crosslinking agent described in the said resin composition for display substrates.
  • the present invention also provides a varnish in which the composition is dissolved in at least one solvent.
  • Preferred specific examples of the solvent are the same as the specific examples of the solvent described in the varnish in which the resin composition for display substrate is dissolved in at least one solvent.
  • this invention provides the cured film obtained by baking at 230 degreeC or more using the said varnish.
  • the method for producing the cured film is the same as the cured film obtained by baking at 230 ° C. or higher using a varnish in which the resin composition for display substrate is dissolved in at least one solvent.
  • Mw polymer weight average molecular weight
  • Mw distribution was measured using a GPC apparatus (Shodex [registered trademark] columns SB803HQ and SB804HQ) manufactured by JASCO Corporation, and dimethylformamide as the elution solvent at a flow rate of 0.9 mL. / Min and column temperature of 40 ° C.
  • Mw was made into the polystyrene conversion value.
  • Example 2 PDA 0.246 g (0.0023 mol) and FDA 0.528 g (0.0015 mol) were dissolved in 17.8 g of NMP, BP-TME 1.01 g (0.0019 mol) and PMDA 0.413 g (0. 0019 mol) was added, followed by reaction at 23 ° C. for 24 hours under a nitrogen atmosphere. Mw of the obtained polymer was 88,600 and molecular weight distribution was 3.1. This solution was used as a resin composition for display substrates.
  • Comparative Example 1 has high rigidity, the film is brittle, the film is cracked and torn when peeled from the glass substrate, and the peeled film is also easily broken, so the film strength is insufficient as a display substrate. there were.
  • the film produced using the resin composition for display substrates obtained from Examples 1 to 6 is not easily cracked or broken when peeled from the glass substrate, and the peeled film is also cracked. It was difficult to form a film having a sufficiently high film strength and a uniform self-supporting thickness of 11 ⁇ m to 15 ⁇ m.
  • the linear expansion coefficient was measured by raising the temperature from 50 ° C. to 400 ° C. under the condition of 10 ° C./min.
  • the linear expansion coefficient is indicated by a coefficient on the low temperature (50 ° C. to 250 ° C.) side and on the high temperature (250 ° C. to 400 ° C.) side. The results are shown in Table 3.

Abstract

[Problem] To provide a resin composition for display substrates that is capable of forming a useful polyimide film having high heat resistance, a moderate coefficient of linear expansion, and moderate flexibility. [Solution] This resin composition for display substrates comprises a polyamic acid including a structural unit represented by formula (1) and a structural unit represented by formula (3), or a polyimide including a structural unit represented by formula (2) and a structural unit represented by formula (4). (In formulae (1) to (4): X1 represents a tetravalent organic group having an aromatic group and two carbonyl groups; Y1 represents a divalent aromatic group or aliphatic group; Y2 represents a divalent aromatic group having a fluorene skeleton; and n and m each represent a natural number.)

Description

ポリアミック酸およびポリイミドPolyamic acid and polyimide
　本発明はディスプレイ基板用樹脂組成物に関し、詳細には適度な線膨張係数、適度な柔軟性を有する有用なポリイミドフィルムを形成することができるディスプレイ基板用樹脂組成物に関する。 The present invention relates to a resin composition for a display substrate, and more particularly to a resin composition for a display substrate capable of forming a useful polyimide film having an appropriate linear expansion coefficient and an appropriate flexibility.
　ポリイミド樹脂は、耐熱性が高く難燃性で電気絶縁性に優れていることから、電気・電子材料分野において幅広く使用されている。具体的には、フィルムとしてフレキシブル印刷配線版や耐熱性接着テープの基材、樹脂ワニスとして半導体の絶縁皮膜、保護皮膜などに使用されている。
　一方、有機ＥＬ（Ｅｌｅｃｔｒｏｌｕｍｉｎｅｓｃｅｎｃｅ）ディスプレイや液晶ディスプレイなどの表示装置は、高精細のみが要求されてきたが、情報機器などへ急速にその用途を拡大している。例えば、超薄型・軽量化の要求を満たすために、プラスチックフィルムを基板として使用するフレキシブルディスプレイが注目されている。
　従来、高精細なディスプレイには、アクティブマトリックス駆動のパネルが使用されている。マトリックス状の画素電極に加えて、薄膜アクティブ素子を含むアクティブマトリックス層を形成するには、その製造プロセスにおいて２００℃以上の高温処理を必要とし、しかも、きわめて正確な位置合わせが必要である。しかし、フレキシブル化のために、ガラス基板からプラスチック材料に変化することで、耐熱性、寸法安定性に劣るため、その上にアクティブ素子をじかに形成するのは非常に困難であった。 Polyimide resins are widely used in the field of electrical and electronic materials because of their high heat resistance, flame retardancy, and excellent electrical insulation. Specifically, it is used as a film for flexible printed wiring boards and heat-resistant adhesive tapes as a film, and as a resin varnish for semiconductor insulating films, protective films, and the like.
On the other hand, display devices such as an organic EL (Electroluminescence) display and a liquid crystal display have been demanded only for high definition, but their applications are rapidly expanding to information devices and the like. For example, a flexible display using a plastic film as a substrate is attracting attention in order to satisfy the demand for ultra-thin and light weight.
Conventionally, an active matrix driving panel is used for a high-definition display. In order to form an active matrix layer including a thin film active element in addition to a matrix-like pixel electrode, a high temperature treatment of 200 ° C. or higher is required in the manufacturing process, and extremely accurate alignment is required. However, since it is inferior in heat resistance and dimensional stability by changing from a glass substrate to a plastic material for flexibility, it is very difficult to directly form an active element thereon.
　そこで、斯かる問題を回避するために、ガラス基板上にポリイミドフィルムを形成し、製造条件が制限されず、アモルファスシリコンＴＦＴ素子やカラーフィルタなどを高精細で位置合わせて形成して転写層とした後、その転写層をプラスチックフィルム上に転写・形成することにより、表示素子を製造する方法が提案されている（特許文献１及び２）。
　ところで、前記工程で必要とされるポリイミドの特性として、線膨張係数が挙げられる。しかし、多くのポリイミド系ではフィルムの線膨張係数は６０乃至８０ｐｐｍ／Ｋの範囲であり、低線膨張特性を有していない。このような中、線膨張係数が低いポリイミドフィルムが開発されているが、汎用性に乏しい酸二無水物を原料に用いているため、得られる製品が高価になってしまう（特許文献３）。 Therefore, in order to avoid such a problem, a polyimide film is formed on a glass substrate, the manufacturing conditions are not limited, and an amorphous silicon TFT element, a color filter, etc. are formed with high-definition alignment to form a transfer layer. Thereafter, a method of manufacturing a display element by transferring and forming the transfer layer on a plastic film has been proposed (Patent Documents 1 and 2).
By the way, a linear expansion coefficient is mentioned as a characteristic of the polyimide required at the said process. However, in many polyimide systems, the linear expansion coefficient of the film is in the range of 60 to 80 ppm / K and does not have low linear expansion characteristics. Under such circumstances, a polyimide film having a low linear expansion coefficient has been developed. However, since an acid dianhydride having poor versatility is used as a raw material, the resulting product becomes expensive (Patent Document 3).
特開２００１－３５６３７０号公報JP 2001-356370 A 特表２０１０－５３９２９３号公報Special table 2010-539293 国際公開第２００８／０４７５９１号パンフレットInternational Publication No. 2008/047591 Pamphlet
　本発明は、このような事情に鑑みてなされたものであり、汎用性に乏しい酸二無水物を原料に用いなくても、製造プロセスに耐えうる耐熱性を有し、適度な線膨張係数及び適度な柔軟性を有する有用な硬化膜を形成することができるディスプレイ基板用樹脂組成物の提供を目的とする。なお、ここでいう適度な柔軟性とは、自己支持性があり、かつ９０度に曲げても割れない程度の高い柔軟性をいう。 The present invention has been made in view of such circumstances, and has heat resistance that can withstand the manufacturing process without using acid dianhydride having poor versatility as a raw material, and has an appropriate linear expansion coefficient and It aims at providing the resin composition for display substrates which can form the useful cured film which has moderate softness | flexibility. In addition, moderate softness | flexibility here means self-supporting property and the high softness | flexibility of the grade which is not cracked even if it bends 90 degree | times.
　本発明者は、上記目的を達成するために鋭意検討を重ねた結果、酸二無水物成分としてビフェニル骨格を有する酸無水物とピロメリット酸無水物、ジアミン成分としてフルオレン骨格を有するジアミンとを組み合わせて用いることにより、該酸二無水物成分と該ジアミン成分から誘導されるポリアミック酸又はポリイミドを含むディスプレイ基板用樹脂組成物から、高い耐熱性、適度な線膨張係数及び適度な柔軟性を有する有用な硬化膜が得られることを見出し、本発明を完成させた。 As a result of intensive studies to achieve the above object, the present inventor combined an acid anhydride having a biphenyl skeleton as an acid dianhydride component with pyromellitic anhydride and a diamine having a fluorene skeleton as a diamine component. It is useful to have high heat resistance, moderate linear expansion coefficient, and moderate flexibility from the resin composition for display substrates containing the polyamic acid or polyimide derived from the acid dianhydride component and the diamine component. The present invention was completed by finding that a cured film can be obtained.
　すなわち、本発明は、第１観点として、下記式（１）で表される構造単位及び式（３）で表される構造単位を含むポリアミック酸又は下記式（２）で表される構造単位及び式（４）で表される構造単位を含むポリイミドを含有するディスプレイ基板用樹脂組成物に関する。
Figure JPOXMLDOC01-appb-C000012
 ［式（１）乃至式（４）中、
　Ｘ１は芳香族基と２つ以上のカルボニル基を有する４価の有機基を表し、
　Ｙ１は２価の芳香族基又は脂肪族基を表し、
　Ｙ２はフルオレン骨格を有する２価の芳香族基を表し、
　ｎ及びｍは自然数を表す。］
　第２観点として、前記Ｙ２が下記式（５）で表される基を表す、第１観点に記載のディスプレイ基板用樹脂組成物に関する。
Figure JPOXMLDOC01-appb-C000013
 （式中、
　Ｒ０乃至Ｒ７は、それぞれ独立して、水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基、カルボキシル基、Ｗ１で置換されていてもよいフェニル基、Ｗ１で置換されていてもよいナフチル基、Ｗ１で置換されていてもよいチエニル基又はＷ１で置換されていてもよいフリル基を表し、
　Ｗ１は、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基又はカルボキシル基を表す。なお、○は結合手を表す。）
　第３観点として、前記Ｙ２が下記式（５ａ）で表される第２観点に記載のディスプレイ基板用樹脂組成物に関する。
Figure JPOXMLDOC01-appb-C000014
 （式中、○は結合手を表す。）
　第４観点として、前記Ｙ１が下記式（６）で表される、第１観点乃至第３観点のうちいずれか１つに記載のディスプレイ基板用樹脂組成物に関する。
Figure JPOXMLDOC01-appb-C000015
 （式中、
　Ｒ８乃至Ｒ１１は、それぞれ独立して、水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基、カルボキシル基、Ｗ１で置換されていてもよいフェニル基、Ｗ１で置換されていてもよいナフチル基、Ｗ１で置換されていてもよいチエニル基又はＷ１で置換されていてもよいフリル基を表し、
　Ｗ１は、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基又はカルボキシル基を表し、
　ｑは１又は２の整数を表す。なお、○は結合手を表す。）
　第５観点として、前記式（６）で表される２価の芳香族基がフェニレンジアミンから誘導されたものである、第３観点に記載のディスプレイ基板用樹脂組成物に関する。
　第６観点として、前記Ｒ８乃至Ｒ１１が水素原子を表す、第５観点に記載のディスプレイ基板用樹脂組成物に関する。
　第７観点として、前記Ｘ１は下記式（７）で表される基、式（８）で表される基又はこれら双方の基を表す、第１観点乃至第６観点のうちいずれか１項に記載のディスプレイ基板用樹脂組成物に関する。
Figure JPOXMLDOC01-appb-C000016
 （式（７）及び式（８）中、
　Ｒ1２乃至Ｒ２３は、それぞれ独立して、水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基、カルボキシル基、Ｗ１で置換されていてもよいフェニル基、Ｗ１で置換されていてもよいナフチル基、Ｗ１で置換されていてもよいチエニル基又はＷ１で置換されていてもよいフリル基を表し、
　Ｗ１は、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基又はカルボキシル基を表し、
　Ｚ1及びＺ２は、それぞれ独立して、－ＮＨ－、－ＮＺ３－又は酸素原子を表し、
　Ｚ３は、炭素原子数１乃至１０のアルキル基を表し、
　ｐは１又は２の整数を表す。なお、○は結合手を表す。）
　第８観点として、前記ｐが２の整数を表す、第７観点に記載のディスプレイ基板用樹脂組成物に関する。
　第９観点として、前記Ｒ1２乃至Ｒ２３が水素原子を表す、第８観点に記載のディスプレイ基板用樹脂組成物に関する。
　第１０観点として、前記ポリアミック酸が更に式（９）で表される構造単位を含む、第１観点乃至第９観点のいずれか１つに記載のディスプレイ基板用樹脂組成物に関する。
Figure JPOXMLDOC01-appb-C000017
 ［式（９）中、
　Ｘ１は芳香族基と２つ以上のカルボニル基を有する４価の有機基を表し、
　Ｙ３はエーテル結合を有する２価の基を表し、
　ｌは自然数を表す。］
　第１１観点として、前記ポリイミドが更に式（１０）で表される構造単位を含む、第１観点乃至第９観点のいずれか１つに記載のディスプレイ基板用樹脂組成物に関する。
Figure JPOXMLDOC01-appb-C000018
 ［式（１０）中、
　Ｘ１は芳香族基と２つ以上のカルボニル基を有する４価の有機基を表し、
　Ｙ３はエーテル結合を有する２価の基を表し、
　ｌは自然数を表す。］
　第１２観点として、前記式（１）中のｎと前記式（３）中のｍとがｎ／（ｎ＋ｍ）≧６０％の関係である、第１観点乃至第１１観点のいずれか１つに記載のディスプレイ基板用樹脂組成物に関する。
　第１３観点として、前記式（２）中のｎと前記式（４）中のｍとがｎ／（ｎ＋ｍ）≧６０％の関係である、第１観点乃至第１１観点のいずれか１つに記載のディスプレイ基板用樹脂組成物に関する。
　第１４観点として、さらに架橋剤を含む、第１観点乃至第１３観点のいずれか１つに記載のディスプレイ基板用樹脂組成物に関する。
　第１５観点として、前記架橋剤が２つ以上のエポキシ基を有する化合物である、第１４観点に記載のディスプレイ基板用樹脂組成物に関する。
　第１６観点として、前記架橋剤が芳香族基を有する化合物である、第１５観点に記載のディスプレイ基板用樹脂組成物に関する。
　第１７観点として、前記架橋剤が６つ以下のエポキシ基を有する化合物であって、かつ該化合物はエポキシ基と芳香族基とを結合する炭素原子数１乃至１０のアルキル基を有する、第１６観点に記載のディスプレイ基板用樹脂組成物に関する。
　第１８観点として、前記ポリアミック酸又はポリイミド１００質量部に対して、前記架橋剤が２０質量部以下である、第１４観点乃至第１７観点のうちいずれか１つに記載のディスプレイ基板用樹脂組成物に関する。
　第１９観点として、第１観点乃至第１８観点のいずれか１つに記載のディスプレイ基板用樹脂組成物が少なくとも１種の溶剤に溶解していることを特徴とする、ワニスに関する。
　第２０観点として、第１９観点に記載のワニスを用いて２３０℃以上で焼成することにより得られる、硬化膜に関する。
　第２１観点として、基板上に第２０観点に記載の硬化膜からなる層を少なくとも一層備える、構造体に関する。
　第２２観点として、下記式（１）で表される構造単位及び式（３）で表される構造単位を含むポリアミック酸に関する。
Figure JPOXMLDOC01-appb-C000019
 ［式（１）及び式（３）中、
　Ｘ１は芳香族基と２つ以上のカルボニル基を有する４価の有機基を表し、
　Ｙ１は２価の芳香族基又は脂肪族基を表し、
　Ｙ２はフルオレン骨格を有する２価の芳香族基を表し、
　ｎ及びｍは自然数を表す。］
　第２３観点として、更に式（９）で表される構造単位を含む第２２観点に記載のポリアミック酸に関する。
Figure JPOXMLDOC01-appb-C000020
 ［式（９）中、
　Ｘ１は芳香族基と２つ以上のカルボニル基を有する４価の有機基を表し、
　Ｙ３はエーテル結合を有する２価の基を表し、
　ｌは自然数を表す。］
　第２４観点として、下記式（２）で表される構造単位及び式（４）で表される構造単位を含むポリイミドに関する。
Figure JPOXMLDOC01-appb-C000021
 ［式（２）及び式（４）中、
　Ｘ１は芳香族基と２つ以上のカルボニル基を有する４価の有機基を表し、
　Ｙ１は２価の芳香族基又は脂肪族基を表し、
　Ｙ２はフルオレン骨格を有する２価の芳香族基を表し、
　ｎ及びｍは自然数を表す。］
　第２５観点として、更に式（１０）で表される構造単位を含む第２４観点に記載のポリイミドに関する。
Figure JPOXMLDOC01-appb-C000022
 ［式（１０）中、
　Ｘ１は芳香族基と２つ以上のカルボニル基を有する４価の有機基を表し、
　Ｙ３はエーテル結合を有する２価の基を表し、
　ｌは自然数を表す。］
　第２６観点として、第２２観点又は第２３観点に記載のポリアミック酸と架橋剤とを含む組成物に関する。
　第２７観点として、第２４観点又は第２５観点に記載のポリイミドと架橋剤とを含む組成物に関する。
　第２８観点として、第２６観点又は第２７観点に記載の組成物が少なくとも１種の溶剤に溶解していることを特徴とする、ワニスに関する。
　第２９観点として、第２８観点に記載のワニスを用いて２３０℃以上で焼成することにより得られる、硬化膜に関する。 That is, as a first aspect, the present invention provides a polyamic acid containing a structural unit represented by the following formula (1) and a structural unit represented by the formula (3), or a structural unit represented by the following formula (2) and It is related with the resin composition for display substrates containing the polyimide containing the structural unit represented by Formula (4).
Figure JPOXMLDOC01-appb-C000012
 [In Formula (1) thru | or Formula (4),
X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups,
Y 1 represents a divalent aromatic group or aliphatic group,
Y 2 represents a divalent aromatic group having a fluorene skeleton,
n and m represent natural numbers. ]
As a second aspect, it represents a group wherein Y 2 is represented by the following formula (5) relates to a display substrate resin composition according to the first aspect.
Figure JPOXMLDOC01-appb-C000013
 (Where
R 0 to R 7 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom. , nitro group, formyl group, cyano group, carboxyl group, W 1 with an optionally substituted phenyl group, W 1 with an optionally substituted naphthyl group, W 1 with an optionally substituted thienyl group or W Represents a furyl group optionally substituted by 1 ,
W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group. Represents a group. In addition, (circle) represents a bond. )
As a third aspect, the Y 2 is to a display substrate for resin composition according to the second aspect represented by the following formula (5a).
Figure JPOXMLDOC01-appb-C000014
 (In the formula, ○ represents a bond.)
As a fourth aspect, regarding the Y 1 is represented by the following formula (6), a display substrate resin composition according to any one of the first aspect to the third aspect.
Figure JPOXMLDOC01-appb-C000015
 (Where
R 8 to R 11 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom. , nitro group, formyl group, cyano group, carboxyl group, W 1 with an optionally substituted phenyl group, W 1 with an optionally substituted naphthyl group, W 1 with an optionally substituted thienyl group or W Represents a furyl group optionally substituted by 1 ,
W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group. Represents a group,
q represents an integer of 1 or 2. In addition, (circle) represents a bond. )
As a fifth aspect, the present invention relates to the display substrate resin composition according to the third aspect, in which the divalent aromatic group represented by the formula (6) is derived from phenylenediamine.
As a sixth aspect, the present invention relates to the resin composition for display substrates according to the fifth aspect, in which R 8 to R 11 represent hydrogen atoms.
As a seventh aspect, the X 1 represents a group represented by the following formula (7), a group represented by the formula (8), or both groups, and any one of the first to sixth aspects. It relates to the resin composition for display substrates as described in above.
Figure JPOXMLDOC01-appb-C000016
 (In Formula (7) and Formula (8),
R 12 to R 23 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, hydroxy group, a halogen atom , nitro group, formyl group, cyano group, carboxyl group, W 1 with an optionally substituted phenyl group, W 1 with an optionally substituted naphthyl group, W 1 with an optionally substituted thienyl group or W Represents a furyl group optionally substituted by 1 ,
W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group. Represents a group,
Z 1 and Z 2 each independently represent —NH—, —NZ 3 — or an oxygen atom,
Z 3 represents an alkyl group having 1 to 10 carbon atoms,
p represents an integer of 1 or 2. In addition, (circle) represents a bond. )
As an eighth aspect, the present invention relates to the resin composition for display substrates according to the seventh aspect, wherein p represents an integer of 2.
As a ninth aspect, the present invention relates to the resin composition for a display substrate according to the eighth aspect, in which R 12 to R 23 represent a hydrogen atom.
As a tenth aspect, the present invention relates to the resin composition for a display substrate according to any one of the first aspect to the ninth aspect, wherein the polyamic acid further includes a structural unit represented by the formula (9).
Figure JPOXMLDOC01-appb-C000017
 [In Formula (9),
X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups,
Y 3 represents a divalent group having an ether bond,
l represents a natural number. ]
As an 11th viewpoint, it is related with the resin composition for display substrates as described in any one of the 1st viewpoint thru | or a 9th viewpoint in which the said polyimide further contains the structural unit represented by Formula (10).
Figure JPOXMLDOC01-appb-C000018
 [In the formula (10),
X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups,
Y 3 represents a divalent group having an ether bond,
l represents a natural number. ]
As a twelfth aspect, in any one of the first aspect to the eleventh aspect, n in the formula (1) and m in the formula (3) have a relationship of n / (n + m) ≧ 60%. It is related with the resin composition for display substrates of description.
As a thirteenth aspect, in any one of the first to eleventh aspects, n in the formula (2) and m in the formula (4) have a relationship of n / (n + m) ≧ 60%. It is related with the resin composition for display substrates of description.
As a 14th viewpoint, it is related with the resin composition for display substrates as described in any one of the 1st viewpoint thru | or a 13th viewpoint containing a crosslinking agent further.
As a fifteenth aspect, the present invention relates to the resin composition for display substrates according to the fourteenth aspect, in which the crosslinking agent is a compound having two or more epoxy groups.
As a sixteenth aspect, the present invention relates to the display substrate resin composition according to the fifteenth aspect, in which the crosslinking agent is a compound having an aromatic group.
According to a seventeenth aspect, in the sixteenth aspect, the crosslinking agent has a compound having 6 or less epoxy groups, and the compound has an alkyl group having 1 to 10 carbon atoms that bonds the epoxy group and the aromatic group. It is related with the resin composition for display substrates as described in a viewpoint.
As a 18th aspect, the resin composition for a display substrate according to any one of the 14th aspect to the 17th aspect, wherein the crosslinking agent is 20 parts by mass or less with respect to 100 parts by mass of the polyamic acid or polyimide. About.
According to a nineteenth aspect, the present invention relates to a varnish, wherein the display substrate resin composition according to any one of the first to eighteenth aspects is dissolved in at least one solvent.
As a 20th viewpoint, it is related with the cured film obtained by baking at 230 degreeC or more using the varnish as described in a 19th viewpoint.
As a 21st viewpoint, it is related with a structure provided with at least one layer which consists of a cured film as described in a 20th viewpoint on a board | substrate.
As a 22nd viewpoint, it is related with the polyamic acid containing the structural unit represented by the structural unit represented by following formula (1), and Formula (3).
Figure JPOXMLDOC01-appb-C000019
 [In Formula (1) and Formula (3),
X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups,
Y 1 represents a divalent aromatic group or aliphatic group,
Y 2 represents a divalent aromatic group having a fluorene skeleton,
n and m represent natural numbers. ]
As a 23rd viewpoint, it is related with the polyamic acid as described in a 22nd viewpoint further including the structural unit represented by Formula (9).
Figure JPOXMLDOC01-appb-C000020
 [In Formula (9),
X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups,
Y 3 represents a divalent group having an ether bond,
l represents a natural number. ]
As a 24th viewpoint, it is related with the polyimide containing the structural unit represented by following structural formula (2), and the structural unit represented by Formula (4).
Figure JPOXMLDOC01-appb-C000021
 [In Formula (2) and Formula (4),
X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups,
Y 1 represents a divalent aromatic group or aliphatic group,
Y 2 represents a divalent aromatic group having a fluorene skeleton,
n and m represent natural numbers. ]
As a twenty-fifth aspect, the present invention relates to the polyimide according to the twenty-fourth aspect, which further includes a structural unit represented by the formula (10).
Figure JPOXMLDOC01-appb-C000022
 [In the formula (10),
X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups,
Y 3 represents a divalent group having an ether bond,
l represents a natural number. ]
As a 26th viewpoint, it is related with the composition containing the polyamic acid as described in a 22nd viewpoint or a 23rd viewpoint, and a crosslinking agent.
As a 27th viewpoint, it is related with the composition containing the polyimide and crosslinking agent as described in a 24th viewpoint or a 25th viewpoint.
As a twenty-eighth aspect, the present invention relates to a varnish characterized in that the composition according to the twenty-sixth aspect or the twenty-seventh aspect is dissolved in at least one solvent.
As a 29th viewpoint, it is related with the cured film obtained by baking at 230 degreeC or more using the varnish as described in a 28th viewpoint.
　本発明のディスプレイ基板用樹脂組成物は、ポリアミック酸又はポリイミドが、芳香族基と２つ以上のカルボニル基を有する酸二無水物とフルオレン骨格を含む芳香族ジアミンから誘導される特定の構造を含むことにより、高い耐熱性、適度な線膨張係数及び適度な柔軟性を有する有用な硬化膜を形成することができる。したがって、該硬化膜は、フレキシブルディスプレイ用ベースフィルム等に使用することができる。 The resin composition for display substrates of the present invention includes a specific structure in which the polyamic acid or polyimide is derived from an aromatic diamine containing an dianhydride having an aromatic group and two or more carbonyl groups and a fluorene skeleton. Thus, a useful cured film having high heat resistance, an appropriate linear expansion coefficient, and an appropriate flexibility can be formed. Therefore, the cured film can be used as a base film for flexible displays.
［ディスプレイ基板用樹脂組成物］
　本発明は、下記式（１）で表される構造単位及び式（３）で表される構造単位を含むポリアミック酸又は下記式（２）で表される構造単位及び式（４）で表される構造単位を含むポリイミドを含有するディスプレイ基板用樹脂組成物に関する。
Figure JPOXMLDOC01-appb-C000023
 ［式（１）乃至式（４）中、
　Ｘ１は芳香族基と２つのカルボニル基を有する４価の有機基を表し、
　Ｙ１は２価の芳香族基又は脂肪族基を表し、
　Ｙ２はフルオレン骨格を有する２価の芳香族基を表し、
　ｎ及びｍは自然数を表す。］ [Resin composition for display substrate]
The present invention is represented by a polyamic acid containing a structural unit represented by the following formula (1) and a structural unit represented by the formula (3), or a structural unit represented by the following formula (2) and the formula (4). The present invention relates to a resin composition for a display substrate containing polyimide containing a structural unit.
Figure JPOXMLDOC01-appb-C000023
 [In Formula (1) thru | or Formula (4),
X 1 represents a tetravalent organic group having an aromatic group and two carbonyl groups,
Y 1 represents a divalent aromatic group or aliphatic group,
Y 2 represents a divalent aromatic group having a fluorene skeleton,
n and m represent natural numbers. ]
　本発明のディスプレイ基板用樹脂組成物における固形分の割合は、１乃至１００質量％、又は５乃至１００質量％、又は５０乃至１００質量％、又は８０乃至１００質量％である。
　ここで、固形分とはディスプレイ基板用樹脂組成物の全成分から溶剤を除去した残りの成分である。
　本発明のディスプレイ基板用樹脂組成物における上記ポリアミック酸又はポリイミドの含有量は、該樹脂組成物の固形分の含有量に基づいて、８乃至９９．９質量％、好ましくは４０乃至９９質量％、更に好ましくは７０乃至９９質量％である。 The ratio of the solid content in the resin composition for display substrates of the present invention is 1 to 100% by mass, or 5 to 100% by mass, or 50 to 100% by mass, or 80 to 100% by mass.
Here, solid content is the remaining component which removed the solvent from all the components of the resin composition for display substrates.
The content of the polyamic acid or polyimide in the resin composition for display substrates of the present invention is 8 to 99.9 mass%, preferably 40 to 99 mass%, based on the solid content of the resin composition. More preferably, it is 70 to 99% by mass.
　本発明のディスプレイ基板用樹脂組成物は、ポリアミック酸又はポリイミドを含む。 The resin composition for display substrate of the present invention contains polyamic acid or polyimide.
＜ポリアミック酸＞
　本発明のディスプレイ基板用樹脂組成物に含まれるポリアミック酸は、酸無水物成分とジアミン成分とを溶剤中で重合させることで得られる。
　ポリアミック酸は、公知の方法、例えば、窒素などの不活性ガス雰囲気中において、下記式（１１）：
Figure JPOXMLDOC01-appb-C000024
 （式中、Ｘ１は芳香族基と２つ以上のカルボニル基を有する４価の有機基を表す。）で表される少なくとも１種の酸二無水物と、下記式（１２）：
　　　Ｈ２Ｎ－Ｙ１－ＮＨ２　　　　　　（１２）
（式中、Ｙ１は２価の芳香族基又は脂肪族基を表す。）で表される少なくとも１種のジアミンと、下記式（１３）：
　　　Ｈ２Ｎ－Ｙ２－ＮＨ２　　　　　　（１３）
（式中、Ｙ２はフルオレン骨格を有する２価の芳香族基を表す。）で表される少なくとも１種のジアミンとを溶剤に溶解し、反応させることで得られる。 <Polyamic acid>
The polyamic acid contained in the display substrate resin composition of the present invention is obtained by polymerizing an acid anhydride component and a diamine component in a solvent.
The polyamic acid is represented by the following formula (11) in a known method, for example, in an inert gas atmosphere such as nitrogen:
Figure JPOXMLDOC01-appb-C000024
 (Wherein X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups), and the following formula (12):
H 2 N—Y 1 —NH 2 (12)
(Wherein Y 1 represents a divalent aromatic group or aliphatic group) and at least one diamine represented by the following formula (13):
H 2 N—Y 2 —NH 2 (13)
(Wherein, Y 2 is represented. The divalent aromatic group having a fluorene skeleton) and at least one diamine represented by dissolving in a solvent, is obtained by reacting.
　この時の反応温度は、－２０乃至１００℃、好ましくは２０乃至６０℃である。反応時間は、１乃至７２時間である。 The reaction temperature at this time is −20 to 100 ° C., preferably 20 to 60 ° C. The reaction time is 1 to 72 hours.
　本発明では、ポリアミック酸の反応溶液をそのまま、又は、希釈して使用することができ、或いは反応溶液から沈殿回収したポリアミック酸を適当な溶剤に再溶解させて使用することができる。希釈及び再溶解に用いる溶剤は、得られたポリアミック酸を溶解させるものであれば特に限定されないが、例えば、２－ピロリドン、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン、Ｎ－ビニル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、３－メトキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－エトキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－プロポキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－イソプロポキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－ｓｅｃ－ブトキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－ｔｅｒｔ－ブトキシ－Ｎ，Ｎ－ジメチルプロピルアミド、γ－ブチロラクトン等を挙げることができる。これらの溶剤は、単独で又は２種以上を組み合わせて使用してもよい。 In the present invention, the polyamic acid reaction solution can be used as it is or after dilution, or the polyamic acid precipitated and recovered from the reaction solution can be used by re-dissolving in a suitable solvent. The solvent used for the dilution and re-dissolution is not particularly limited as long as it can dissolve the obtained polyamic acid. For example, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N- Vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropylamide, 3-propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethylpropylamide, 3-tert-butoxy -N, N-dimethylpropylamide, γ-butyrolactone and the like can be mentioned. These solvents may be used alone or in combination of two or more.
　前記式（１１）で表される酸二無水物としては、Ｘ１が下記式（７）で表される酸二無水物及びＸ１が下記式（８）で表される酸二無水物が好ましく、これらの酸二無水物を併用しても良い。
Figure JPOXMLDOC01-appb-C000025
 （式（７）及び式（８）中、
　Ｒ1２乃至Ｒ２３は、それぞれ独立して、水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基、カルボキシル基、Ｗ１で置換されていてもよいフェニル基、Ｗ１で置換されていてもよいナフチル基、Ｗ１で置換されていてもよいチエニル基又はＷ１で置換されていてもよいフリル基を表し、
　Ｗ１は、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基又はカルボキシル基を表し、
　Ｚ1及びＺ２は、それぞれ独立して、－ＮＨ－、－ＮＺ３－又は酸素原子を表し、
　Ｚ３は、炭素原子数１乃至１０のアルキル基を表し、
　ｐは１又は２の整数を表す。なお、○は結合手を表す。式（８）はピロメリット酸無水物から誘導された基を表す。） As the acid dianhydride represented by the formula (11), an acid dianhydride and X 1 where X 1 is represented by the following formula (7) is an acid dianhydride represented by the following formula (8) Preferably, these acid dianhydrides may be used in combination.
Figure JPOXMLDOC01-appb-C000025
 (In Formula (7) and Formula (8),
R 12 to R 23 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom. , nitro group, formyl group, cyano group, carboxyl group, W 1 with an optionally substituted phenyl group, W 1 with an optionally substituted naphthyl group, W 1 with an optionally substituted thienyl group or W Represents a furyl group optionally substituted by 1 ,
W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group. Represents a group,
Z 1 and Z 2 each independently represent —NH—, —NZ 3 — or an oxygen atom,
Z 3 represents an alkyl group having 1 to 10 carbon atoms,
p represents an integer of 1 or 2. In addition, (circle) represents a bond. Formula (8) represents a group derived from pyromellitic anhydride. )
　前記式（７）において、前記ｐが２の整数であることが好ましい。 In the formula (7), it is preferable that the p is an integer of 2.
　このようなＸ１が式（７）で表される酸二無水物としては、例えば、ｐ－フェニレンビス（トリメリット酸モノエステル無水物）、２－メチル－１，４－フェニレンビス（トリメリット酸モノエステル無水物）、２，５－ジメチル－１，４－フェニレンビス（トリメリット酸モノエステル無水物）、２，３，５，６－テトラメチル－１，４－フェニレンビス（トリメリット酸モノエステル無水物）、２－トリフルオロメチル－１，４－フェニレンビス（トリメリット酸モノエステル無水物）、２，５－ジトリフルオロメチル－１，４－フェニレンビス（トリメリット酸モノエステル無水物）、２－クロロ－１，４－フェニレンビス（トリメリット酸モノエステル無水物）、２，５－ジクロロ－１，４－フェニレンビス（トリメリット酸モノエステル無水物）、２－フルオロ－１，４－フェニレンビス（トリメリット酸モノエステル無水物）及び２，５－ジフルオロ－１，４－フェニレンビス（トリメリット酸モノエステル無水物）、並びにＮ，Ｎ’－（１，４－フェニレン）ビス（１，３－ジオキソ－１，３－ジヒドロベンゾフラン－５－カルボキシアミド）及びＮ，Ｎ’－（１，４－フェニレン）ビス（Ｎ－メチル－１，３－ジオキソ－１，３－ジヒドロベンゾフラン－５－カルボキシアミド）等が挙げられる。
　前記酸二無水物の中でも、本発明の樹脂組成物から得られる硬化膜が十分に低い線膨張係数及び十分に高い強度を有するものとする観点から、前記式（７）中のＲ１２乃至Ｒ２１が水素原子を表し、Ｚ１及びＺ２が酸素原子を表し、かつｍが２の整数を表す化合物である、４，４－ビフェニルビス（トリメリット酸モノエステル酸無水物）（下記式（１５））が好ましい。
Figure JPOXMLDOC01-appb-C000026
 　また、Ｘ１が式（８）で表される酸二無水物としては、ピロメリット酸二無水物、３－フルオロピロメリット酸二無水物、３－クロロピロメリット酸二無水物、３－ブロモピロメリット酸二無水物、３－ヒドロキシピロメリット酸二無水物、３－メチルピロメリット酸二無水物、３－トリフルオロメチルピロメリット酸二無水物、３－トリクロロメチルピロメリット酸二無水物、３－トリブロモメチルピロメリット酸二無水物、３，６－ジフルオロピロメリット酸二無水物、３，６－ジクロロピロメリット酸二無水物、３，６－ジブロモピロメリット酸二無水物、３，６－ジヒドロキシピロメリット酸二無水物、３，６－ジメチルピロメリット酸二無水物、３，６－ビストリフルオロメチルピロメリット酸二無水物、３，６－ビストリクロロメチルピロメリット酸二無水物、３，６－ビストリブロモメチルピロメリット酸二無水物等が挙げられ、特にピロメリット酸無水物が好ましい。 Examples of such acid dianhydrides in which X 1 is represented by the formula (7) include p-phenylenebis (trimellitic acid monoester anhydride), 2-methyl-1,4-phenylenebis (trimellitic). Acid monoester anhydride), 2,5-dimethyl-1,4-phenylenebis (trimellitic acid monoester anhydride), 2,3,5,6-tetramethyl-1,4-phenylenebis (trimellitic acid) Monoester anhydride), 2-trifluoromethyl-1,4-phenylenebis (trimellitic acid monoester anhydride), 2,5-ditrifluoromethyl-1,4-phenylenebis (trimellitic acid monoester anhydride) ), 2-chloro-1,4-phenylenebis (trimellitic acid monoester anhydride), 2,5-dichloro-1,4-phenylenebis (trimellitic acid monoe) Steal anhydride), 2-fluoro-1,4-phenylenebis (trimellitic acid monoester anhydride) and 2,5-difluoro-1,4-phenylenebis (trimellitic acid monoester anhydride), and N, N ′-(1,4-phenylene) bis (1,3-dioxo-1,3-dihydrobenzofuran-5-carboxamide) and N, N ′-(1,4-phenylene) bis (N-methyl-1) , 3-dioxo-1,3-dihydrobenzofuran-5-carboxamide) and the like.
Among the acid dianhydrides, R 12 to R in the formula (7) from the viewpoint that the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient and a sufficiently high strength. 4,4-biphenylbis (trimellitic acid monoester acid anhydride) (a compound represented by the following formula ( 21) , wherein 21 represents a hydrogen atom, Z 1 and Z 2 represent an oxygen atom, and m represents an integer of 2. 15)) is preferred.
Figure JPOXMLDOC01-appb-C000026
 Examples of the acid dianhydride in which X 1 is represented by the formula (8) include pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3-chloropyromellitic dianhydride, 3-bromo Pyromellitic dianhydride, 3-hydroxypyromellitic dianhydride, 3-methylpyromellitic dianhydride, 3-trifluoromethylpyromellitic dianhydride, 3-trichloromethylpyromellitic dianhydride, 3-tribromomethylpyromellitic dianhydride, 3,6-difluoropyromellitic dianhydride, 3,6-dichloropyromellitic dianhydride, 3,6-dibromopyromellitic dianhydride, 3, 6-dihydroxypyromellitic dianhydride, 3,6-dimethylpyromellitic dianhydride, 3,6-bistrifluoromethylpyromellitic dianhydride, 3,6-bistrichloro Examples thereof include methyl pyromellitic dianhydride and 3,6-bistribromomethyl pyromellitic dianhydride, and pyromellitic anhydride is particularly preferable.
　前記式（１２）で表わされる芳香族ジアミンは、本発明の樹脂組成物から得られる硬化膜が十分に低い線膨張係数を有するものとする観点から、剛直で直線的な分子構造を有するジアミンを使用することが好ましい。なかでも前記式（１２）で表されるジアミンとしては、Ｙ１が下記式（６）で表される構造であるジアミンが特に好ましい。
Figure JPOXMLDOC01-appb-C000027
 （式中、
　Ｒ８乃至Ｒ１１は、それぞれ独立して、水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基、カルボキシル基、Ｗ１で置換されていてもよいフェニル基、Ｗ１で置換されていてもよいナフチル基、Ｗ１で置換されていてもよいチエニル基又はＷ１で置換されていてもよいフリル基を表し、
　Ｗ１は、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基又はカルボキシル基を表し、
　ｑは１又は２の整数を表す。なお、○は結合手を表す。） The aromatic diamine represented by the formula (12) is a diamine having a rigid and linear molecular structure from the viewpoint that the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient. It is preferable to use it. Among these, as the diamine represented by the formula (12), a diamine having a structure in which Y 1 is represented by the following formula (6) is particularly preferable.
Figure JPOXMLDOC01-appb-C000027
 (Where
R 8 to R 11 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom. , nitro group, formyl group, cyano group, carboxyl group, W 1 with an optionally substituted phenyl group, W 1 with an optionally substituted naphthyl group, W 1 with an optionally substituted thienyl group or W Represents a furyl group optionally substituted by 1 ,
W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group. Represents a group,
q represents an integer of 1 or 2. In addition, (circle) represents a bond. )
　前記式（６）で表される２価の芳香族基がフェニレンジアミンから誘導されたものであることが好ましい。
　また、本発明の樹脂組成物から得られる硬化膜が十分に低い線膨張係数及び十分に高い強度を有するものとする観点から、前記式（６）において、前記Ｒ８乃至Ｒ１１が水素原子であることが好ましい。 The divalent aromatic group represented by the formula (6) is preferably derived from phenylenediamine.
Further, from the viewpoint that the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient and a sufficiently high strength, in the formula (6), R 8 to R 11 are hydrogen atoms. Preferably there is.
　前記式（１２）で表される芳香族ジアミンとしては、例えば、ｐ－フェニレンジアミン、ｏ－フェニレンジアミン、メチル－１，４－フェニレンジアミン、２－トリフルオロメチル－１，４－フェニレンジアミン、２－メトキシ－１，４－フェニレンジアミン、２，５－ジメチル－１，４－フェニレンジアミン、２，５－ビス（トリフルオロメチル）－１，４－フェニレンジアミン、４，４’－ジアミノベンズアニリド、４－アミノフェニル－４’－アミノベンゾエート、ベンジジン、３，３’－ジメトキシベンジジン、３，３’－ジクロロベンジジン、ｏ－トリジン、ｍ－トリジン、２，２’－ビス（トリフルオロメチル）ベンジジン、３，３’－ビス（トリフルオロメチル）ベンジジン、オクタフルオロベンジジン、３，３’，５，５’－テトラメチルベンジジン、２，２’，５，５’－テトラクロロベンジジン等が挙げられるが、これらの中でも、本発明の樹脂組成物から得られる硬化膜が十分に低い線膨張係数及び十分に高い強度を有するものとする観点から、ｐ－フェニレンジアミン及びｍ-フェニレンジアミンが特に好ましい。 Examples of the aromatic diamine represented by the formula (12) include p-phenylenediamine, o-phenylenediamine, methyl-1,4-phenylenediamine, 2-trifluoromethyl-1,4-phenylenediamine, 2 -Methoxy-1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,5-bis (trifluoromethyl) -1,4-phenylenediamine, 4,4'-diaminobenzanilide, 4-aminophenyl-4′-aminobenzoate, benzidine, 3,3′-dimethoxybenzidine, 3,3′-dichlorobenzidine, o-tolidine, m-tolidine, 2,2′-bis (trifluoromethyl) benzidine, 3,3′-bis (trifluoromethyl) benzidine, octafluorobenzidine, 3,3 ′, 5,5 -Tetramethylbenzidine, 2,2 ', 5,5'-tetrachlorobenzidine and the like, among these, the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient and a sufficiently high From the viewpoint of having strength, p-phenylenediamine and m-phenylenediamine are particularly preferable.
　前記式（１２）で表わされる脂肪族ジアミンとしては、例えば、４，４’－メチレンビス（シクロヘキシルアミン）、４，４’－メチレンビス（３－メチルシクロヘキシルアミン）、イソホロンジアミン、トランス－１，４－シクロヘキサンジアミン、シス－１，４－シクロヘキサンジアミン、１，４－シクロヘキサンビス（メチルアミン）、２，５－ビス（アミノメチル）ビシクロ〔２．２．１〕ヘプタン、２，６－ビス（アミノメチル）ビシクロ〔２．２．１〕ヘプタン、３，８－ビス（アミノメチル）トリシクロ〔５．２．１．０〕デカン、１，３－ジアミノアダマンタン、２，２－ビス（４－アミノシクロヘキシル）プロパン、２，２－ビス（４－アミノシクロヘキシル）ヘキサフルオロプロパン、１，３－プロパンジアミン、１，４－テトラメチレンジアミン、１，５－ペンタメチレンジアミン、１，６－ヘキサメチレンジアミン、１，７－ヘプタメチレンジアミン、１，８－オクタメチレンジアミン、１，９－ノナメチレンジアミン等が挙げられる。
　前記脂肪族ジアミンの中でも、本発明の樹脂組成物から得られる硬化膜が十分に低い線膨張係数を有するものとする観点から、剛直で直線的な分子構造を有するジアミンを使用することが好ましく、例えばトランス－１，４－シクロヘキサンジアミンが好適に用いられる。 Examples of the aliphatic diamine represented by the formula (12) include 4,4′-methylenebis (cyclohexylamine), 4,4′-methylenebis (3-methylcyclohexylamine), isophoronediamine, trans-1,4- Cyclohexanediamine, cis-1,4-cyclohexanediamine, 1,4-cyclohexanebis (methylamine), 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,6-bis (aminomethyl) ) Bicyclo [2.2.1] heptane, 3,8-bis (aminomethyl) tricyclo [5.2.1.0] decane, 1,3-diaminoadamantane, 2,2-bis (4-aminocyclohexyl) Propane, 2,2-bis (4-aminocyclohexyl) hexafluoropropane, 1,3-propanediamine, 1,4 Tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylene diamine, 1,8-octamethylene diamine, 1,9-nonamethylenediamine, and the like.
Among the aliphatic diamines, from the viewpoint that the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient, it is preferable to use a diamine having a rigid and linear molecular structure, For example, trans-1,4-cyclohexanediamine is preferably used.
　また、前記式（１３）で表されるジアミンも、本発明の樹脂組成物から得られる硬化膜が十分に低い線膨張係数を有するものとする観点から、剛直で直線的な分子構造を有するジアミンを使用することが好ましい。なかでも前記式（１３）で表されるジアミンとしては、Ｙ２がフルオレン骨格を有する芳香族基であるジアミンが好ましく、またＹ２が下記式（５）で表される構造である基が特に好ましい。
Figure JPOXMLDOC01-appb-C000028
 （式中、
　Ｒ０乃至Ｒ７は、それぞれ独立して、水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基、カルボキシル基、Ｗ１で置換されていてもよいフェニル基、Ｗ１で置換されていてもよいナフチル基、Ｗ１で置換されていてもよいチエニル基又はＷ１で置換されていてもよいフリル基を表し、
　Ｗ１は、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基又はカルボキシル基を表す。なお、○は結合手を表す。） The diamine represented by the formula (13) is also a diamine having a rigid and linear molecular structure from the viewpoint that the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient. Is preferably used. Among them, as the diamine represented by the formula (13), a diamine in which Y 2 is an aromatic group having a fluorene skeleton is preferable, and a group in which Y 2 is a structure represented by the following formula (5) is particularly preferable. preferable.
Figure JPOXMLDOC01-appb-C000028
 (Where
R 0 to R 7 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom. , nitro group, formyl group, cyano group, carboxyl group, W 1 with an optionally substituted phenyl group, W 1 with an optionally substituted naphthyl group, W 1 with an optionally substituted thienyl group or W Represents a furyl group optionally substituted by 1 ,
W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group. Represents a group. In addition, (circle) represents a bond. )
　前記式（１３）で表されるジアミンとしては、例えば、９，９－ビス(４－アミノフェニル)フルオレン、９，９－ビス(４－アミノ－３－フルオロフェニル)フルオレン、９，９－ビス(４－アミノ－３－クロロフェニル)フルオレン、９，９－ビス(４－アミノ－３－ブロモフェニル)フルオレン、９，９－ビス(４－アミノ－３－ヒドロキシフェニル)フルオレン、９，９－ビス(４－アミノ－３－メチルフェニル)フルオレン等が挙げられ、特に、Ｙ２が下記式（５ａ）で表される基である９，９－ビス(４－アミノフェニル)フルオレンが好ましい。
Figure JPOXMLDOC01-appb-C000029
 Examples of the diamine represented by the formula (13) include 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-fluorophenyl) fluorene, and 9,9-bis. (4-amino-3-chlorophenyl) fluorene, 9,9-bis (4-amino-3-bromophenyl) fluorene, 9,9-bis (4-amino-3-hydroxyphenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl) fluorene and the like can be mentioned, and 9,9-bis (4-aminophenyl) fluorene in which Y 2 is a group represented by the following formula (5a) is particularly preferable.
Figure JPOXMLDOC01-appb-C000029
　本発明のディスプレイ基板用樹脂組成物は、それから得られるフィルムの線膨張係数や機械強度を調節するため、更に、前記酸無水物と前記式（１２）および式（１３）で表されるジアミンに加えて下記式（１４）：
　　　Ｈ２Ｎ－Ｙ３－ＮＨ２　　　　　　（１４）
（式中、Ｙ３はエーテル結合を有する２価の基を表す。）
で表されるエーテル結合を主鎖中に有するジアミンとを共重合させたものであることが好ましい。式（１４）で表されるジアミンの例としては２，２－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパン、２，２－ビス〔４－（４－アミノフェノキシ）フェニル〕ヘキサフロオロプロパン、４，４’－ビス（４－アミノフェノキシ）ビフェニル、ビス〔４－（４－アミノフェノキシ）フェニル〕スルフォン、ビス〔４－（３－アミノフェノキシ）フェニル〕スルフォン、４，４’－ジアミノジフェニルエーテル、３，４’－ジアミノジフェニルエーテル、ビス〔４－（４－アミノフェノキシ）フェニル〕エーテル、１，４－ビス（４－アミノフェノキシ）ベンゼン、１，３－ビス（４－アミノフェノキシ）ベンゼン等を挙げることができ、これらは単独または２種以上を組み合わせて用いられる。中でも４，４’－ジアミノジフェニルエーテル、４，４’－ビス（４－アミノフェノキシ）ビフェニルが特に好ましい。 In order to adjust the linear expansion coefficient and mechanical strength of the film obtained from the resin composition for a display substrate of the present invention, the resin anhydride and the diamine represented by the formula (12) and the formula (13) are further added. In addition, the following formula (14):
H 2 N—Y 3 —NH 2 (14)
(In the formula, Y 3 represents a divalent group having an ether bond.)
It is preferable to copolymerize with the diamine which has the ether bond represented by these in a principal chain. Examples of diamines represented by formula (14) are 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoro. Propane, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4'-diamino Diphenyl ether, 3,4'-diaminodiphenyl ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, etc. These may be used alone or in combination of two or more. Of these, 4,4′-diaminodiphenyl ether and 4,4′-bis (4-aminophenoxy) biphenyl are particularly preferred.
　ポリアミック酸の生成反応に使用される溶剤としては特に限定されないが、例えば、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジエチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ－メチルピロリドン、３－メトキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－エトキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－プロポキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－イソプロポキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－ｓｅｃ－ブトキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－ｔｅｒｔ－ブトキシ－Ｎ，Ｎ－ジメチルプロピルアミド、ヘキサメチルホスホルアミド、ジメチルスルホオキシド、γ－ブチロラクトン、１，３－ジメチル－２－イミダゾリジノン、１，２－ジメトキシエタン－ビス（２－メトキシエチル）エーテル、テトラヒドロフラン、１，４－ジオキサン、ピコリン、ピリジン、アセトン、クロロホルム、トルエン、キシレン等の非プロトン性溶剤、及びフェノール、ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾール、ｏ－クロロフェノール、ｍ－クロロフェノール、ｐ－クロロフェノール等のプロトン性溶剤等が挙げられる。これらの溶剤は単独で又は２種類以上を組み合わせて使用してもよい。 The solvent used in the polyamic acid production reaction is not particularly limited. For example, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, 3-methoxy-N , N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropylamide, 3-propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethylpropylamide, 3-tert-butoxy-N, N-dimethylpropylamide, hexamethylphosphoramide, dimethylsulfoxide, γ-butyrolactone, 1, 3-Dimethyl-2-imidazolidinone, 1,2-dimethoxy Aprotic solvents such as ethane-bis (2-methoxyethyl) ether, tetrahydrofuran, 1,4-dioxane, picoline, pyridine, acetone, chloroform, toluene, xylene, and phenol, o-cresol, m-cresol, p- Examples thereof include protic solvents such as cresol, o-chlorophenol, m-chlorophenol, and p-chlorophenol. These solvents may be used alone or in combination of two or more.
　上記反応において、ジアミン成分の割合は、上記式（１２）で表されるジアミンと上記式（１３）で表されるジアミンとのモル比が、６０／４０乃至９９／１であることが好ましく、本発明の樹脂組成物から得られる硬化膜が十分に低い線膨張係数及び十分に高い強度を有するものとする観点から、７０／３０乃至９０／１０がより好ましい。 In the above reaction, the ratio of the diamine component is such that the molar ratio of the diamine represented by the above formula (12) and the diamine represented by the above formula (13) is 60/40 to 99/1, From the viewpoint that the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient and a sufficiently high strength, 70/30 to 90/10 is more preferable.
　また、上記反応において、酸二無水物成分とジアミン成分との割合は、モル比で酸二無水物成分／ジアミン成分＝０．８乃至１．２であることが好ましい。通常の重縮合反応と同様に、このモル比が１に近いほど生成する重合体の重合度は大きくなる。重合度が小さすぎるとポリイミド硬化膜の強度が不十分となり、また重合度が大きすぎるとポリイミド硬化膜形成時の作業性が悪くなる場合がある。 In the above reaction, the ratio of the acid dianhydride component to the diamine component is preferably acid dianhydride component / diamine component = 0.8 to 1.2 in terms of molar ratio. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1, the higher the degree of polymerization of the polymer produced. When the degree of polymerization is too small, the strength of the polyimide cured film becomes insufficient, and when the degree of polymerization is too large, workability at the time of forming the polyimide cured film may be deteriorated.
　生成されるポリアミック酸の重量平均分子量は、ポリアミック酸を含むディスプレイ基板用樹脂組成物から得られる硬化膜の強度を維持するために、ポリスチレン換算にて３，０００乃至３００，０００が好ましい。重量平均分子量が３，０００未満では、できあがったフィルムが脆くなる可能性があり、一方、重量平均分子量が３００，０００を超えるとポリアミック酸のワニスの粘度が高くなり過ぎる可能性があり、その結果、取扱いが難しくなるからである。
　なお、斯かる数値範囲を満たすために、上記式（１）及び式（３）中のｎとｍとは、ｎ＋ｍで通常、６乃至１８０であり、好ましくは１０乃至１００であり、より好ましくは１０乃至５０である。 The weight average molecular weight of the produced polyamic acid is preferably 3,000 to 300,000 in terms of polystyrene in order to maintain the strength of the cured film obtained from the resin composition for display substrate containing polyamic acid. If the weight average molecular weight is less than 3,000, the resulting film may become brittle. On the other hand, if the weight average molecular weight exceeds 300,000, the viscosity of the polyamic acid varnish may be too high. This is because handling becomes difficult.
In order to satisfy such a numerical range, n and m in the above formulas (1) and (3) are n + m, usually 6 to 180, preferably 10 to 100, more preferably 10 to 50.
　上記のようにして、得られた上記式（１）で表される構造単位及び式（３）で表される構造単位からなるポリアミック酸における構造単位の繰り返し数は、上記式（１）中のｎと上記式（３）中のｍとが、ｎ／（ｎ＋ｍ）≧６０％の関係であることが好ましい。
　また、ポリアミック酸が上記式（１）で表される構造単位及び上記式（３）で表される構造単位に加え、上記式（９）で表される構造単位からなる場合、該ポリアミック酸における構造単位の繰り返し数は、上記式（１）中のｎと上記式（３）中のｍと上記式（９）とが通常、ｎ：ｍ：ｌ＝５０：２５：２５乃至９６：２：２の関係であり、好ましくはｎ：ｍ：ｌ＝６０：２０：２０乃至９０：５：５であり、より好ましくは、７０：１５：１５～９０：５：５である。 As described above, the number of repeating structural units in the polyamic acid composed of the structural unit represented by the above formula (1) and the structural unit represented by the formula (3) is represented by the formula (1). It is preferable that n and m in the above formula (3) have a relationship of n / (n + m) ≧ 60%.
In addition to the structural unit represented by the above formula (1) and the structural unit represented by the above formula (3), in addition to the structural unit represented by the above formula (9), As for the number of repeating structural units, n in the above formula (1), m in the above formula (3) and the above formula (9) are usually n: m: l = 50: 25: 25 to 96: 2: The relationship is preferably n: m: l = 60: 20: 20 to 90: 5: 5, more preferably 70:15:15 to 90: 5: 5.
＜ポリイミド＞
　本発明のディスプレイ基板用樹脂組成物に含まれるポリイミドは、上述のように合成したポリアミック酸を、加熱により脱水閉環（熱イミド化）して得ることができる。なお、この際、ポリアミック酸を溶剤中でイミドに転化させ、溶剤可溶性のポリイミドとして用いることも可能である。また、公知の脱水閉環触媒を使用して化学的に閉環する方法も採用することができる。加熱による方法は、１００乃至５００℃、好ましくは１２０乃至４００℃の任意の温度で行うことができる。化学的に閉環する方法は、例えば、ピリジンやトリエチルアミンなどと、無水酢酸などとの存在下で行うことができ、この際の温度は、－２０乃至２００℃の任意の温度を選択することができる。 <Polyimide>
The polyimide contained in the resin composition for display substrates of the present invention can be obtained by subjecting the polyamic acid synthesized as described above to dehydration ring closure (thermal imidization) by heating. At this time, polyamic acid can be converted to imide in a solvent and used as a solvent-soluble polyimide. Moreover, the method of chemically ring-closing using a well-known dehydration ring-closing catalyst is also employable. The method by heating can be performed at an arbitrary temperature of 100 to 500 ° C., preferably 120 to 400 ° C. The method of chemically cyclizing can be performed, for example, in the presence of pyridine, triethylamine or the like and acetic anhydride, and the temperature at this time can be selected from -20 to 200 ° C. .
　本発明では、ポリイミドの反応溶液をそのまま、又は、希釈して使用することができ、或いは反応溶液にメタノール、エタノールなどの貧溶媒を加えて沈殿回収したポリイミドを適当な溶剤に再溶解させて使用することができる。希釈及び再溶解に用いる溶剤は、得られたポリイミドを溶解させるものであれば特に限定されないが、例えば、ｍ－クレゾール、２－ピロリドン、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン、Ｎ－ビニル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、３－メトキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－エトキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－プロポキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－イソプロポキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－ｓｅｃ－ブトキシ－Ｎ，Ｎ－ジメチルプロピルアミド、３－ｔｅｒｔ－ブトキシ－Ｎ，Ｎ－ジメチルプロピルアミド、γ－ブチロラクトン、などが挙げられる。これらの溶剤は、単独で又は２種以上を組み合わせて使用してもよい。 In the present invention, the polyimide reaction solution can be used as it is or after dilution, or a poor solvent such as methanol or ethanol is added to the reaction solution and the recovered polyimide is redissolved in an appropriate solvent. can do. The solvent used for dilution and re-dissolution is not particularly limited as long as it can dissolve the obtained polyimide. For example, m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropylamide, 3-propoxy -N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethylpropylamide, 3- and tert-butoxy-N, N-dimethylpropylamide, γ-butyrolactone, and the like. These solvents may be used alone or in combination of two or more.
　生成されるポリイミドの重量平均分子量は、ポリイミドを含むディスプレイ基板用樹脂組成物から得られる硬化膜の強度を維持するために、ポリスチレン換算にて３，０００乃至３００，０００が好ましい。重量平均分子量が３，０００未満では、できあがったフィルムが脆くなる可能性があり、一方、重量平均分子量が３００，０００を超えるとポリイミドのワニスの粘度が高くなり過ぎる可能性があり、その結果、取扱いが難しくなるからである。
　なお、斯かる数値範囲を満たすために、上記式（２）及び式（４）中のｎとｍとは、ｎ＋ｍで通常６乃至１８０であり、好ましくは１０乃至１００であり、より好ましくは１０乃至５０である。 The weight average molecular weight of the polyimide produced is preferably 3,000 to 300,000 in terms of polystyrene in order to maintain the strength of the cured film obtained from the resin composition for display substrate containing polyimide. If the weight average molecular weight is less than 3,000, the resulting film may be brittle, while if the weight average molecular weight exceeds 300,000, the viscosity of the polyimide varnish may be too high, and as a result, This is because handling becomes difficult.
In order to satisfy such a numerical range, n and m in the above formulas (2) and (4) are usually n + m and are usually 6 to 180, preferably 10 to 100, more preferably 10 Thirty to fifty.
　上記のようにして、得られた上記式（２）で表される構造単位及び式（４）で表される構造単位からなるポリイミドにおける構造単位の繰り返し数は、上記式（２）中のｎと上記式（４）中のｍとが、ｎ／（ｎ＋ｍ）≧６０％の関係であることが好ましい。
　また、前記ポリイミドが上記式（２）で表される構造単位及び上記式（４）で表される構造単位に加え、上記式（１０）で表される構造単位からなる場合、該ポリイミドにおける構造単位の繰り返し数は、上記式（２）中のｎと上記式（４）中のｍと上記式（１０）とが通常、ｎ：ｍ：ｌ＝５０：２５：２５乃至９６：２：２の関係であり、好ましくはｎ：ｍ：ｌ＝６０：２０：２０乃至９０：５：５であり、より好ましくは、７０：１５：１５～９０：５：５である。 As described above, the number of repeating structural units in the polyimide composed of the structural unit represented by the above formula (2) and the structural unit represented by the formula (4) is n in the above formula (2). And m in the above formula (4) preferably have a relationship of n / (n + m) ≧ 60%.
In addition to the structural unit represented by the above formula (2) and the structural unit represented by the above formula (4), in addition to the structural unit represented by the above formula (10), the polyimide has a structure. As for the number of repeating units, n in the above formula (2), m in the above formula (4) and the above formula (10) are usually n: m: l = 50: 25: 25 to 96: 2: 2. Preferably, n: m: l = 60: 20: 20 to 90: 5: 5, and more preferably 70:15:15 to 90: 5: 5.
　本発明のディスプレイ基板用樹脂組成物は、溶剤を含むことができる。そのような溶剤としては、例えば、段落［００１４］に記載された溶剤等が挙げられる。 The resin composition for a display substrate of the present invention can contain a solvent. Examples of such solvents include the solvents described in paragraph [0014].
　本発明のディスプレイ基板用樹脂組成物は、架橋剤（以下、架橋性化合物ともいう。）を含むことができる。
＜架橋剤＞
　架橋性化合物は、そのポジ型感光性樹脂組成物を用いて得られる塗膜を、硬化膜に転換する工程で、ポリアミック酸、またはポリイミドの少なくとも一方に含有される有機基と、反応し得る基を有する化合物であれば特に限定されない。そのような化合物としては、例えば、エポキシ基を２個以上含有する化合物や、アミノ基の水素原子が、メチロール基、アルコキシメチル基又はその両方で置換された基を有する、メラミン誘導体、ベンゾグアナミン誘導体又はグリコールウリル等が挙げられる。このメラミン誘導体及びベンゾグアナミン誘導体は、二量体又は三量体であっても良く、又、単量体、２量体及び３量体から任意に選ばれる混合物であっても良い。これらのメラミン誘導体及びベンゾグアナミン誘導体は、トリアジン環１個当たり、メチロール基又はアルコキシメチル基を平均３個以上６個未満有するものが好ましい。
　また、本発明に用いられる架橋剤は、単独で又は２種以上を組み合わせて使用してもよい。 The resin composition for display substrates of the present invention can contain a crosslinking agent (hereinafter also referred to as a crosslinkable compound).
<Crosslinking agent>
The crosslinkable compound is a group capable of reacting with an organic group contained in at least one of polyamic acid or polyimide in the step of converting a coating film obtained by using the positive photosensitive resin composition into a cured film. If it is a compound which has this, it will not specifically limit. Examples of such a compound include a compound containing two or more epoxy groups, a melamine derivative, a benzoguanamine derivative, or a group in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group, or both. Examples include glycoluril. The melamine derivative and benzoguanamine derivative may be a dimer or a trimer, or may be a mixture arbitrarily selected from a monomer, a dimer and a trimer. These melamine derivatives and benzoguanamine derivatives preferably have an average of 3 or more and less than 6 methylol groups or alkoxymethyl groups per one triazine ring.
Moreover, you may use the crosslinking agent used for this invention individually or in combination of 2 or more types.
　以下に、架橋性化合物の具体例を挙げるが、これに限定されない。
　エポキシ基を２個以上含有する化合物としては、エポリードＧＴ－４０１、エポリードＧＴ－４０３、エポリードＧＴ－３０１、エポリードＧＴ－３０２、セロキサイド２０２１、セロキサイド３０００（以上、ダイセル化学工業（株）製）等のシクロヘキセン構造を有するエポキシ化合物；エピコート１００１、エピコート１００２、エピコート１００３、エピコート１００４、エピコート１００７、エピコート１００９、エピコート１０１０、エピコート８２８（以上、ジャパンエポキシレジン（株）製）等のビスフェノールＡ型エポキシ化合物；エピコート８０７（ジャパンエポキシレジン（株）製）等のビスフェノールＦ型エポキシ化合物；エピコート１５２、エピコート１５４（以上、ジャパンエポキシレジン（株）製）、ＥＰＰＮ２０１、ＥＰＰＮ２０２（以上、日本化薬（株）製）等のフェノールノボラック型エポキシ化合物；ＥＣＯＮ－１０２、ＥＣＯＮ－１０３Ｓ、ＥＣＯＮ－１０４Ｓ、ＥＣＯＮ－１０２０、ＥＣＯＮ－１０２５、ＥＣＯＮ－１０２７（以上、日本化薬（株）製）、エピコート１８０Ｓ７５（ジャパンエポキシレジン（株）製）等のクレゾールノボラック型エポキシ化合物；Ｖ８０００－Ｃ７（ＤＩＣ（株）製）等のナフタレン型エポキシ化合物；デナコールＥＸ－２５２（ナガセケムテックス（株）製）、ＣＹ１７５、ＣＹ１７７、ＣＹ１７９、アラルダイトＣＹ－１８２、アラルダイトＣＹ－１９２、アラルダイトＣＹ－１８４（以上、ＢＡＳＦ社製）、エピクロン２００、エピクロン４００（以上、ＤＩＣ（株）製）、エピコート８７１、エピコート８７２（以上、ジャパンエポキシレジン（株）製）、ＥＤ－５６６１、ＥＤ－５６６２（以上、セラニーズコーティング（株）製）等の脂環式エポキシ化合物；デナコールＥＸ－６１１、デナコールＥＸ－６１２、デナコールＥＸ－６１４、デナコールＥＸ－６２２、デナコールＥＸ－４１１、デナコールＥＸ－５１２、デナコールＥＸ－５２２、デナコールＥＸ－４２１、デナコールＥＸ－３１３、デナコールＥＸ－３１４、デナコールＥＸ－３１２（以上、ナガセケムテックス（株）製）等の脂肪族ポリグリシジルエーテル化合物が挙げられる。 Although the specific example of a crosslinkable compound is given to the following, it is not limited to this.
Examples of the compound containing two or more epoxy groups include Epolide GT-401, Epolide GT-403, Epolide GT-301, Epolide GT-302, Celoxide 2021, and Celoxide 3000 (manufactured by Daicel Chemical Industries, Ltd.). Epoxy compounds having a cyclohexene structure; bisphenol A type epoxy compounds such as Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010, Epicoat 828 (above, manufactured by Japan Epoxy Resins Co., Ltd.); Bisphenol F type epoxy compound such as 807 (manufactured by Japan Epoxy Resin Co., Ltd.); Epicoat 152, Epicoat 154 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPP 201, EPPN202 (above, Nippon Kayaku Co., Ltd.) and other phenol novolac epoxy compounds; ECON-102, ECON-103S, ECON-104S, ECON-1020, ECON-1025, ECON-1027 (above, Nippon Kayaku) Yakuhin Co., Ltd.), Crecoat novolak type epoxy compounds such as Epicote 180S75 (Japan Epoxy Resin Co., Ltd.); Naphthalene type epoxy compounds such as V8000-C7 (DIC Co., Ltd.); Denacol EX-252 (Nagase Chem) Manufactured by Tex Co., Ltd.), CY175, CY177, CY179, Araldite CY-182, Araldite CY-192, Araldite CY-184 (above, manufactured by BASF), Epicron 200, Epicron 400 (above, manufactured by DIC Corporation), Epicote 871 Alicyclic epoxy compounds such as Epicoat 872 (above, Japan Epoxy Resin Co., Ltd.), ED-5661, ED-5661 (above, Celanese Coating Co., Ltd.); Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-411, Denacol EX-512, Denacol EX-522, Denacol EX-421, Denacol EX-313, Denacol EX-314, Denacol EX-312 (above, Nagase ChemteX Aliphatic polyglycidyl ether compounds such as those manufactured by KK
　アミノ基の水素原子がメチロール基、アルコキシメチル基又はその両方で置換された基を有する、メラミン誘導体、ベンゾグアナミン誘導体又はグリコールウリルとしては、トリアジン環１個当たりメトキシメチル基が平均３．７個置換されているＭＸ－７５０、トリアジン環１個当たりメトキシメチル基が平均５．８個置換されているＭＷ－３０（以上、（株）三和ケミカル製）；サイメル３００、サイメル３０１、サイメル３０３、サイメル３５０、サイメル３７０、サイメル７７１、サイメル３２５、サイメル３２７、サイメル７０３、サイメル７１２等のメトキシメチル化メラミン；サイメル２３５、サイメル２３６、サイメル２３８、サイメル２１２、サイメル２５３、サイメル２５４等のメトキシメチル化ブトキシメチル化メラミン；サイメル５０６、サイメル５０８等のブトキシメチル化メラミン；サイメル１１４１のようなカルボキシル基含有メトキシメチル化イソブトキシメチル化メラミン；サイメル１１２３のようなメトキシメチル化エトキシメチル化ベンゾグアナミン；サイメル１１２３－１０のようなメトキシメチル化ブトキシメチル化ベンゾグアナミン；サイメル１１２８のようなブトキシメチル化ベンゾグアナミン；サイメル１１２５－８０のようなカルボキシル基含有メトキシメチル化エトキシメチル化ベンゾグアナミン；サイメル１１７０のようなブトキシメチル化グリコールウリル；サイメル１１７２のようなメチロール化グリコールウリル（以上、三井サイアナミッド（株）製）等が挙げられる。
　また、本発明のディスプレイ基板用樹脂組成物における架橋剤の含有量は特に限定されないが、樹脂組成物の保存安定性をより向上させる観点から、ポリアミック酸又はポリイミド１００質量部に対して、２０質量部以下が好ましく、本発明の樹脂組成物から得られる硬化膜が十分に低い線膨張係数を有するものとする観点から、１５質量部以下がより好ましい。 As the melamine derivative, benzoguanamine derivative, or glycoluril having a group in which the hydrogen atom of the amino group is substituted with a methylol group, an alkoxymethyl group, or both, an average of 3.7 methoxymethyl groups are substituted per triazine ring. MX-750, MW-30 substituted with an average of 5.8 methoxymethyl groups per triazine ring (above, manufactured by Sanwa Chemical Co., Ltd.); Cymel 300, Cymel 301, Cymel 303, Cymel 350 Methoxymethylated melamine such as Cymel 370, Cymel 771, Cymel 325, Cymel 327, Cymel 703, Cymel 712, etc .; Mela Butoxymethylated melamines such as Cymel 506 and Cymel 508; carboxyl group-containing methoxymethylated isobutoxymethylated melamines such as Cymel 1141; methoxymethylated ethoxymethylated benzoguanamines such as Cymel 1123; Methoxymethylated butoxymethylated benzoguanamine; butoxymethylated benzoguanamine such as Cymel 1128; methoxymethylated ethoxymethylated benzoguanamine containing carboxyl groups such as Cymel 1125-80; butoxymethylated glycoluril such as Cymel 1170; Cymel 1172 Such as methylolated glycoluril (manufactured by Mitsui Cyanamid Co., Ltd.).
In addition, the content of the crosslinking agent in the resin composition for display substrates of the present invention is not particularly limited, but from the viewpoint of further improving the storage stability of the resin composition, 20 masses with respect to 100 mass parts of polyamic acid or polyimide. From the viewpoint that the cured film obtained from the resin composition of the present invention has a sufficiently low linear expansion coefficient, 15 parts by mass or less is more preferable.
［ワニス及び硬化膜］
　本発明のディスプレイ基板用樹脂組成物からなる硬化膜を形成する具体的な方法としては、まず、樹脂組成物を溶剤に溶解又は分散してワニスの形態（膜形成材料）とし、該ワニスを基板上にキャストコート法、スピンコート法、ブレードコート法、ディップコート法、ロールコート法、バーコート法、ダイコート法、インクジェット法、印刷法（凸版、凹版、平版、スクリーン印刷等）等によって塗布して塗膜を得る。そして得られた塗膜を、ホットプレート、オーブン等で焼成することにより硬化膜が形成される。焼成温度としては、通常１００乃至５００℃、好ましくは１００乃至４００℃である。
　また前記基板としては、例えば、プラスチック（ポリカーボネート、ポリメタクリレート、ポリスチレン、ポリエステル、ポリオレフィン、エポキシ、メラミン、トリアセチルセルロース、ＡＢＳ、ＡＳ、ノルボルネン系樹脂等）、金属、木材、紙、ガラス、スレート等を挙げることができる。 [Varnish and cured film]
As a specific method for forming a cured film comprising the resin composition for a display substrate of the present invention, first, the resin composition is dissolved or dispersed in a solvent to form a varnish (film forming material), and the varnish is used as a substrate. Apply by cast coating method, spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, die coating method, ink jet method, printing method (letter plate, intaglio plate, planographic plate, screen printing, etc.) A coating film is obtained. And the cured film is formed by baking the obtained coating film with a hotplate, oven, etc. FIG. The firing temperature is usually 100 to 500 ° C, preferably 100 to 400 ° C.
Examples of the substrate include plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, slate, and the like. Can be mentioned.
　前記ワニスの形態において使用する溶剤としては、ディスプレイ基板用樹脂組成物を溶解させるものであれば特に限定されないが、例えば、上記ポリアミック酸の生成反応において使用される溶剤等が挙げられる。これら溶剤は単独で又は２種以上を組み合わせて使用してもよい。
　また上記溶剤に樹脂組成物を溶解又は分散させる濃度は任意であるが、ディスプレイ基板用樹脂組成物と溶剤の総質量（合計質量）に対して、ディスプレイ基板用樹脂組成物の濃度は５乃至４０質量％であり、樹脂組成物の保存安定性をより向上させる観点から好ましくは１０乃至２０質量％であり、樹脂組成物をより均一に塗布させる観点からより好ましくは１０乃至１５質量％である。
　ディスプレイ基板用樹脂組成物から形成される硬化膜の厚さは特に限定されないが、通常１乃至５０μｍ、好ましくは５乃至４０μｍである。 The solvent used in the form of the varnish is not particularly limited as long as it dissolves the resin composition for a display substrate, and examples thereof include a solvent used in the reaction for producing the polyamic acid. These solvents may be used alone or in combination of two or more.
Further, the concentration at which the resin composition is dissolved or dispersed in the solvent is arbitrary, but the concentration of the resin composition for display substrate is 5 to 40 with respect to the total mass (total mass) of the resin composition for display substrate and the solvent. It is preferably 10 to 20% by mass from the viewpoint of further improving the storage stability of the resin composition, and more preferably 10 to 15% by mass from the viewpoint of more uniformly applying the resin composition.
Although the thickness of the cured film formed from the resin composition for display substrates is not specifically limited, Usually, 1-50 micrometers, Preferably it is 5-40 micrometers.
　また、本発明は、下記式（１）で表される構造単位及び式（３）で表される構造単位を含むポリアミック酸を提供し、式（２）で表される構造単位及び式（４）で表される構造単位を含むポリイミドを提供する。
Figure JPOXMLDOC01-appb-C000030
 　上記式（１）乃至式（４）中、Ｘ１、Ｙ１、Ｙ２、ｎ及びｍの好ましい具体例は、前記ディスプレイ基板用樹脂組成物に記載されたＸ１、Ｙ１、Ｙ２、ｎ及びｍの具体例と同じである。
　また、本発明は、更に式（９）で表される構造単位を含むポリアミック酸、又は式（１０）で表される構造単位を含むポリイミドを提供する。
Figure JPOXMLDOC01-appb-C000031
 ［式（９）及び式（１０）中、
　Ｘ１は芳香族基と２つ以上のカルボニル基を有する４価の有機基を表し、
　Ｙ３はエーテル結合を有する２価の基を表し、
　ｌは自然数を表す。］
　また、本発明は、前記ポリアミック酸と架橋剤とを含む組成物を提供し、前記ポリイミドと架橋剤とを含む組成物を提供する。
　架橋剤の好ましい具体例は、前記ディスプレイ基板用樹脂組成物に記載された架橋剤の具体例と同じである。
　また、本発明は、前記組成物が少なくとも１種の溶剤に溶解しているワニスを提供する。溶剤の好ましい具体例は、前記ディスプレイ基板用樹脂組成物が少なくとも１種の溶剤に溶解しているワニスに記載された溶剤の具体例と同じである。
　また、本発明は、前記ワニスを用いて２３０℃以上で焼成することにより得られる硬化膜を提供する。硬化膜の作製方法は、前記ディスプレイ基板用樹脂組成物が少なくとも１種の溶剤に溶解しているワニスを用いて２３０℃以上で焼成することにより得られる硬化膜と同じである。 Moreover, this invention provides the polyamic acid containing the structural unit represented by following formula (1) and the structural unit represented by Formula (3), and the structural unit and formula (4) represented by Formula (2) The polyimide containing the structural unit represented by this is provided.
Figure JPOXMLDOC01-appb-C000030
 In the above formulas (1) to (4), preferred specific examples of X 1 , Y 1 , Y 2 , n and m are X 1 , Y 1 , Y 2 and the like described in the resin composition for display substrates. The same as the specific examples of n and m.
The present invention further provides a polyamic acid containing a structural unit represented by formula (9) or a polyimide containing a structural unit represented by formula (10).
Figure JPOXMLDOC01-appb-C000031
 [In Formula (9) and Formula (10),
X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups,
Y 3 represents a divalent group having an ether bond,
l represents a natural number. ]
Moreover, this invention provides the composition containing the said polyamic acid and a crosslinking agent, and provides the composition containing the said polyimide and a crosslinking agent.
The preferable specific example of a crosslinking agent is the same as the specific example of the crosslinking agent described in the said resin composition for display substrates.
The present invention also provides a varnish in which the composition is dissolved in at least one solvent. Preferred specific examples of the solvent are the same as the specific examples of the solvent described in the varnish in which the resin composition for display substrate is dissolved in at least one solvent.
Moreover, this invention provides the cured film obtained by baking at 230 degreeC or more using the said varnish. The method for producing the cured film is the same as the cured film obtained by baking at 230 ° C. or higher using a varnish in which the resin composition for display substrate is dissolved in at least one solvent.
　以下、実施例を挙げて、本発明をより具体的に説明するが、本発明は下記の実施例に限定されるものではない。
［実施例で用いる略記号］
　以下の実施例で用いる略記号の意味は、次のとおりである。
＜酸二無水物＞
ＰＭＤＡ：ピロメリット酸無水物
ＢＰ－ＴＭＥ：４，４－ビフェニルビス（トリメリット酸モノエステル酸無水物）（下記式（１５））
Figure JPOXMLDOC01-appb-C000032
 ＜ジアミン＞
ＰＤＡ：ｐ－フェニレンジアミン
ＦＤＡ：９，９－ビス(４－アミノフェニル)フルオレン
ＯＤＡ：４，４’－ジアミノジフェニルエーテル
ＢＡＰＢ：４，４’－ビス（４－アミノフェノキシ）ビフェニル
＜溶剤＞
ＮＭＰ：Ｎ－メチルピロリドン EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
[Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
<Acid dianhydride>
PMDA: pyromellitic anhydride BP-TME: 4,4-biphenylbis (trimellitic acid monoester anhydride) (formula (15) below)
Figure JPOXMLDOC01-appb-C000032
 <Diamine>
PDA: p-phenylenediamine FDA: 9,9-bis (4-aminophenyl) fluorene ODA: 4,4′-diaminodiphenyl ether BAPB: 4,4′-bis (4-aminophenoxy) biphenyl <solvent>
NMP: N-methylpyrrolidone
［数平均分子量及び重量平均分子量の測定］
　ポリマーの重量平均分子量（以下、Ｍｗと略す。）と分子量分布は、日本分光（株）製ＧＰＣ装置（Ｓｈｏｄｅｘ［登録商標］カラムＳＢ８０３ＨＱ及びＳＢ８０４ＨＱ）を用い、溶出溶媒としてジメチルホルムアミドを流量０．９ｍＬ／分、カラム温度４０℃の条件で測定した。なお、Ｍｗはポリスチレン換算値とした。 [Measurement of number average molecular weight and weight average molecular weight]
The polymer weight average molecular weight (hereinafter abbreviated as Mw) and molecular weight distribution were measured using a GPC apparatus (Shodex [registered trademark] columns SB803HQ and SB804HQ) manufactured by JASCO Corporation, and dimethylformamide as the elution solvent at a flow rate of 0.9 mL. / Min and column temperature of 40 ° C. In addition, Mw was made into the polystyrene conversion value.
（ポリアミック酸およびディスプレイ基板用樹脂組成物（ワニス）の合成）
＜実施例１＞
　ＰＤＡ　０．３５７ｇ（０．００３３モル）とＦＤＡ　０．２８８ｇ（０．０００８３モル）をＮＭＰ　１７．８ｇに溶解し、ＢＰ－ＴＭＥ　１．１０ｇ（０．００２１モル）とＰＭＤＡ　０．４５１ｇ（０．００２１モル）を添加した後、窒素雰囲気下、２３℃で２４時間反応させた。得られたポリマーのＭｗは７５，７００、分子量分布は２．９であった。この溶液をディスプレイ基板用樹脂組成物とした。 (Synthesis of polyamic acid and resin composition for display substrate (varnish))
<Example 1>
PDA 0.357 g (0.0033 mol) and FDA 0.288 g (0.00083 mol) were dissolved in 17.8 g of NMP, BP-TME 1.10 g (0.0021 mol) and PMDA 0.451 g (0.001 mol). The reaction was allowed to proceed for 24 hours at 23 ° C. under a nitrogen atmosphere. Mw of the obtained polymer was 75,700, and molecular weight distribution was 2.9. This solution was used as a resin composition for display substrates.
＜実施例２＞
　ＰＤＡ　０．２４６ｇ（０．００２３モル）とＦＤＡ　０．５２８ｇ（０．００１５モル）をＮＭＰ　１７．８ｇに溶解し、ＢＰ－ＴＭＥ　１．０１ｇ（０．００１９モル）とＰＭＤＡ　０．４１３ｇ（０．００１９モル）を添加した後、窒素雰囲気下、２３℃で２４時間反応させた。得られたポリマーのＭｗは８８，６００、分子量分布は３．１であった。この溶液をディスプレイ基板用樹脂組成物とした。 <Example 2>
PDA 0.246 g (0.0023 mol) and FDA 0.528 g (0.0015 mol) were dissolved in 17.8 g of NMP, BP-TME 1.01 g (0.0019 mol) and PMDA 0.413 g (0. 0019 mol) was added, followed by reaction at 23 ° C. for 24 hours under a nitrogen atmosphere. Mw of the obtained polymer was 88,600 and molecular weight distribution was 3.1. This solution was used as a resin composition for display substrates.
＜実施例３＞
　ＰＤＡ　０．４６６ｇ（０．００４３モル）とＦＤＡ　０．１８８ｇ（０．０００５モル）とＯＤＡ　０．１０８ｇ（０．０００５モル）をＮＭＰ　１８．０ｇに溶解し、ＢＰ－ＴＭＥ　０．１４４ｇ（０．０００３モル）とＰＭＤＡ　１．０９ｇ（０．００５０モル）を添加した後、窒素雰囲気下、２３℃で２４時間反応させた。得られたポリマーのＭｗは６５，８００、分子量分布は２．２であった。この溶液をディスプレイ基板用樹脂組成物とした。 <Example 3>
PDA 0.466 g (0.0043 mol), FDA 0.188 g (0.0005 mol) and ODA 0.108 g (0.0005 mol) were dissolved in NMP 18.0 g, and BP-TME 0.144 g (0. 0003 mol) and 1.09 g (0.0050 mol) of PMDA were added, followed by reaction at 23 ° C. for 24 hours in a nitrogen atmosphere. Mw of the obtained polymer was 65,800, and molecular weight distribution was 2.2. This solution was used as a resin composition for display substrates.
＜実施例４＞
　ＰＤＡ　０．２９６ｇ（０．００２７モル）とＦＤＡ　０．３１８ｇ（０．０００９モル）とＢＡＰＢ　０．３３７ｇ（０．０００９モル）をＮＭＰ　１８．０ｇに溶解し、ＢＰ－ＴＭＥ　０．１２２ｇ（０．０００２モル）とＰＭＤＡ　０．９２７ｇ（０．００４２モル）を添加した後、窒素雰囲気下、２３℃で２４時間反応させた。得られたポリマーのＭｗは６４，２００、分子量分布は２．５であった。この溶液をディスプレイ基板用樹脂組成物とした。 <Example 4>
PDA 0.296 g (0.0027 mol), FDA 0.318 g (0.0009 mol) and BAPB 0.337 g (0.0009 mol) were dissolved in NMP 18.0 g, and BP-TME 0.122 g (0.009 mol) was added. 0002 mol) and 0.927 g (0.0042 mol) of PMDA were added, followed by reaction at 23 ° C. for 24 hours in a nitrogen atmosphere. The obtained polymer had Mw of 64,200 and a molecular weight distribution of 2.5. This solution was used as a resin composition for display substrates.
＜実施例５＞
　ＰＤＡ　０．４４６ｇ（０．００４１モル）とＦＤＡ　０．１８０ｇ（０．０００５モル）とＢＡＰＢ　０．１９０ｇ（０．０００５モル）をＮＭＰ　１８．０ｇに溶解し、ＢＰ－ＴＭＥ　０．１３８ｇ（０．０００３モル）とＰＭＤＡ　１．０５ｇ（０．００４８モル）を添加した後、窒素雰囲気下、２３℃で２４時間反応させた。得られたポリマーのＭｗは１０２，０００、分子量分布は２．７であった。この溶液をディスプレイ基板用樹脂組成物とした。 <Example 5>
PDA 0.446 g (0.0041 mol), FDA 0.180 g (0.0005 mol) and BAPB 0.190 g (0.0005 mol) were dissolved in NMP 18.0 g, and BP-TME 0.138 g (0. 0003 mol) and 1.05 g (0.0048 mol) of PMDA were added, followed by reaction at 23 ° C. for 24 hours in a nitrogen atmosphere. Mw of the obtained polymer was 102,000, and molecular weight distribution was 2.7. This solution was used as a resin composition for display substrates.
＜実施例６＞
　ＰＤＡ　０．５３７ｇ（０．００５０モル）とＦＤＡ　０．０９６１ｇ（０．０００３モル）とＢＡＰＢ　０．１０２ｇ（０．０００３モル）をＮＭＰ　１８．０ｇに溶解し、ＢＰ－ＴＭＥ　０．１４７ｇ（０．０００３モル）とＰＭＤＡ　１．１２ｇ（０．００５１モル）を添加した後、窒素雰囲気下、２３℃で２４時間反応させた。得られたポリマーのＭｗは８２，９００、分子量分布は２．６であった。この溶液をディスプレイ基板用樹脂組成物とした。 <Example 6>
PDA (0.537 g, 0.0050 mol), FDA (0.0961 g, 0.0003 mol), and BAPB (0.102 g, 0.0003 mol) were dissolved in NMP (18.0 g), and BP-TME (0.147 g, 0.003 mol). 0003 mol) and 1.12 g (0.0051 mol) of PMDA were added, followed by reaction at 23 ° C. for 24 hours in a nitrogen atmosphere. Mw of the obtained polymer was 82,900, and molecular weight distribution was 2.6. This solution was used as a resin composition for display substrates.
＜比較例１＞
　ＰＤＡ　０．４９１ｇ（０．００４５モル）をＮＭＰ　１７．８ｇに溶解し、ＢＰ－ＴＭＥ　１．２１ｇ（０．００２３モル）とＰＭＤＡ　０．４９５ｇ（０．００２３モル）を添加した後、窒素雰囲気下、２３℃で２４時間反応させた。得られたポリマーのＭｗは８４，０００、分子量分布は２．７であった。この溶液をディスプレイ基板用樹脂組成物とした。 <Comparative Example 1>
0.491 g (0.0045 mol) of PDA was dissolved in 17.8 g of NMP, 1.21 g (0.0023 mol) of BP-TME and 0.495 g (0.0023 mol) of PMDA were added, and then in a nitrogen atmosphere. And reacted at 23 ° C. for 24 hours. Mw of the obtained polymer was 84,000, and molecular weight distribution was 2.7. This solution was used as a resin composition for display substrates.
（耐熱性評価）
　実施例１乃至６および比較例１より得られたディスプレイ基板用樹脂組成物をドクターブレードでガラス基板上に塗布し、実施例１乃至２および比較例１は１２０℃で１０分間、続いて２４０℃で１０分間、続いて３００℃で３０分間ベークを行い、実施例３乃至６は１２０℃で３０分間、続いて１５０℃で３０分間、続いて１８０℃で３０分間、続いて２１０℃で３０分間、続いて２４０℃で３０分間、続いて３００℃で２０分間、続いて４００℃で６０分間、窒素雰囲気下でベークを行って得られた膜の耐熱性について、ＴＧ－ＤＴＡ（ブルカーエイエックスエス社製、ＴＧ／ＤＴＡ２０００ＳＡ）にて、５０℃から５００℃まで１０℃／分で昇温し５質量％の質量減少を生ずる温度から評価した。結果を表１に示す。 (Heat resistance evaluation)
The resin compositions for display substrates obtained from Examples 1 to 6 and Comparative Example 1 were applied onto a glass substrate with a doctor blade. Examples 1 to 2 and Comparative Example 1 were at 120 ° C. for 10 minutes, and subsequently at 240 ° C. Bake for 10 minutes at 300 ° C. for 30 minutes, and Examples 3 to 6 were 120 ° C. for 30 minutes, followed by 150 ° C. for 30 minutes, followed by 180 ° C. for 30 minutes, followed by 210 ° C. for 30 minutes. Subsequently, regarding the heat resistance of the film obtained by baking at 240 ° C. for 30 minutes, subsequently at 300 ° C. for 20 minutes, then at 400 ° C. for 60 minutes in a nitrogen atmosphere, TG-DTA (Bruker AXS (TG / DTA2000SA, manufactured by the company), the temperature was raised from 50 ° C. to 500 ° C. at a rate of 10 ° C./min and evaluated from the temperature at which a mass loss of 5% by mass occurred. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000033
　表１より実施例１および実施例３乃至６より得られたディスプレイ基板用樹脂組成物を用いて作製した膜は、比較例１より高い耐熱性を示した。 From Table 1, the film produced using the resin composition for display substrates obtained from Example 1 and Examples 3 to 6 showed higher heat resistance than Comparative Example 1.
（自己支持性評価）
　実施例１乃至６および比較例１より得られたディスプレイ基板用樹脂組成物をドクターブレードでガラス基板上に塗布し、実施例１乃至２および比較例１は１２０℃で１０分間、続いて２４０℃で１０分間、続いて３００℃で３０分間ベークを行い、実施例３乃至６は１２０℃で３０分間、続いて１５０℃で３０分間、続いて１８０℃で３０分間、続いて２１０℃で３０分間、続いて２４０℃で３０分間、続いて３００℃で２０分間、続いて４００℃で６０分間、窒素雰囲気下でベークを行って得られた膜について、ガラス基板から当該膜を剥離する際、および剥離したフィルムを手で曲げたり引っ張ったりしたときのフィルムの壊れやすさ（クラック、ひび、破れなど）を目視で確認することにより自己支持性を評価した。その結果を表２に示す。 (Self-supporting evaluation)
The resin compositions for display substrates obtained from Examples 1 to 6 and Comparative Example 1 were applied onto a glass substrate with a doctor blade. Examples 1 to 2 and Comparative Example 1 were at 120 ° C. for 10 minutes, and subsequently at 240 ° C. Bake for 10 minutes at 300 ° C. for 30 minutes, and Examples 3 to 6 were 120 ° C. for 30 minutes, followed by 150 ° C. for 30 minutes, followed by 180 ° C. for 30 minutes, followed by 210 ° C. for 30 minutes. A film obtained by baking at 240 ° C. for 30 minutes, subsequently at 300 ° C. for 20 minutes, then at 400 ° C. for 60 minutes in a nitrogen atmosphere, when peeling the film from the glass substrate, and The self-supporting property was evaluated by visually checking the fragility (crack, crack, tear, etc.) of the film when the peeled film was bent or pulled by hand. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000034
　表２より比較例１は剛直性が高くなり、フィルムが脆く、ガラス基板から剥離する際にフィルムにクラック、破れが生じ、また剥離したフィルムも割れやすいため、ディスプレイ基板として膜強度が不十分であった。これに対し、実施例１乃至６より得られたディスプレイ基板用樹脂組成物を用いて作製した膜は、ガラス基板から剥離する際にフィルムにクラック、破れが生じにくく、また、剥離したフィルムも割れにくく膜強度が十分高く、厚さ１１μｍ乃至１５μｍの均一な自己支持性を有する膜を形成することができた。 From Table 2, Comparative Example 1 has high rigidity, the film is brittle, the film is cracked and torn when peeled from the glass substrate, and the peeled film is also easily broken, so the film strength is insufficient as a display substrate. there were. On the other hand, the film produced using the resin composition for display substrates obtained from Examples 1 to 6 is not easily cracked or broken when peeled from the glass substrate, and the peeled film is also cracked. It was difficult to form a film having a sufficiently high film strength and a uniform self-supporting thickness of 11 μm to 15 μm.
（線膨張係数評価）
　実施例１乃至６および比較例１より得られたディスプレイ基板用樹脂組成物をドクターブレードでガラス基板上に塗布し、実施例１乃至２および比較例１は１２０℃で１０分間、続いて２４０℃で１０分間、続いて３００℃で３０分間ベークを行い、実施例３乃至６は１２０℃で３０分間、続いて１５０℃で３０分間、続いて１８０℃で３０分間、続いて２１０℃で３０分間、続いて２４０℃で３０分間、続いて３００℃で２０分間、続いて４００℃で６０分間、窒素雰囲気下でベークを行って得られた膜について、ＴＭＡ－６０（島津製作所社製）を用いて、５０℃から４００℃まで１０℃／分の条件で昇温して線膨張係数を測定した。なお、線膨張係数は低温（５０℃～２５０℃）側と高温（２５０℃～４００℃）側の係数で示した。その結果を表３に示す。 (Evaluation of linear expansion coefficient)
The resin compositions for display substrates obtained from Examples 1 to 6 and Comparative Example 1 were applied onto a glass substrate with a doctor blade. Examples 1 to 2 and Comparative Example 1 were at 120 ° C. for 10 minutes, and subsequently at 240 ° C. Bake for 10 minutes at 300 ° C. for 30 minutes, and Examples 3 to 6 were 120 ° C. for 30 minutes, followed by 150 ° C. for 30 minutes, followed by 180 ° C. for 30 minutes, followed by 210 ° C. for 30 minutes. Then, TMA-60 (manufactured by Shimadzu Corporation) was used for the film obtained by baking at 240 ° C. for 30 minutes, subsequently at 300 ° C. for 20 minutes, and subsequently at 400 ° C. for 60 minutes in a nitrogen atmosphere. The linear expansion coefficient was measured by raising the temperature from 50 ° C. to 400 ° C. under the condition of 10 ° C./min. The linear expansion coefficient is indicated by a coefficient on the low temperature (50 ° C. to 250 ° C.) side and on the high temperature (250 ° C. to 400 ° C.) side. The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000035
　表３より実施例１乃至６より得られたディスプレイ基板用樹脂組成物を用いて作製した膜は、ディスプレイ基板として適度な線膨張係数を示した。これに対し、比較例１は自己支持膜が得られないため測定できなかった。 From Table 3, the film produced using the resin composition for display substrates obtained from Examples 1 to 6 exhibited an appropriate linear expansion coefficient as a display substrate. In contrast, Comparative Example 1 could not be measured because a self-supporting film could not be obtained.

Claims (29)

  1. 下記式（１）で表される構造単位及び式（３）で表される構造単位を含むポリアミック酸又は下記式（２）で表される構造単位及び式（４）で表される構造単位を含むポリイミドを含有するディスプレイ基板用樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     ［式（１）乃至式（４）中、
    　Ｘ１は芳香族基と２つ以上のカルボニル基を有する４価の有機基を表し、
    　Ｙ１は２価の芳香族基又は脂肪族基を表し、
    　Ｙ２はフルオレン骨格を有する２価の芳香族基を表し、
    　ｎ及びｍは自然数を表す。］     A structural unit represented by the following formula (1) and a polyamic acid containing a structural unit represented by the formula (3) or a structural unit represented by the following formula (2) and a structural unit represented by the formula (4) The resin composition for display substrates containing the containing polyimide.
    Figure JPOXMLDOC01-appb-C000001
     [In Formula (1) thru | or Formula (4),
    X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups,
    Y 1 represents a divalent aromatic group or aliphatic group,
    Y 2 represents a divalent aromatic group having a fluorene skeleton,
    n and m represent natural numbers. ]
  2. 前記Ｙ２が下記式（５）で表される基を表す、請求項１に記載のディスプレイ基板用樹脂組成物。
    Figure JPOXMLDOC01-appb-C000002
     （式中、
    　Ｒ０乃至Ｒ７は、それぞれ独立して、水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基、カルボキシル基、Ｗ１で置換されていてもよいフェニル基、Ｗ１で置換されていてもよいナフチル基、Ｗ１で置換されていてもよいチエニル基又はＷ１で置換されていてもよいフリル基を表し、
    　Ｗ１は、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基又はカルボキシル基を表す。なお、○は結合手を表す。）     The resin composition for display substrates according to claim 1, wherein Y 2 represents a group represented by the following formula (5).
    Figure JPOXMLDOC01-appb-C000002
     (Where
    R 0 to R 7 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom. , nitro group, formyl group, cyano group, carboxyl group, W 1 with an optionally substituted phenyl group, W 1 with an optionally substituted naphthyl group, W 1 with an optionally substituted thienyl group or W Represents a furyl group optionally substituted by 1 ,
    W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group. Represents a group. In addition, (circle) represents a bond. )
  3. 前記Ｙ２が下記式（５ａ）で表される、請求項３に記載のディスプレイ基板用樹脂組成物。　　
    Figure JPOXMLDOC01-appb-C000003
     （式中、○は結合手を表す。）     The resin composition for display substrates according to claim 3, wherein Y 2 is represented by the following formula (5a).
    Figure JPOXMLDOC01-appb-C000003
     (In the formula, ○ represents a bond.)
  4. 前記Ｙ１が下記式（６）で表される、請求項１乃至請求項４のうちいずれか１項に記載のディスプレイ基板用樹脂組成物。
    Figure JPOXMLDOC01-appb-C000004
     （式中、
    　Ｒ８乃至Ｒ１１は、それぞれ独立して、水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基、カルボキシル基、Ｗ１で置換されていてもよいフェニル基、Ｗ１で置換されていてもよいナフチル基、Ｗ１で置換されていてもよいチエニル基又はＷ１で置換されていてもよいフリル基を表し、
    　Ｗ１は、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基又はカルボキシル基を表し、
    　ｑは１又は２の整数を表す。なお、○は結合手を表す。）     The resin composition for display substrates according to claim 1, wherein Y 1 is represented by the following formula (6).
    Figure JPOXMLDOC01-appb-C000004
     (Where
    R 8 to R 11 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom. , nitro group, formyl group, cyano group, carboxyl group, W 1 with an optionally substituted phenyl group, W 1 with an optionally substituted naphthyl group, W 1 with an optionally substituted thienyl group or W Represents a furyl group optionally substituted by 1 ,
    W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group. Represents a group,
    q represents an integer of 1 or 2. In addition, (circle) represents a bond. )
  5. 前記式（６）で表される２価の芳香族基がフェニレンジアミンから誘導されたものである、請求項４に記載のディスプレイ基板用樹脂組成物。 The resin composition for display substrates according to claim 4, wherein the divalent aromatic group represented by the formula (6) is derived from phenylenediamine.
  6. 前記Ｒ８乃至Ｒ１１が水素原子を表す、請求項５に記載のディスプレイ基板用樹脂組成物。 The resin composition for display substrates according to claim 5, wherein R 8 to R 11 represent hydrogen atoms.
  7. 前記Ｘ１は下記式（７）で表される基、式（８）で表される基又はこれら双方の基を表す、請求項１乃至請求項６のうちいずれか１項に記載のディスプレイ基板用樹脂組成物。
    Figure JPOXMLDOC01-appb-C000005
     （式（７）及び式（８）中、
    　Ｒ1２乃至Ｒ２３は、それぞれ独立して、水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基、カルボキシル基、Ｗ１で置換されていてもよいフェニル基、Ｗ１で置換されていてもよいナフチル基、Ｗ１で置換されていてもよいチエニル基又はＷ１で置換されていてもよいフリル基を表し、
    　Ｗ１は、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のハロアルキル基、炭素原子数１乃至１０のアルコキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、ホルミル基、シアノ基又はカルボキシル基を表し、
    　Ｚ1及びＺ２は、それぞれ独立して、－ＮＨ－、－ＮＺ３－又は酸素原子を表し、
    　Ｚ３は、炭素原子数１乃至１０のアルキル基を表し、
    　ｐは１又は２の整数を表す。なお、○は結合手を表す。）     The display substrate according to any one of claims 1 to 6, wherein X 1 represents a group represented by the following formula (7), a group represented by the formula (8), or both groups. Resin composition.
    Figure JPOXMLDOC01-appb-C000005
     (In Formula (7) and Formula (8),
    R 12 to R 23 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, or a halogen atom. , nitro group, formyl group, cyano group, carboxyl group, W 1 with an optionally substituted phenyl group, W 1 with an optionally substituted naphthyl group, W 1 with an optionally substituted thienyl group or W Represents a furyl group optionally substituted by 1 ,
    W 1 is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, or a carboxyl group. Represents a group,
    Z 1 and Z 2 each independently represent —NH—, —NZ 3 — or an oxygen atom,
    Z 3 represents an alkyl group having 1 to 10 carbon atoms,
    p represents an integer of 1 or 2. In addition, (circle) represents a bond. )
  8. 前記ｐが２の整数を表す、請求項７に記載のディスプレイ基板用樹脂組成物。 The resin composition for display substrates according to claim 7, wherein the p represents an integer of 2.
  9. 前記Ｒ1２乃至Ｒ２３が水素原子を表す、請求項８に記載のディスプレイ基板用樹脂組成物。 The resin composition for display substrates according to claim 8, wherein R 12 to R 23 represent hydrogen atoms.
  10. 　前記ポリアミック酸が更に式（９）で表される構造単位を含む、請求項１乃至請求項９のいずれか１項に記載のディスプレイ基板用樹脂組成物。
    Figure JPOXMLDOC01-appb-C000006
     ［式（９）中、
    　Ｘ１は芳香族基と２つ以上のカルボニル基を有する４価の有機基を表し、
    　Ｙ３はエーテル結合を有する２価の基を表し、
    　ｌは自然数を表す。］     The resin composition for display substrates of any one of Claims 1 thru | or 9 in which the said polyamic acid contains the structural unit further represented by Formula (9).
    Figure JPOXMLDOC01-appb-C000006
     [In Formula (9),
    X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups,
    Y 3 represents a divalent group having an ether bond,
    l represents a natural number. ]
  11. 　前記ポリイミドが更に式（１０）で表される構造単位を含む、請求項１乃至請求項９のいずれか１項に記載のディスプレイ基板用樹脂組成物。
    Figure JPOXMLDOC01-appb-C000007
     ［式（１０）中、
    　Ｘ１は芳香族基と２つ以上のカルボニル基を有する４価の有機基を表し、
    　Ｙ３はエーテル結合を有する２価の基を表し、
    　ｌは自然数を表す。］     The resin composition for display substrates of any one of Claims 1 thru | or 9 in which the said polyimide further contains the structural unit represented by Formula (10).
    Figure JPOXMLDOC01-appb-C000007
     [In the formula (10),
    X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups,
    Y 3 represents a divalent group having an ether bond,
    l represents a natural number. ]
  12. 前記式（１）中のｎと前記式（３）中のｍとがｎ／（ｎ＋ｍ）≧６０％の関係である、請求項１乃至請求項１１のいずれか１項に記載のディスプレイ基板用樹脂組成物。 12. The display substrate according to claim 1, wherein n in the formula (1) and m in the formula (3) satisfy a relationship of n / (n + m) ≧ 60%. Resin composition.
  13. 前記式（２）中のｎと前記式（４）中のｍとがｎ／（ｎ＋ｍ）≧６０％の関係である、請求項１乃至請求項１１のいずれか１項に記載のディスプレイ基板用樹脂組成物。 12. The display substrate according to claim 1, wherein n in the formula (2) and m in the formula (4) have a relationship of n / (n + m) ≧ 60%. Resin composition.
  14. さらに架橋剤を含む、請求項１乃至請求項１３のいずれか１項に記載のディスプレイ基板用樹脂組成物。 Furthermore, the resin composition for display substrates of any one of Claims 1 thru | or 13 containing a crosslinking agent.
  15. 前記架橋剤が２つ以上のエポキシ基を有する化合物である、請求項１４に記載のディスプレイ基板用樹脂組成物。 The resin composition for display substrates of Claim 14 whose said crosslinking agent is a compound which has a 2 or more epoxy group.
  16. 前記架橋剤が芳香族基を有する化合物である、請求項１５に記載のディスプレイ基板用樹脂組成物。 The resin composition for display substrates of Claim 15 whose said crosslinking agent is a compound which has an aromatic group.
  17. 前記架橋剤が６つ以下のエポキシ基を有する化合物であって、かつ該化合物はエポキシ基と芳香族基とを結合する炭素原子数１乃至１０のアルキル基を有する、請求項１６に記載のディスプレイ基板用樹脂組成物。 The display according to claim 16, wherein the cross-linking agent is a compound having 6 or less epoxy groups, and the compound has an alkyl group having 1 to 10 carbon atoms for bonding an epoxy group and an aromatic group. Resin composition for substrates.
  18. 前記ポリアミック酸又はポリイミド１００質量部に対して、前記架橋剤が２０質量部以下である、請求項１４乃至請求項１７のうちいずれか１項に記載のディスプレイ基板用樹脂組成物。 The resin composition for display substrates of any one of Claims 14 thru | or 17 whose said crosslinking agent is 20 mass parts or less with respect to 100 mass parts of said polyamic acids or a polyimide.
  19. 請求項１乃至請求項１８のいずれか１項に記載のディスプレイ基板用樹脂組成物が少なくとも１種の溶剤に溶解していることを特徴とする、ワニス。 A varnish, wherein the resin composition for a display substrate according to any one of claims 1 to 18 is dissolved in at least one solvent.
  20. 請求項１９に記載のワニスを用いて２３０℃以上で焼成することにより得られる、硬化膜。 The cured film obtained by baking at 230 degreeC or more using the varnish of Claim 19.
  21. 基板上に請求項２０に記載の硬化膜からなる層を少なくとも一層備える、構造体。 A structure comprising at least one layer of the cured film according to claim 20 on a substrate.
  22. 下記式（１）で表される構造単位及び式（３）で表される構造単位を含むポリアミック酸。
    Figure JPOXMLDOC01-appb-C000008
     ［式（１）及び式（３）中、
    　Ｘ１は芳香族基と２つ以上のカルボニル基を有する４価の有機基を表し、
    　Ｙ１は２価の芳香族基又は脂肪族基を表し、
    　Ｙ２はフルオレン骨格を有する２価の芳香族基を表し、
    　ｎ及びｍは自然数を表す。］     A polyamic acid comprising a structural unit represented by the following formula (1) and a structural unit represented by the formula (3).
    Figure JPOXMLDOC01-appb-C000008
     [In Formula (1) and Formula (3),
    X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups,
    Y 1 represents a divalent aromatic group or aliphatic group,
    Y 2 represents a divalent aromatic group having a fluorene skeleton,
    n and m represent natural numbers. ]
  23. 更に式（９）で表される構造単位を含む請求項２２に記載のポリアミック酸。
    Figure JPOXMLDOC01-appb-C000009
     ［式（９）中、
    　Ｘ１は芳香族基と２つ以上のカルボニル基を有する４価の有機基を表し、
    　Ｙ３はエーテル結合を有する２価の基を表し、
    　ｌは自然数を表す。］     Furthermore, the polyamic acid of Claim 22 containing the structural unit represented by Formula (9).
    Figure JPOXMLDOC01-appb-C000009
     [In Formula (9),
    X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups,
    Y 3 represents a divalent group having an ether bond,
    l represents a natural number. ]
  24. 下記式（２）で表される構造単位及び式（４）で表される構造単位を含むポリイミド。
    Figure JPOXMLDOC01-appb-C000010
     ［式（２）及び式（４）中、
    　Ｘ１は芳香族基と２つ以上のカルボニル基を有する４価の有機基を表し、
    　Ｙ１は２価の芳香族基又は脂肪族基を表し、
    　Ｙ２はフルオレン骨格を有する２価の芳香族基を表し、
    　ｎ及びｍは自然数を表す。］     A polyimide containing a structural unit represented by the following formula (2) and a structural unit represented by the formula (4).
    Figure JPOXMLDOC01-appb-C000010
     [In Formula (2) and Formula (4),
    X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups,
    Y 1 represents a divalent aromatic group or aliphatic group,
    Y 2 represents a divalent aromatic group having a fluorene skeleton,
    n and m represent natural numbers. ]
  25. 更に式（１０）で表される構造単位を含む請求項２４に記載のポリイミド。
    Figure JPOXMLDOC01-appb-C000011
     ［式（１０）中、
    　Ｘ１は芳香族基と２つ以上のカルボニル基を有する４価の有機基を表し、
    　Ｙ３はエーテル結合を有する２価の基を表し、
    　ｌは自然数を表す。］     Furthermore, the polyimide of Claim 24 containing the structural unit represented by Formula (10).
    Figure JPOXMLDOC01-appb-C000011
     [In the formula (10),
    X 1 represents a tetravalent organic group having an aromatic group and two or more carbonyl groups,
    Y 3 represents a divalent group having an ether bond,
    l represents a natural number. ]
  26. 請求項２２又は請求項２３に記載のポリアミック酸と架橋剤とを含む組成物。 A composition comprising the polyamic acid according to claim 22 or 23 and a crosslinking agent.
  27. 請求項２４又は請求項２５に記載のポリイミドと架橋剤とを含む組成物。 A composition comprising the polyimide according to claim 24 or 25 and a crosslinking agent.
  28. 請求項２６又は請求項２７に記載の組成物が少なくとも１種の溶剤に溶解していることを特徴とする、ワニス。 A varnish, wherein the composition according to claim 26 or 27 is dissolved in at least one solvent.
  29. 請求項２８に記載のワニスを用いて２３０℃以上で焼成することにより得られる、硬化膜。 The cured film obtained by baking at 230 degreeC or more using the varnish of Claim 28.
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