WO2017221776A1 - ポリイミド樹脂、ポリイミド樹脂組成物、それを用いたタッチパネルおよびその製造方法、カラーフィルタおよびその製造方法、液晶素子およびその製造方法、有機ｅｌ素子およびその製造方法 - Google Patents

ポリイミド樹脂、ポリイミド樹脂組成物、それを用いたタッチパネルおよびその製造方法、カラーフィルタおよびその製造方法、液晶素子およびその製造方法、有機ｅｌ素子およびその製造方法 Download PDF

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WO2017221776A1
WO2017221776A1 PCT/JP2017/021902 JP2017021902W WO2017221776A1 WO 2017221776 A1 WO2017221776 A1 WO 2017221776A1 JP 2017021902 W JP2017021902 W JP 2017021902W WO 2017221776 A1 WO2017221776 A1 WO 2017221776A1
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polyimide resin
group
polyimide
film
resin film
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PCT/JP2017/021902
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English (en)
French (fr)
Japanese (ja)
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佐伯昭典
河原佳奈
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東レ株式会社
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Priority to KR1020187033962A priority Critical patent/KR102134263B1/ko
Priority to CN201780035474.1A priority patent/CN109348718B/zh
Priority to JP2017532182A priority patent/JP6292351B1/ja
Publication of WO2017221776A1 publication Critical patent/WO2017221776A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • 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
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G02F1/133516—Methods for their manufacture, e.g. printing, electro-deposition or photolithography
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/842—Containers
    • H10K50/8426—Peripheral sealing arrangements, e.g. adhesives, sealants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass

Definitions

  • the present invention relates to a polyimide resin, a polyimide resin composition, a touch panel using the same, a manufacturing method thereof, a color filter and a manufacturing method thereof, a liquid crystal element and a manufacturing method thereof, an organic EL element and a manufacturing method thereof.
  • Organic film is more flexible than glass, has the characteristics of being hard to break and lightweight. Recently, the movement to make the display flexible by replacing the substrate of the flat panel display with an organic film has been activated.
  • the resin used for the organic film examples include polyester, polyamide, polyimide, polycarbonate, polyethersulfone, acrylic, and epoxy.
  • polyimide is a highly heat-resistant resin and is suitable as a display substrate.
  • wholly aromatic polyimides that are particularly excellent in heat resistance are derived from aromatic dianhydrides and aromatic diamines. All aromatic polyimides have an absorption band in the visible light wavelength region derived from intramolecular and intermolecular charge transfer complexes. Therefore, a film made of wholly aromatic polyimide has the property of coloring yellow to brown, and the property of having high birefringence. Due to these properties, the wholly aromatic polyimide cannot be used as a display substrate that requires high transparency and low birefringence.
  • Patent Document 1 discloses that polyimides obtained from alicyclic acid dianhydrides and various aromatic or alicyclic diamines have high transparency and low birefringence.
  • Patent Document 2 discloses that a polyimide obtained from 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 2,2′-bis (trifluoromethyl) benzidine (TFMB) has high transparency. Have a high Tg.
  • Patent Document 3 discloses an alicyclic acid dianhydride and an amine having a hydroxyl group, specifically 2,2-bis [3- (3-aminobenzamido) -4-hydroxyphenyl] hexafluoropropane (HFHA). It is described that the polyimide obtained from the above has heat resistance, light transmittance, and low birefringence.
  • HFHA 2,2-bis [3- (3-aminobenzamido) -4-hydroxyphenyl] hexafluoropropane
  • Patent Document 4 discloses that a polyimide obtained from tetracarboxylic acid and diamine, each containing an aromatic fluorine compound and an alicyclic compound, has high transparency, high heat resistance, low birefringence, and It is described that the coefficient of linear thermal expansion (CTE) is low.
  • CTE linear thermal expansion
  • the polyimide described in Patent Document 3 has a disclosure that laser peeling is possible, but has a problem of high CTE.
  • an object of the present invention is to provide a polyimide resin having excellent light transmittance, low birefringence, low linear thermal expansibility, and laser peelability.
  • the present invention is a polyimide resin characterized in that the structural unit represented by the general formula (1) is a main component and the structural unit represented by the general formula (2) is contained in an amount of 2 mol% to 30 mol% of the total structural units. It is.
  • R 1 is a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure is directly or crosslinked.
  • 4 represents a tetravalent organic group having 4 to 40 carbon atoms connected to each other via R.
  • R 2 represents a divalent organic group represented by the general formula (3), and R 3 represents the following general formula ( 4) or (5) is represented.
  • R 4 to R 11 each independently represents a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 3 carbon atoms which may be substituted with a halogen atom.
  • X 1 represents a direct bond, an oxygen atom And a divalent crosslinked structure selected from a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms which may be substituted with a halogen atom, an ester bond, an amide bond or a sulfide bond.
  • the present invention it is possible to provide a polyimide resin film having excellent light transmittance, low birefringence, low linear thermal expansibility, and laser peelability.
  • the polyimide resin of the present invention can be suitably used as a support substrate for displays such as touch panels, color filters, liquid crystal elements, and organic EL elements.
  • displays such as touch panels, color filters, liquid crystal elements, and organic EL elements.
  • Sectional drawing which shows an example of the touchscreen containing the polyimide resin film which concerns on embodiment of this invention
  • Sectional drawing which shows an example of the touchscreen containing the polyimide resin film which concerns on embodiment of this invention
  • Sectional drawing which shows an example of the color filter containing the polyimide resin film which concerns on embodiment of this invention
  • Sectional drawing which shows an example of the color filter containing the polyimide resin film which concerns on embodiment of this invention
  • Sectional drawing which shows an example of the liquid crystal element containing the polyimide resin film which concerns on embodiment of this invention
  • Sectional drawing which shows an example of the organic EL element containing the polyimide resin film which concerns on embodiment of this invention
  • the polyimide resin according to the embodiment of the present invention is mainly composed of the structural unit represented by the general formula (1), and the structural unit represented by the general formula (2) is 2 mol% or more and 30 mol% or less of the total structural units. Including.
  • R 1 is a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure directly or via a crosslinked structure.
  • R 2 represents a divalent organic group represented by the general formula (3).
  • R 3 represents the following general formula (4) or (5).
  • R 4 to R 11 each independently represents a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 3 carbon atoms which may be substituted with a halogen atom.
  • X 1 is selected from a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms which may be substituted with a halogen atom, an ester bond, an amide bond or a sulfide bond.
  • a cross-linked structure is selected from a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms which may be substituted with a halogen atom, an ester bond, an amide bond or a sulfide bond.
  • the structural units represented by the general formulas (1) and (2) are repeating structural units in the polyimide resin according to the embodiment of the present invention. Hereinafter, these structural units are referred to as “repeating structural units” or simply Sometimes called “repeat unit”.
  • the main component means that the structural unit represented by the general formula (1) has 50 mol% or more of the total structural unit of the polymer.
  • the CTE of the polyimide resin is lowered.
  • membrane using the polyimide resin on a support substrate can be reduced.
  • all the structural units are all the structural units which comprise the polyimide which has a repeating unit represented by General formula (1) and (2). Specifically, it is the total amount (mol basis) of the repeating units represented by the general formulas (1) and (2).
  • the polyimide also includes a structure other than the repeating units represented by the general formulas (1) and (2), the repeating unit represented by the general formulas (1) and (2) and the general formula (1) and It is the total amount (mol basis) with the structure other than the repeating unit represented by (2).
  • the content of the structural unit represented by the general formula (1) is 70 mol% or more of the total structural unit of the polymer.
  • the CTE of polyimide can be kept low while providing good laser peelability.
  • the content of the repeating structural unit represented by the general formula (2) is more preferably 5 mol% or more and 30 mol% or less.
  • R 1 in the general formulas (1) and (2) represents the structure of the acid component, and is a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or And a tetravalent organic group having 4 to 40 carbon atoms in which organic groups having a monocyclic alicyclic structure are connected to each other directly or via a crosslinked structure.
  • some hydrogen atoms may be substituted with halogen.
  • the acid dianhydride having an alicyclic structure that can be used in the present invention is not particularly limited, but 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclo Pentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-tetra Methyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2, 3,4-cyclobutanetetracarboxylic dianhydride, 2,3,4-tricarboxycyclopentylacetic acid dianhydride, 1,2,3,4-cycloheptanetetracarboxylic dianhydride, 2,3,4,5 -Tetra Hydrofurantetrac
  • R 1 in the general formulas (1) and (2) is preferably at least one selected from structures represented by the following general formulas (6) to (10).
  • R 12 to R 55 each independently represents a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 3 carbon atoms which may be substituted with a halogen atom.
  • R 1 is an acid dianhydride that gives a structure represented by the following chemical formulas (11) to (13) from the viewpoint of being commercially available and easy to obtain and from the viewpoint of reactivity with the diamine compound.
  • 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride, 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride Things are preferred.
  • An acid dianhydride that gives a structure represented by the chemical formula (11) is a product name “PMDA-HH” from Wako Pure Chemical Industries, Ltd., and an acid dianhydride that gives a structure represented by the chemical formula (12) is “ It is commercially available as “PMDA-HS”.
  • these acid dianhydrides can be used individually or in combination of 2 or more types.
  • R 2 in the general formula (1) represents the structure of the diamine component, and is represented by the general formula (3).
  • the diamine giving the structure represented by the general formula (3) is not particularly limited, but 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 2,2- Bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4 , 4'-diaminodiphenyl sulfide, benzidine, 2,2'-bis (trifluoromethyl) benzidine, 3,3'-bis (trifluoromethyl) benzidine, 2,2'-dimethylbenzidine, 3,3'-dimethyl Benzidine, 2,2 ', 3,3'-tetramethylbenzidine, 4,4-diaminobenzanily , 4-amin
  • R 2 is preferably at least one selected from, for example, structures represented by the chemical formulas (14) to (17) from the viewpoint of availability, transparency of the polyimide resin, and low CTE properties. .
  • R 56 to R 87 each independently represents a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 3 carbon atoms which may be substituted with a halogen atom.
  • R 2 is preferably a diamine that gives a structure represented by the following chemical formulas (18) to (21).
  • the diamine represented by the chemical formula (18) is 2,2'-dimethylbenzidine (m-TB). This is preferable because Tg of polyimide can be improved and CTE can be reduced.
  • the diamine that gives the structure represented by the chemical formula (19) is 2,2'-bis (trifluoromethyl) benzidine (TFMB). This is preferable because the transparency of polyimide can be improved, birefringence can be reduced, and CTE can be further reduced.
  • TFMB 2,2'-bis (trifluoromethyl) benzidine
  • the diamine that gives the structure represented by the chemical formula (20) is 4,4′-diaminodiphenyl sulfide (4,4′-DDS). This is preferable because the Tg of polyimide can be improved.
  • the diamine that gives the structure represented by the chemical formula (21) is 4,4'-diaminobenzanilide (DABA). This is preferable because residual stress generated between the polyimide film and the inorganic film can be reduced and substrate warpage can be suppressed.
  • DABA 4,4'-diaminobenzanilide
  • TFMB is particularly preferable because it can satisfy all of high transparency, low birefringence, and low CTE required for a transparent support substrate.
  • R 3 in the general formula (2) represents the structure of the diamine component, and is represented by the general formula (4) or (5).
  • the oxazole ring of the general formula (5) is generated by dehydration ring closure from the structure represented by the general formula (4).
  • the polyimide resin according to the embodiment of the present invention may contain other structural units as long as the effects of the present invention are not hindered.
  • other structural units include polyimide, which is a polycyclic amide dehydration ring, polybenzoxazole, a polyhydroxyamide dehydration ring closure, and the like.
  • acid dianhydrides used for other structural units include aromatic acid dianhydrides and aliphatic acid dianhydrides.
  • the aromatic dianhydride is not particularly limited, but pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4 ′ -Biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-terphenyltetracarboxylic dianhydride, 4,4 ' -Oxydiphthalic dianhydride, 3,4'-oxydiphthalic dianhydride, 3,3'-oxydiphthalic dianhydride, diphenylsulfone-3,3 ', 4,4'-tetracarboxylic dianhydride, benzophenone ⁇ 3,3 ′, 4,4′-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis
  • the aliphatic acid dianhydride is not particularly limited, but 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride and derivatives thereof, etc. Is mentioned.
  • diamine compounds used for other structural units include aromatic diamine compounds, alicyclic diamine compounds, and aliphatic diamine compounds.
  • the aromatic diamine compound is not particularly limited, but 1,4-bis (4-aminophenoxy) benzene, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine Bis ⁇ 4- (4-aminophenoxyphenyl) ⁇ sulfone, bis ⁇ 4- (3-aminophenoxyphenyl) ⁇ sulfone, bis (4-aminophenoxy) biphenyl, bis ⁇ 4- (4-aminophenoxy) phenyl ⁇ Ether, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexa Fluoropropane, 3-aminophenyl-4-aminobenzenesulfonate, 4-aminophenyl-4-amino Benzene,
  • the alicyclic diamine compound is not particularly limited, but is cyclobutanediamine, isophoronediamine, bicyclo [2.2.1] heptanebismethylamine, tricyclo [3.3.1.13,7] decane-1,3- Diamine, 1,2-cyclohexyldiamine, 1,3-cyclohexyldiamine, 1,4-cyclohexyldiamine, 4,4′-diaminodicyclohexylmethane, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 3, 3′-diethyl-4,4′-diaminodicyclohexylmethane, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodicyclohexylmethane, 3,3 ′, 5,5′-tetraethyl-4, 4'-diaminodicyclohexylmethane, 3,5-
  • the aliphatic diamine compound is not particularly limited, but ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1 , 8-diaminooctane, 1,9-diaminononane, alkylenediamines such as 1,10-diaminodecane, bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, etc.
  • Ethylene glycol diamines and 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, ⁇ , ⁇ -bis (3-aminopropyl) poly Examples include siloxane diamines such as dimethylsiloxane.
  • aromatic diamine compounds alicyclic diamine compounds, or aliphatic diamine compounds can be used alone or in combination of two or more.
  • the polyimide resin according to the embodiment of the present invention further has a structural unit represented by the general formula (22).
  • R 1 is as described above.
  • X 2 and X 3 may be the same or different, and are composed of an aromatic ring, an aliphatic ring, a chain hydrocarbon group, or a combination thereof, or an amide group, ester group, ether group, alkylene
  • the structure is a combination of one or more groups selected from the group consisting of a group, an oxyalkylene group, a vinylene group and a haloalkylene group.
  • the structural unit represented by the general formula (22) preferably contains a structural unit represented by the following general formula (23).
  • the diamine that gives this structure is 3-aminophenyl-4-aminobenzenesulfonate.
  • R 1 is a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure directly or via a crosslinked structure.
  • the polyimide resin which concerns on embodiment of this invention contains the structural unit represented by General formula (23) in the range of 1 mol% or more and 25 mol% or less, and contains in the range of 3 mol% or more and 20 mol% or less. Is more preferable.
  • the structural unit represented by the general formula (23) within the above range, it is possible to improve transparency and glass transition temperature while maintaining the mechanical properties and flexibility of the polyimide resin.
  • the polyimide resin according to the embodiment of the present invention preferably has a structure represented by the general formula (24) in the acid dianhydride residue and / or diamine residue constituting the polyimide.
  • the polyimide resin has a structure represented by the general formula (24)
  • residual stress generated between the polyimide resin and the inorganic film can be reduced, and substrate warpage can be suppressed.
  • the transparency of the polyimide resin film can be further increased and the birefringence can be further decreased.
  • R 88 and R 89 each independently represent a monovalent organic group having 1 to 20 carbon atoms.
  • m represents an integer of 3 to 200.
  • Examples of the monovalent organic group having 1 to 20 carbon atoms in R 88 and R 89 include a hydrocarbon group, an amino group, an alkoxy group, and an epoxy group.
  • Examples of the hydrocarbon group for R 88 and R 89 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.
  • the alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, t- A butyl group, a pentyl group, a hexyl group, etc. are mentioned.
  • the cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms, and specific examples include a cyclopentyl group and a cyclohexyl group.
  • the aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, and a naphthyl group.
  • Examples of the alkoxy group for R 88 and R 89 include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a phenoxy group, a propenyloxy group, and a cyclohexyloxy group.
  • R 88 and R 89 in the general formula (24) are preferably a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms or an aromatic group having 6 to 10 carbon atoms. This is because the obtained polyimide film has high heat resistance and low residual stress.
  • the monovalent aliphatic hydrocarbon having 1 to 3 carbon atoms is preferably a methyl group
  • the aromatic group having 6 to 10 carbon atoms is preferably a phenyl group.
  • M in the general formula (24) is an integer of 3 to 200, preferably 10 to 200, more preferably 20 to 150, still more preferably 30 to 100, and particularly preferably 30 to 60.
  • m is within the above range, the residual stress of polyimide can be reduced. Moreover, it can suppress that a polyimide film becomes cloudy or the mechanical strength of a polyimide film falls.
  • a polyimide resin having a structure represented by the general formula (24) can be obtained by using a silicone compound represented by the following general formula (25) as a monomer component.
  • a plurality of R 90 are each independently a single bond or a divalent organic group having 1 to 20 carbon atoms
  • a plurality of R 91 , R 92 and R 93 are each independently a carbon
  • L 1 , L 2 and L 3 are each independently an amino group, an acid anhydride group, a carboxyl group, a hydroxy group, an epoxy group, a mercapto group, and R 94.
  • One group selected from the group consisting of R 94 is a monovalent organic group having 1 to 20 carbon atoms.
  • n is an integer of 3 to 200
  • o is an integer of 0 to 197.
  • the divalent organic group having 1 to 20 carbon atoms in R 90 includes an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, and an arylene having 6 to 20 carbon atoms. Groups and the like.
  • the alkylene group having 1 to 20 carbon atoms is preferably an alkylene group having 1 to 10 carbon atoms, and examples thereof include a methylene group, a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.
  • the cycloalkylene group having 3 to 20 carbon atoms is preferably a cycloalkylene group having 3 to 10 carbon atoms, and examples thereof include a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a cycloheptylene group.
  • the arylene group having 6 to 20 carbon atoms is preferably an aromatic group having 3 to 20 carbon atoms, and examples thereof include a phenylene group and a naphthylene group.
  • the divalent organic group having 1 to 20 carbon atoms in R 90 is preferably a divalent aliphatic hydrocarbon having 3 to 20 carbon atoms.
  • each group in R 91 to R 93 includes the same groups as those in R 88 and R 89 described above.
  • the amino group in L 1 , L 2 and L 3 includes not only the amino group itself but also reactive derivatives thereof.
  • the reactive derivative of an amino group include an isocyanate group and a bis (trialkylsilyl) amino group.
  • Specific examples of the compound represented by the general formula (25) when L 1 , L 2 and L 3 are amino groups include X22-1660B-3 (Shin-Etsu Chemical Co., Ltd.), which is an amino-modified methylphenyl silicone at both ends.
  • X22-169A (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,400), X22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd., number-average molecular weight 1,300), both ends amino-modified dimethyl silicone , 600), X22-161B (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,000), KF8012 (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 4,400), BY16-835U (manufactured by Toray Dow Corning Co., Ltd .; number average molecular weight 900) ), Silaplane FM3311 (manufactured by Chisso; number average molecular weight 1000).
  • the acid anhydride groups in L 1 , L 2 and L 3 include not only the acid anhydride group itself but also reactive derivatives thereof.
  • the reactive derivative of the acid anhydride group include an acid esterified product of a carboxyl group and an acid chloride of the carboxyl group.
  • Specific examples in which L 1 , L 2 and L 3 are acid anhydride groups include groups represented by the following formulas.
  • Specific examples of the compound represented by the general formula (25) when L 1 , L 2 and L 3 are acid anhydride groups include X22-168AS (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,000).
  • X22-168A manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 2,000
  • X22-168B manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,200
  • X22-168-P5-8 manufactured by Shin-Etsu Chemical Co., Ltd., number average
  • DMS-Z21 manufactured by Gerest, number average molecular weight 600 to 800
  • Specific examples of the compound represented by the general formula (25) when L 1 , L 2 and L 3 are hydroxy groups include KF-6000 (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 900), KF-6001 ( Shin-Etsu Chemical, number average molecular weight 1,800), KF-6002 (manufactured by Shin-Etsu Chemical, number average molecular weight 3,200), KF-6003 (manufactured by Shin-Etsu Chemical, number average molecular weight 5,000), and the like.
  • KF-6000 manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 900
  • KF-6001 Shin-Etsu Chemical, number average molecular weight 1,800
  • KF-6002 manufactured by Shin-Etsu Chemical, number average molecular weight 3,200
  • KF-6003 manufactured by Shin-Etsu Chemical, number average molecular weight 5,000
  • the compound having a hydroxy group is considered to
  • a specific example of the compound represented by the general formula (25) when L 1 , L 2 and L 3 are epoxy groups is X22-163 (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight) 400), KF-105 (manufactured by Shin-Etsu Chemical, number average molecular weight 980), X22-163A (manufactured by Shin-Etsu Chemical, number average molecular weight 2,000), X22-163B (manufactured by Shin-Etsu Chemical, number average molecular weight 3,500), X22 -163C (manufactured by Shin-Etsu Chemical, number average molecular weight 5,400), both terminal alicyclic epoxy type, X22-169AS (manufactured by Shin-Etsu Chemical, number average molecular weight 1,000), X22-169B (manufactured by Shin-Etsu Chemical, number Average molecular weight 3,400).
  • Specific examples of the compound represented by the general formula (25) when L 1 , L 2 and L 3 are mercapto groups include X22-167B (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,400), X22- 167C (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 4,600) and the like.
  • the compound having a mercapto group is considered to react with other tetracarboxylic dianhydride monomers.
  • L 1 , L 2 and L 3 are each independently selected from the group consisting of an amino group, an acid anhydride group and R 94 from the viewpoint of improving the molecular weight of the polyimide precursor or the heat resistance of the resulting polyimide.
  • each group is independently an amino group.
  • the polyimide resin which concerns on embodiment of this invention is obtained by carrying out the imide ring closure of the polyimide precursor containing the structural unit represented by the following general formula (26), and the structural unit represented by General formula (27). .
  • Y 1 to Y 4 each independently represent a hydrogen atom, a monovalent organic group having 1 to 10 carbon atoms, or a monovalent alkylsilyl group having 1 to 10 carbon atoms.
  • R 1 is a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure directly or via a crosslinked structure.
  • R 2 represents a divalent organic group represented by the above general formula (3).
  • R 3 represents the above general formula (4) or (5).
  • the imidization method is not particularly limited, and examples thereof include thermal imidization and chemical imidization. Among these, thermal imidization is preferable from the viewpoint of heat resistance of the polyimide resin film and transparency in the visible light region.
  • Polyimide precursor resins such as polyamic acid, polyamic acid ester, and polyamic acid silyl ester can be synthesized by a reaction between a diamine compound and an acid dianhydride or a derivative thereof.
  • the derivatives include tetracarboxylic acids of the acid dianhydrides, mono-, di-, tri-, or tetra-esters of the tetracarboxylic acids, acid chlorides, and the like, and specifically include methyl groups, ethyl groups, and n-propyl.
  • the reaction method of the polymerization reaction is not particularly limited as long as the target polyimide precursor resin can be produced, and a known reaction method can be used.
  • a predetermined amount of all diamine components and a solvent are charged into a reactor and dissolved, and then a predetermined amount of acid dianhydride component is charged and the mixture is charged at room temperature to 150 ° C. for 0.5 to 30 hours.
  • Examples include a stirring method.
  • the polyimide resin and polyimide precursor resin according to the embodiment of the present invention may be sealed at both ends with a terminal sealing agent in order to adjust the molecular weight to a preferable range.
  • a terminal sealing agent examples include monoamines and monohydric alcohols.
  • the terminal blocking agent that reacts with the diamine compound include acid anhydrides, monocarboxylic acids, monoacid chloride compounds, monoactive ester compounds, dicarbonates, and vinyl ethers.
  • various organic groups can be introduce
  • Monoamines used for the acid anhydride group end-capping agent include 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-amino.
  • Examples of the monohydric alcohol used as the acid anhydride group terminal blocking agent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3 -Pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, 2-nonanol, 1- Decanol, 2-decanol, 1-undecanol, 2-undecanol, 1-dodecanol, 2-dodecanol, 1-tridecanol, 2-tridecanol, 1-tetradecanol, 2-tetradecanol, 1-pentadecanol, 2- Pentadecanol, 1-hexadecanol, 2 He
  • Examples of the acid anhydride, monocarboxylic acid, monoacid chloride compound and monoactive ester compound used as an amino group terminal blocking agent include phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3- Acid anhydrides such as hydroxyphthalic anhydride, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8- Carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1 Hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mer
  • dicarbonate compound used as the amino group terminal blocking agent examples include di-tert-butyl dicarbonate, dibenzyl dicarbonate, dimethyl dicarbonate, and diethyl dicarbonate.
  • vinyl ether compound used as the amino group-end capping agent examples include chloroformate-tert-butyl, chloroformate-n-butyl, isobutylchloroformate, benzylchloroformate, allylchloroformate, ethylchloroformate, isopropylchloroformate, etc.
  • Isocyanates such as chloroformates, butyl isocyanate, 1-naphthyl isocyanate, octadecyl isocyanate, phenyl isocyanate, butyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, 2-ethylhexyl vinyl ether, isobutyl vinyl ether, isopropyl vinyl ether, n -Propyl vinyl ether, tert-butyl vinyl ether, benzyl vinyl ether and the like.
  • Examples of other compounds used as the amino group-end blocking agent include benzyl chloroformate, benzoyl chloride, fluorenylmethyl chloroformate, 2,2,2-trichloroethyl chloroformate, allyl chloroformate, methanesulfonic acid chloride, Examples thereof include p-toluenesulfonic acid chloride and phenyl isocyanate.
  • the introduction ratio of the acid anhydride group terminal sealing agent is preferably in the range of 0.1 to 60 mol%, particularly preferably 0.5 to 50 mol%, relative to the acid dianhydride component.
  • the introduction ratio of the amino group terminal blocking agent is preferably in the range of 0.1 to 100 mol%, particularly preferably 0.5 to 70 mol%, relative to the diamine component.
  • a plurality of different end groups may be introduced by reacting a plurality of end-capping agents.
  • the end-capping agent introduced into the polyimide precursor resin or the polyimide resin can be easily detected by the following method. For example, by dissolving a polymer having an end capping agent dissolved in an acidic solution and decomposing it into an amine component and an acid anhydride component, which are constituent units of the polymer, this is measured by gas chromatography (GC) or NMR measurement, The end capping agent can be easily detected.
  • the polymer in which the end-capping agent has been introduced can be easily detected directly by pyrolysis gas chromatography (PGC), infrared spectrum, 1 H-NMR spectrum measurement and 13 C-NMR spectrum measurement.
  • PPC pyrolysis gas chromatography
  • the polyimide resin according to the embodiment of the present invention can be mixed with an appropriate component to obtain a polyimide resin composition.
  • the component that may be contained in the polyimide resin composition is not particularly limited, and examples thereof include an ultraviolet absorber, a thermal crosslinking agent, an inorganic filler, a surfactant, an internal release agent, and a colorant.
  • the polyimide resin composition according to the embodiment of the present invention preferably contains an ultraviolet absorber.
  • an ultraviolet absorber it is greatly suppressed that physical properties such as transparency and mechanical properties of polyimide are deteriorated when exposed to sunlight for a long period of time.
  • the ultraviolet absorber is not particularly limited and known ones can be used. From the viewpoints of transparency and non-coloring properties, benzotriazole compounds, benzophenone compounds, and triazine compounds are preferably used.
  • the ultraviolet absorber is preferably a compound having a molecular weight of 1000 or less.
  • the ultraviolet absorber is a low molecular weight compound having a molecular weight of 1000 or less, the light resistance of the resin film can be improved without increasing the haze of the polyimide resin film.
  • the ultraviolet absorber is preferably a compound represented by the general formula (28) or (29).
  • the UV absorber has a high density of aromatic rings in the molecule, thereby improving affinity with polyimide resins having many imide rings and aromatic rings in the molecule, and suppressing an increase in the haze value of the resin film. .
  • the heat resistance of the ultraviolet absorber is improved, sublimation of the ultraviolet absorber can be suppressed even when heated at a high temperature in the process of imidization of the resin.
  • R 95 to R 105 each independently represent a hydrogen atom, a hydroxyl group, a monovalent organic group, or a monovalent organic group bonded through an oxygen atom.
  • Examples of the ultraviolet absorber represented by the general formula (28) include Tinuvin 400 (molecular weight: 640, manufactured by BASF), Tinuvin 405 (molecular weight: 584, manufactured by BASF), Tinuvin 460 (molecular weight: 630, manufactured by BASF), and the like. Can be mentioned.
  • Examples of the ultraviolet absorber represented by the general formula (29) include RUVA-93 (molecular weight: 323, manufactured by Otsuka Chemical), LA-31 (molecular weight: 659, manufactured by ADEKA), and the like.
  • the content of the ultraviolet absorber in the polyimide resin composition is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polyimide resin.
  • light resistance resistance to light, particularly ultraviolet light
  • the polyimide resin composition according to the embodiment of the present invention may contain a thermal crosslinking agent.
  • a thermal crosslinking agent an epoxy compound or a compound having at least two alkoxymethyl groups or methylol groups is preferable. By having at least two of these groups, a crosslinked structure is formed by a condensation reaction with the resin and the same kind of molecules, and the mechanical strength and chemical resistance of the cured film after heat treatment can be improved.
  • Preferred examples of the epoxy compound include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl (glycidyloxypropyl), epoxy group-containing silicone such as siloxane, etc.
  • the present invention is not limited to these at all.
  • Epicron 850-S Epicron HP-4032, Epicron HP-7200, Epicron HP-820, Epicron HP-4700, Epicron EXA-4710, Epicron HP-4770, Epicron EXA-859CRP, Epicron EXA-1514 Epicron EXA-4880, Epicron EXA-4850-150, Epicron EXA-4850-1000, Epicron EXA-4816, Epicron EXA-4822 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Recare Resin BEO-60E, Recare Resin BPO-20E, Rica Resin HBE-100, Portugal Resin DME-100 (above trade name, Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S (above trade name, Adeka Co., Ltd.), PG-10 CG-500, EG-200 (above trade name, manufactured by Osaka Gas Chemical Co., Ltd.), NC-3000, NC-6000 (above trade name, manufactured by Nippon Meth
  • Examples of the compound having at least two alkoxymethyl groups or methylol groups include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, and DML.
  • the content of the thermal crosslinking agent in the polyimide resin composition is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the polyimide resin.
  • the polyimide resin composition contains a thermal crosslinking agent within the above range, the mechanical properties and chemical resistance of the resin can be improved without impairing the transparency of the resin.
  • a coupling agent such as a silane coupling agent or a titanium coupling agent can be added to the polyimide resin composition according to the embodiment of the present invention in order to improve the adhesion to the substrate.
  • the content of the coupling agent in the polyimide resin composition is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyimide resin.
  • the polyimide resin composition according to the embodiment of the present invention may contain an inorganic filler.
  • the inorganic filler include silica fine particles, alumina fine particles, titania fine particles, zirconia fine particles, and the like.
  • the shape of the inorganic filler is not particularly limited, and examples thereof include a spherical shape, an elliptical shape, a flat shape, a rod shape, and a fiber shape.
  • the inorganic filler preferably has a small particle size in order to prevent light scattering.
  • the average particle size of the inorganic filler is preferably 0.5 to 100 nm, more preferably 0.5 to 30 nm.
  • the content of the inorganic filler in the polyimide resin composition is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the polyimide resin.
  • the polyimide resin composition contains an inorganic filler within the above range, the CTE and birefringence of the polyimide resin can be reduced without impairing flexibility.
  • the organoinorganic filler sol may be treated with a silane coupling agent. If the terminal functional group of the silane coupling agent has an epoxy group or an amino group, the affinity with polyamic acid, polyimide or polyimide oxazole is increased by bonding with the carboxylic acid of the polyamic acid, making it more effective. Can be dispersed.
  • Examples of those having an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyl. Examples thereof include diethoxysilane and 3-glycidoxypropyltriethoxysilane.
  • the treatment can be performed by adding a silane coupling agent to an organoinorganic filler sol having a controlled concentration and stirring at room temperature to 80 ° C. for 0.5 to 2 hours.
  • the polyimide resin composition according to the embodiment of the present invention can contain a surfactant.
  • coating a polyimide resin composition can be improved because a polyimide resin composition contains surfactant.
  • the surfactant include fluorine-based surfactants such as Fluorard (trade name, manufactured by Sumitomo 3M Co., Ltd.), Megafuck (trade name, manufactured by DIC Corporation), Sulflon (trade name, manufactured by Asahi Glass Co., Ltd.), and the like. .
  • KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Corporation), Polyflow, Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), BYK (manufactured by Big Chemie Corporation), etc.
  • an organic siloxane surfactant such as polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) can be mentioned.
  • the content of the surfactant in the polyimide resin composition is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the polyimide resin.
  • the polyimide resin composition according to the embodiment of the present invention can contain an internal release agent.
  • the polyimide resin composition contains an internal release agent, the peelability of the polyimide resin film from the support substrate can be improved.
  • the internal mold release agent include long chain fatty acids.
  • the content of the internal release agent in the polyimide resin composition is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polyimide resin.
  • the polyimide resin composition according to the embodiment of the present invention can contain a colorant.
  • the color tone of the polyimide resin film can be adjusted by adding a colorant to the polyimide resin composition.
  • organic pigments are preferable from the viewpoint of heat resistance and transparency. Among them, those having high transparency and excellent light resistance, heat resistance, and chemical resistance are preferable. Specific examples of typical organic pigments are represented by the color index (CI) number, and the following are preferably used, but are not limited thereto.
  • yellow pigments examples include pigment yellow (hereinafter abbreviated as PY) 12, 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 125, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 168, 185, etc. are used.
  • pigment orange (hereinafter abbreviated as PO) 13, 36, 38, 43, 51, 55, 59, 61, 64, 65, 71, or the like is used.
  • red pigments examples include pigment red (hereinafter abbreviated as PR) 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 209, 215, 216, 217, 220. 223, 224, 226, 227, 228, 240, 254, etc. are used.
  • PR pigment red
  • purple pigments examples include pigment violet (hereinafter abbreviated as PV) 19, 23, 29, 30, 32, 37, 40, 50, and the like.
  • PV pigment violet
  • blue pigments examples include Pigment Bull (hereinafter abbreviated as PB) 15, 15: 3, 15: 4, 15: 6, 22, 60, 64, and the like.
  • green pigments examples include pigment green (hereinafter abbreviated as PG) 7, 10, 36, 58, and the like.
  • These pigments may be subjected to surface treatment such as rosin treatment, acidic group treatment, basic treatment, etc., if necessary.
  • a polyimide precursor resin composition is applied on a substrate.
  • the substrate for example, a silicon wafer, ceramics, gallium arsenide, soda lime glass, non-alkali glass, or the like is used.
  • alkali-free glass is preferable from the viewpoint of surface smoothness and dimensional stability during heating.
  • the coating method include a slit die coating method, a spin coating method, a spray coating method, a roll coating method, and a bar coating method, and these methods may be used in combination.
  • the slit die coating method is preferable from the viewpoint of the surface smoothness and film thickness uniformity of the coating film.
  • the substrate coated with the polyimide precursor resin composition is dried to obtain a polyimide precursor resin composition film.
  • a hot plate an oven, an infrared ray, a vacuum chamber, or the like is used.
  • the object to be heated is held and heated directly on the plate or on a jig such as a proxy pin installed on the plate.
  • a material of the proxy pin there is a metal material such as aluminum or sterylene, or a synthetic resin such as polyimide resin or “Teflon” (registered trademark), and any proxy pin may be used.
  • the height of the proxy pin varies depending on the size of the substrate, the type of the resin layer to be heated, the purpose of heating, etc.
  • the height of the proxy pin is preferably about 2 to 12 mm.
  • the heating temperature varies depending on the type and purpose of the object to be heated, and it is preferably performed in the range of room temperature to 180 ° C. for 1 minute to several hours.
  • heating is performed in a range of 180 ° C. or higher and 450 ° C. or lower to convert the polyimide precursor resin composition coating into a polyimide resin coating. And this polyimide resin film is peeled from a board
  • the method include a method of immersing in a chemical solution such as hydrofluoric acid, and a method of irradiating a laser to the interface between the polyimide resin coating and the substrate.
  • the polyimide resin film obtained as described above has high transparency, high heat resistance, low birefringence, low linear thermal expansion, flexibility and good laser releasability, and is suitable as a flexible substrate. Can be used.
  • the transmittance at a wavelength of 400 nm is preferably 85% or more, more preferably 90% or more, and further preferably 95% or more.
  • the glass transition temperature is preferably 280 ° C. or higher, more preferably 300 ° C. or higher, and further preferably 350 ° C. or higher.
  • the birefringence is preferably 0.04 or less, and more preferably 0.03 or less.
  • the residual stress is preferably 35 MPa or less, more preferably 30 MPa or less, and further preferably 25 MPa or less.
  • the laminated body which concerns on embodiment of this invention has an inorganic film
  • An example of the inorganic film is a gas barrier layer.
  • This laminate can be suitably used as a support substrate in electronic devices such as touch panels, color filters, liquid crystal elements, and organic EL elements.
  • the gas barrier layer plays a role of preventing permeation of water vapor, oxygen and the like.
  • Examples of the material constituting the soot gas barrier layer include metal oxides, metal nitrides, metal oxynitrides, and metal carbonitrides.
  • Examples of the metal element contained in these include aluminum (Al), silicon (Si), titanium (Ti), tin (Sn), zinc (Zn), zirconium (Zr), indium (In), and niobium (Nb). , Molybdenum (Mo), tantalum (Ta), calcium (Ca), and the like.
  • the gas barrier layer contains at least one of silicon oxide, silicon nitride, silicon oxynitride, and silicon carbonitride.
  • the inorganic film can be produced by a vapor deposition method in which a film is formed by depositing a material from the vapor phase, such as a sputtering method, a vacuum deposition method, an ion plating method, or a plasma CVD method. Among them, it is preferable to use a sputtering method or a plasma CVD method because a more uniform film having a high oxygen barrier property can be obtained.
  • the number of layers of the inorganic film may be a single layer or a multilayer of two or more layers.
  • the multilayer film include a gas barrier layer in which the first layer is made of SiN, the second layer is made of SiO, and a gas barrier layer in which the first layer is made of SiON and the second layer is made of SiO.
  • the total thickness of the inorganic film is preferably 10 nm or more, and more preferably 50 nm or more, from the viewpoint of improving the oxygen barrier property.
  • the total thickness of the inorganic film is preferably 1 ⁇ m or less, and more preferably 200 nm or less.
  • the polyimide resin film according to the embodiment of the present invention is used for flexible devices such as liquid crystal displays, organic EL displays, touch panels, electronic paper, color filters, micro LED displays, display devices such as solar cells, CMOS, and other light receiving devices. can do.
  • the manufacturing process of the flexible device includes a process of forming circuits necessary for the display device and the light receiving device on the polyimide resin film formed on the substrate.
  • an amorphous silicon TFT can be formed on a flexible substrate.
  • a structure necessary for the device can be formed thereon by a known method.
  • the flexible polyimide device film can be obtained by peeling the solid polyimide resin film having a circuit or the like formed on the surface thereof from the substrate using a known method such as laser irradiation.
  • a touch panel according to an embodiment of the present invention includes a resin film containing the above-described polyimide resin.
  • An example of the configuration of a touch panel according to an embodiment of the present invention will be described with reference to the drawings.
  • FIG. 1A shows a basic configuration of a touch panel 1 including a polyimide resin film according to an embodiment of the present invention.
  • a black picture frame 3 On the polyimide resin film 2, a black picture frame 3, a first transparent wiring 4, and a second transparent wiring 7 are formed.
  • a lead-out wiring 6 is provided on the black frame 3, and an insulating film 5 is provided on the first transparent wiring 4 so as to cover the first transparent wiring 4, and the first transparent wiring 4 and the second transparent wiring 7. Is formed so as to be electrically connected to the lead-out wiring 6.
  • the protective film 8 is formed so as to cover these members.
  • FIG. 1B is a modification of the touch panel having the configuration shown in FIG. 1A.
  • a gas barrier layer 9 that is an inorganic film is further formed between the polyimide resin film 2 and the black picture frame 3, the first transparent wiring 4, the second transparent wiring 7, and the like.
  • the touch panel manufacturing method using the polyimide resin according to the embodiment of the present invention includes, for example, the following steps (1) to (5).
  • the steps (1) to (3) and (5) can be performed according to the above-described method for producing a polyimide resin film.
  • the transparent wiring, the insulating film, and the lead-out wiring are formed as follows.
  • a conductive film is formed and patterned on a polyimide resin film to form a first transparent wiring.
  • a known metal film, a metal oxide film, a film containing a carbon material such as carbon nanotube or graphene, and the like can be applied.
  • a metal oxide film Is preferably applied.
  • the metal oxide film include indium oxide, cadmium oxide, or tin oxide, and tin, tellurium, cadmium, molybdenum, tungsten, fluorine, zinc, germanium, or the like added as impurities, zinc oxide, or titanium oxide.
  • a film made of a metal oxide such as one to which aluminum is added as an impurity can be given.
  • a metal oxide such as one to which aluminum is added as an impurity
  • an indium oxide thin film containing 2 to 15% by mass of tin oxide or zinc oxide is preferably used because of its excellent transparency and conductivity.
  • the first transparent wiring can be formed by any method as long as the target thin film and pattern can be formed.
  • a vapor deposition method in which a metal oxide is deposited from the vapor phase to form a film such as a sputtering method, a vacuum evaporation method, an ion plating method, or a plasma CVD method, is suitable.
  • a pattern formation method for example, a novolac-based positive resist is applied, followed by drying, exposure, development and etching with an acid to pattern the metal oxide film, and finally the positive resist is stripped with an alkali.
  • the film thickness of the first transparent wiring is preferably 20 to 500 nm, more preferably 50 to 300 nm.
  • the insulating film may be either an organic film or an inorganic film.
  • the organic film to be an insulating film can be formed by applying a general acrylic or polyimide resist, drying, exposing, developing and thermosetting.
  • a second transparent wiring is formed on the polyimide resin film and the insulating film.
  • the second transparent wiring can be formed by the same method as the first transparent wiring.
  • the lead-out wiring is formed so as to be electrically connected to the first transparent wiring and the second transparent wiring.
  • a method for forming the lead-out wiring for example, there is a method of patterning a metal film having a three-layer structure of Mo layer, Al layer, and Mo layer, all formed by a sputtering method, in the same manner as the first transparent wiring.
  • a black frame may be formed between the polyimide resin and the lead-out wiring. By forming the lead wiring on the black frame, the lead wiring is not visually recognized.
  • the black picture frame can be formed by the following method, for example.
  • a black resin composition for a black frame made of polyamic acid in which a black pigment is dispersed is applied by a method such as a spin coater or a die coater so that the film thickness after curing becomes 1 ⁇ m. This is dried under reduced pressure at 60 Pa or less and then semi-cured in a hot air oven or hot plate at 110 to 140 ° C.
  • a positive resist is applied by a method such as a spin coater or a die coater so that the film thickness after pre-baking becomes 1.2 ⁇ m. This is dried under reduced pressure at 80 Pa and then pre-baked in a hot air oven or hot plate at 80 to 110 ° C. to form a resist film. Thereafter, exposure is selectively performed through a photomask by a proximity exposure machine or a projection exposure machine. Then, the exposed portion is removed by immersing in an alkali developer such as 1.5 to 3.0% by weight of potassium hydroxide or tetramethylammonium hydroxide for 20 to 300 seconds.
  • an alkali developer such as 1.5 to 3.0% by weight of potassium hydroxide or tetramethylammonium hydroxide for 20 to 300 seconds.
  • the polyamic acid is converted to polyimide by heating in a hot air oven or hot plate at 200 to 300 ° C. for 10 to 60 minutes to form a black picture frame in which a black pigment is dispersed in the resin film.
  • a black picture frame in which a black pigment is dispersed in the resin film.
  • an insulating film may be formed on the black frame to protect the black frame.
  • the insulating film on the black frame may be formed simultaneously with the formation of the insulating film on the first transparent wiring.
  • the insulating film may be either an organic film or an inorganic film.
  • the organic film to be an insulating film can be formed by applying a general acrylic or polyimide resist, drying, exposing, developing and thermosetting.
  • a protective film may be provided so as to cover each member constituting the touch panel.
  • the protective film may be either an organic film or an inorganic film.
  • the organic film serving as the protective film can be formed, for example, by applying an acrylic polymer solution, drying and heat curing.
  • a gas barrier layer may be provided on the polyimide resin film.
  • the gas barrier property can be imparted to the polyimide resin film, and deterioration of wiring due to moisture or oxygen can be suppressed.
  • the number of gas barrier layers may be a single layer or a multilayer of two or more layers.
  • the multilayer film include a gas barrier layer in which the first layer is made of SiO, the second layer is made of SiN, and the first layer is made of SiO / AlO / ZnO, and the second layer is made of SiO.
  • Color filter which concerns on embodiment of this invention is equipped with the resin film containing the above-mentioned polyimide resin.
  • An example of the configuration of a color filter according to an embodiment of the present invention will be described with reference to the drawings.
  • FIG. 2A shows a basic configuration of the color filter 10 including the polyimide resin film according to the embodiment of the present invention.
  • a black matrix 11 red colored pixels 12R, green colored pixels 12G, and blue colored pixels 12B are formed.
  • the color filter further includes an overcoat layer 13 so as to cover them.
  • FIG. 2B is a modification of the configuration shown in FIG. 2A. In this configuration, a gas barrier layer 9 that is an inorganic film is further formed between the polyimide resin film 2 and each colored pixel and the black matrix 11.
  • the black matrix is preferably a resin black matrix in which a black pigment is dispersed in a resin.
  • the black pigment include carbon black, titanium black, titanium oxide, titanium oxynitride, titanium nitride, or iron tetroxide.
  • carbon black and titanium black are suitable.
  • a red pigment, a green pigment, and a blue pigment can be mixed and used as a black pigment.
  • the resin used for the resin black matrix a polyimide resin is preferable because a thin pattern can be easily formed.
  • the polyimide resin is preferably a polyimide resin obtained by thermosetting a polyamic acid synthesized from an acid anhydride and a diamine after patterning.
  • the acid anhydride, diamine and solvent those mentioned above for the polyimide resin can be used.
  • the resin used for the resin black matrix a photosensitive acrylic resin is also preferable.
  • the resin black matrix using the same preferably contains an alkali-soluble acrylic resin, a photopolymerizable monomer, a polymer dispersant and an additive in which a black pigment is dispersed.
  • alkali-soluble resin examples include a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound.
  • unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid or acid anhydrides.
  • photopolymerizable monomers examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate or dipentaerythritol. Examples include penta (meth) acrylate.
  • photopolymerization initiators examples include benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, ⁇ -hydroxyisobutylphenone , Thioxanthone or 2-chlorothioxanthone.
  • Examples of the solvent for dissolving the photosensitive acrylic resin include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl acetoacetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, Mention may be made of methoxybutyl acetate or 3-methyl-3-methoxybutyl acetate.
  • the colored pixel is generally composed of three colored pixels of red, green, and blue.
  • the brightness of white display of the display device can be improved by forming a colorless and transparent pixel or a very thinly-colored fourth color pixel.
  • a resin containing a pigment or a dye as a colorant is used for the colored pixels of the color filter.
  • pigments used for red colored pixels include PR254, PR149, PR166, PR177, PR209, PY138, PY150, or PYP139.
  • pigments used for green colored pixels include PG7, PG36, PG58, PG37, PB16, PY129, PY138, PY139, PY150, or PY185.
  • pigments used for blue colored pixels include PB15: 6 or PV23.
  • blue dyes include C.I. I. Basic blue (BB) 5, BB7, BB9 or BB26 may be mentioned, and examples of red dye include C.I. I. Acid Red (AR) 51, AR87 or AR289.
  • BB Basic blue
  • AR Acid Red
  • resins used for colored pixels of red, green and blue include acrylic resins, epoxy resins, and polyimide resins, but photosensitive acrylic resins are preferable because the manufacturing cost of the color filter can be reduced.
  • the photosensitive acrylic resin generally contains an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator.
  • alkali-soluble resin examples include a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound.
  • unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid or acid anhydrides.
  • photopolymerizable monomers examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate or dipentaerythritol. Examples include penta (meth) acrylate.
  • photopolymerization initiators examples include benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, ⁇ -hydroxyisobutylphenone , Thioxanthone or 2-chlorothioxanthone.
  • Examples of the solvent for dissolving the photosensitive acrylic resin include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl acetoacetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate , Methoxybutyl acetate or 3-methyl-3-methoxybutyl acetate.
  • a method for producing a color filter using a polyimide resin according to an embodiment of the present invention includes, for example, the following steps (1) to (6).
  • the steps (1) to (3) and (6) can be performed according to the above-described method for producing a polyimide resin film.
  • a black matrix is formed as follows. On the polyimide resin film, a black resin composition for a resin black matrix made of polyamic acid in which a black pigment is dispersed is applied by a method such as a spin coater or a die coater so that the film thickness after curing becomes 1 ⁇ m. This is dried under reduced pressure at 60 Pa or less and then semi-cured in a hot air oven or hot plate at 110 to 140 ° C.
  • a positive resist is applied by a method such as a spin coater or a die coater so that the film thickness after pre-baking becomes 1.2 ⁇ m. This is dried under reduced pressure at 80 Pa and then pre-baked in a hot air oven or hot plate at 80 to 110 ° C. to form a resist film. Thereafter, exposure is selectively performed with ultraviolet rays through a photomask by a proximity exposure machine or a projection exposure machine. Then, the exposed portion is removed by immersing in an alkali developer such as 1.5 to 3.0% by weight of potassium hydroxide or tetramethylammonium hydroxide for 20 to 300 seconds.
  • an alkali developer such as 1.5 to 3.0% by weight of potassium hydroxide or tetramethylammonium hydroxide for 20 to 300 seconds.
  • exposure and development can be performed without applying a positive resist.
  • step (5) colored pixels are formed on the polyimide resin film after the resin black matrix is formed, for example, by the following method.
  • the colored pixels of the color filter are produced using a colorant and a resin.
  • a pigment is used as the colorant, a polymer dispersant and a solvent are mixed with the pigment for dispersion treatment, and then an alkali-soluble resin, a monomer, a photopolymerization initiator, and the like are added.
  • a dye is used as the colorant, a solvent, an alkali-soluble resin, a monomer, a photopolymerization initiator, and the like are added to the dye.
  • the total solid content in this case is the total of the polymer component, the alkali-soluble resin and monomer, which are resin components, and the colorant.
  • the obtained colorant composition is formed on a transparent substrate on which a resin black matrix is formed by a method such as a spin coater or a die coater, so that the film thickness after heat treatment is 0.8 to 3.0 ⁇ m. Apply as follows. This is dried under reduced pressure at 80 Pa and then pre-baked in a hot air oven or hot plate at 80 to 110 ° C. to form a coating film of colorant.
  • the unexposed portion is removed by immersing in an alkaline developer such as a 0.02-1.0 wt% potassium hydroxide aqueous solution or a tetramethylammonium hydroxide aqueous solution for 20 to 300 seconds.
  • an alkaline developer such as a 0.02-1.0 wt% potassium hydroxide aqueous solution or a tetramethylammonium hydroxide aqueous solution for 20 to 300 seconds.
  • the obtained coating film pattern is heated in a hot air oven or hot plate at 180 to 250 ° C. for 5 to 40 minutes to form colored pixels.
  • the patterning process as described above is sequentially performed on the red color pixel, the green color pixel, and the blue color pixel.
  • the order of patterning the colored pixels is not particularly limited.
  • ⁇ A flattening layer may be provided on the color filter.
  • the resin used for forming the planarization layer include an epoxy resin, an acrylic epoxy resin, an acrylic resin, a siloxane resin, or a polyimide resin.
  • the thickness of the planarizing layer is preferably a thickness that makes the surface flat, specifically, 0.5 to 5.0 ⁇ m is more preferable, and 1.0 to 3.0 ⁇ m is even more preferable.
  • a gas barrier film may be formed between the polyimide resin film and the black matrix / colored pixel layer.
  • a laminate having a gas barrier layer on a polyimide resin film it is possible to impart gas barrier properties to the polyimide resin film, and deterioration of colored pixels due to moisture and oxygen can be suppressed.
  • the number of gas barrier layers there is no limitation on the number of gas barrier layers, and it may be a single layer or a multilayer of two or more layers. Examples of the multilayer film include a gas barrier layer in which the first layer is made of SiO, the second layer is made of SiN, and the first layer is made of SiO / AlO / ZnO, and the second layer is made of SiO.
  • a liquid crystal element according to an embodiment of the present invention includes a resin film containing the above-described polyimide resin.
  • An example of a configuration of a liquid crystal element according to an embodiment of the present invention will be described with reference to the drawings.
  • FIG. 3 shows a basic configuration of the liquid crystal element 14 including the polyimide resin film according to the embodiment of the present invention.
  • the polyimide resin film 32 that is the first base material is disposed so as to face the polyimide resin film 42 that is the second base material with a gap.
  • a liquid crystal layer 19 is provided between them.
  • a gas barrier layer 9 that is an inorganic film is provided on the polyimide resin film 42, and a pixel electrode 15 formed of a transparent conductive film such as ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and the like, and A first alignment film 16 is provided.
  • ITO Indium Tin Oxide
  • IZO Indium Zinc Oxide
  • a gas barrier layer 9 that is an inorganic film is provided on the polyimide resin film 42, and a counter electrode 18 is provided on the gas barrier layer 9 so as to face the pixel electrode 15.
  • a second alignment film 17 is provided on the surface of the counter electrode 18 on the liquid crystal layer side.
  • a method for manufacturing a liquid crystal element using a polyimide resin according to an embodiment of the present invention includes, for example, the following steps (1) to (5).
  • the steps (1) to (3) and (5) can be performed according to the above-described method for producing a polyimide resin film.
  • the step (4) can be performed as follows, for example.
  • a gas barrier layer for suppressing permeation of gas such as water vapor and oxygen is formed on the polyimide resin film (first support base and second support base) described above.
  • Preferred gas barrier layers include, for example, metal oxides composed mainly of one or more metals selected from the group consisting of silicon, aluminum, magnesium, zinc, zirconium, titanium, yttrium, and tantalum, silicon, aluminum , Boron metal nitrides, or mixtures thereof.
  • silicon oxide, nitride, or oxynitride is a main component.
  • the gas barrier layer can be produced by a vapor deposition method in which a film is formed by depositing a material from the vapor phase, such as a sputtering method, a vacuum deposition method, an ion plating method, or a plasma CVD method.
  • a vapor deposition method in which a film is formed by depositing a material from the vapor phase
  • the sputtering method is preferable from the viewpoint that particularly excellent gas barrier properties can be obtained.
  • the thickness of the gas barrier layer is preferably 10 to 300 nm, more preferably 30 to 200 nm.
  • the gas barrier layer is preferably formed at a higher temperature, preferably 300 ° C. or higher.
  • a pixel electrode is formed on the gas barrier layer formed on the first support substrate, and a counter electrode is formed on the gas barrier layer formed on the second support substrate.
  • the formation method of the pixel electrode and the counter electrode may be any method as long as the target thin film and pattern can be formed.
  • a gas phase such as sputtering, vacuum deposition, ion plating, plasma CVD, etc.
  • a vapor phase deposition method in which a metal oxide is deposited from the inside to form a film is suitable.
  • the film thicknesses of the pixel electrode and the counter electrode are each preferably 20 to 500 nm, and more preferably 50 to 300 nm.
  • a first alignment film is formed on the pixel electrode, and a second alignment film is formed on the counter electrode.
  • Known materials and methods can be used for forming the alignment film. For example, it can be formed by applying an alignment film made of polyimide resin by a printing method, heating at 250 ° C. for 10 minutes using a hot plate, and subjecting the obtained film to a rubbing treatment.
  • the thickness of the first alignment film and the second alignment film may be any thickness that can align the liquid crystal of the liquid crystal layer, and is preferably 20 nm to 150 nm, respectively.
  • the liquid crystal layer is formed.
  • a known method can be used for forming the liquid crystal layer.
  • the liquid crystal layer can be formed by the following method. First, a sealing agent is applied on the second alignment film by a dispensing method, and heated at 90 ° C. for 10 minutes using a hot plate. On the other hand, a spherical spacer having a diameter of 5.5 ⁇ m is dispersed on the first alignment film. This is superposed on a substrate coated with a sealant, and heated at 160 ° C. for 90 minutes while being pressurized in an oven to cure the sealant to obtain a cell. Subsequently, the cell is allowed to stand for 4 hours at a temperature of 120 ° C. and a pressure of 13.3 Pa.
  • the cell is left for 0.5 hours in nitrogen, and then again filled with a liquid crystal compound under vacuum.
  • the liquid crystal compound is filled by placing the cell in a chamber and reducing the pressure to 13.3 Pa at room temperature, then immersing the liquid crystal inlet in liquid crystal and returning to normal pressure using nitrogen. After filling the liquid crystal, the liquid crystal injection port is sealed with an ultraviolet curable resin. After these steps, a liquid crystal element can be obtained by peeling the polyimide resin film from the support substrate and attaching a polarizing plate to each of the first support substrate and the second support substrate.
  • An organic EL element according to an embodiment of the present invention includes a resin film containing the above-described polyimide resin.
  • An example of the configuration of an organic EL element according to an embodiment of the present invention will be described with reference to the drawings.
  • FIG. 4 shows a basic configuration of the organic EL element 21 including the polyimide resin film according to the embodiment of the present invention.
  • a gas barrier layer 9 that is an inorganic film is further formed on the polyimide resin film 2.
  • a TFT layer 22 made of amorphous, silicon, low-temperature polysilicon, oxide semiconductor, etc., and a planarizing layer 23 are provided.
  • covers the edge part of the 1st electrode 24 which consists of Al / ITO etc., and the 1st electrode 24, A positive hole injection layer, a positive hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer.
  • the organic EL light-emitting layer 26R (red light-emitting layer), 26G (green light-emitting layer), and 26B (blue light-emitting layer) are formed.
  • a second electrode 27 made of ITO or the like is formed and sealed with the gas barrier layer 9. Yes.
  • the method for producing an organic EL element using the polyimide resin according to the embodiment of the present invention includes, for example, the following steps (1) to (5).
  • the steps (1) to (3) and (5) can be performed according to the above-described method for producing a polyimide resin film.
  • the step (4) can be performed as follows, for example.
  • a gas barrier layer is formed on the polyimide resin film described above.
  • Examples of preferable gas barrier layers are the same as those described in the section of the liquid crystal element.
  • a TFT is formed on the gas barrier film.
  • the semiconductor layer for forming the TFT include an amorphous silicon semiconductor, a polycrystalline silicon semiconductor, an oxide semiconductor typified by InGaZnO, and an organic semiconductor typified by pentacene and polythiophene.
  • a specific method for forming the TFT is as follows. For example, a gas barrier film, a gate electrode, a gate insulating film, a polycrystalline silicon semiconductor layer, an etching stopper film, and a source / drain electrode are sequentially formed by a known method using the laminate according to the embodiment of the present invention as a base material. Then, a bottom gate TFT is manufactured.
  • a planarization layer is formed on the TFT.
  • the resin used for forming the planarization layer include an epoxy resin, an acrylic epoxy resin, an acrylic resin, a polysiloxane resin, or a polyimide resin.
  • an electrode and an organic layer are formed thereon. Specifically, a first electrode made of Al / ITO or the like is formed, and then an organic layer having an insulating film covering the end of the first electrode, a hole injection layer, a hole transport layer, light emission A white organic EL light emitting layer comprising a layer, an electron transport layer, and an electron injection layer is provided. Further, a second electrode made of ITO or the like is formed, and a sealing film is formed.
  • an organic EL element can be obtained by peeling the resin film from the support substrate.
  • T Measurement of light transmittance
  • Tg glass transition temperature
  • CTE linear thermal expansion coefficient
  • the temperature raising method was performed under the following conditions. In the first stage, the temperature was raised to 150 ° C. at a temperature rising rate of 5 ° C./min to remove the adsorbed water from the sample. In the second stage, air cooling was performed to room temperature at a temperature lowering rate of 5 ° C./min. In the third stage, this measurement was performed at a temperature elevation rate of 5 ° C./min to determine the glass transition temperature. In addition, the average linear thermal expansion coefficient (CTE) of 50 to 200 ° C. in the third stage was determined. For the measurement, a film obtained by peeling the polyimide resin film prepared in (1) from a silicon wafer was used.
  • Td1 Measurement of 1% weight loss temperature
  • TGA-50 manufactured by Shimadzu Corporation
  • the temperature raising method was performed under the following conditions. In the first stage, the temperature of the sample was increased to 350 ° C. at a temperature increase rate of 3.5 ° C./min to remove the adsorbed water from the sample. In the second stage, the temperature was lowered to a room temperature of 10 ° C./min. In the third stage, the main measurement was performed at a temperature rising rate of 10 ° C./min to obtain a 1% thermogravimetric decrease temperature. For the measurement, a film obtained by peeling the polyimide resin film prepared in (1) from a silicon wafer was used.
  • Measurement of residual stress Measurement was performed using a thin film stress measuring apparatus FLX-3300-T manufactured by KLA-Tencor Corporation. The measurement was performed using the polyimide resin film prepared in (1), and the polyimide resin film was allowed to stand for 24 hours in a room at room temperature of 23 ° C. and humidity of 55% before measurement.
  • a black resin composition for a black frame made of polyamic acid in which a black pigment is dispersed is spin-coated on the surface of a polyimide resin film on a glass substrate prepared by the method (3) and heated to 90 ° C. It was dried for 3 minutes on a hot plate to form a black resin coating film.
  • a positive photoresist (“SRC-100” manufactured by Shipley Co., Ltd.) was spin-coated and pre-baked with a hot plate.
  • a 2.38% tetramethylammonium hydroxide aqueous solution is used to form a photoresist.
  • Development and etching of the black resin coating were simultaneously performed to form a pattern.
  • the black resin coating is heated in a hot air oven at 280 ° C. for 30 minutes to imidize the polyamic acid contained in the black resin coating and form a black picture frame did.
  • first transparent wiring made of ITO was formed on the surface of the polyimide resin film on which the black picture frame was formed as follows. An ITO film was formed on the polyimide resin film by sputtering. A novolac positive resist was applied on the ITO film, dried, exposed, developed and etched with acid to pattern the ITO film, and finally the positive resist was stripped with alkali.
  • an insulating film was formed on the first transparent wiring.
  • the insulating film was formed by applying an acrylic negative resist, drying, exposing, developing, and thermosetting.
  • a lead wiring (metal wiring) electrically connected to the first and second transparent wirings was formed on the black frame.
  • the lead-out wiring was formed by patterning a metal film having a three-layer structure of Mo layer, Al layer, and Mo layer formed by a sputtering method in the same manner as the first transparent wiring.
  • the polyimide resin film was peeled from the glass substrate by irradiating an excimer laser (wavelength 308 nm) from the glass substrate side to obtain a touch panel (FIG. 1A).
  • the obtained touch panel was affixed to an organic EL light emitting panel and evaluated for visibility and operability.
  • the touch panel was connected to an external touch position detection circuit (driver) and touched with a finger according to the instructions displayed on the screen.
  • the operability at that time was determined as follows. Excellent (A): Input was possible without malfunction. Good (B): Some malfunctions were observed, but input was possible without malfunction. Defect (C): There were many malfunctions, and it was not possible to input correctly.
  • a black resin composition for a resin black matrix comprising a polyamic acid in which a black pigment is dispersed is spin-coated on the surface of a polyimide resin film on a glass substrate prepared by the method (3) and dried on a hot plate. Then, a black resin coating film was formed.
  • a positive photoresist (“SRC-100” manufactured by Shipley Co., Ltd.) was spin-coated and pre-baked with a hot plate.
  • a 2.38% tetramethylammonium hydroxide aqueous solution is used to form a photoresist.
  • Development and etching of the resin coating were performed simultaneously to form a pattern.
  • the black resin coating is heated in a hot air oven at 280 ° C. for 30 minutes to imidize the polyamic acid contained in the black resin coating, and the black matrix 4 is formed. Formed. When the thickness of the black matrix was measured, it was 1.4 ⁇ m.
  • the film was developed by being immersed in a developer composed of a 0.2 wt% tetramethylammonium hydroxide aqueous solution, and then washed with pure water. Then, it heat-processed for 30 minutes in 230 degreeC oven, and produced the red pixel.
  • the amount of deviation from the ideal lattice of the black matrix of the color filter on the glass substrate produced by the above method was measured 24 points for each color filter substrate with glass using SMIC-800 (manufactured by Sokkia Topcon). The average of the absolute values of the deviation amounts obtained by measurement was obtained by calculation, and the obtained value was taken as the deviation amount from the ideal lattice of the black matrix at that level. The amount of deviation in each example and comparative example was evaluated. Then, when the BM pattern is created on the glass substrate and when it is created on the polyimide resin, it is evaluated how much the deviation amount is different (this is referred to as “BM positional deviation amount”), The determination was made by the following evaluation method.
  • BM positional deviation amount is 1.8 ⁇ m or less.
  • TFT substrate A gas barrier layer made of SiO was formed on the surface of the polyimide resin film on the glass substrate produced by the method of (3) using a plasma CVD method. Thereafter, a bottom gate type TFT was formed, and an insulating film made of Si 3 N 4 was formed so as to cover the TFT. Next, after forming a contact hole in the insulating film, a wiring (height: 1.0 ⁇ m, not shown) connected to the TFT through the contact hole was formed on the insulating film. This wiring is for connecting an organic EL element and a TFT formed between TFTs or in a later process.
  • a flattening layer was formed on the insulating film in a state where the unevenness due to the wiring was embedded.
  • the planarizing layer is formed by spin-coating a photosensitive polyimide varnish on a substrate, pre-baking on a hot plate (120 ° C. ⁇ 3 minutes), exposing and developing through a mask having a desired pattern, and under an air flow The heat treatment was performed at 230 ° C. for 60 minutes. The applicability when applying the varnish was good. In the flattened layer obtained after exposure, development, and heat treatment, generation of wrinkles and cracks was not observed.
  • the average step of the wiring was 500 nm, and a contact hole of 5 ⁇ m square was formed in the produced planarization layer, and the thickness was about 2 ⁇ m.
  • the first electrode thus obtained corresponds to the anode of the organic EL element.
  • an insulating layer having a shape covering the end of the first electrode was formed.
  • the photosensitive polyimide varnish was also used for the insulating layer.
  • a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask in a vacuum deposition apparatus, and then a red organic EL light emitting layer, a green organic EL light emitting layer, and a blue organic EL light emitting device.
  • a layer was provided.
  • a second electrode made of Al / Mg (Al: reflective electrode) was formed on the entire surface above the substrate. Further, a SiON sealing film was formed by CVD film formation.
  • substrate was taken out from the vapor deposition machine, and the organic EL element was peeled from the glass substrate by irradiating an excimer laser (wavelength 308nm) from the glass substrate side.
  • a voltage is applied to the obtained active matrix organic EL element through a drive circuit to display in red, and the luminance orientation characteristic measuring device C9920-11 (manufactured by Hamamatsu Photonics Co., Ltd.) is used.
  • the color coordinates (x, y) and the color coordinates (x ′, y ′) in the 70 ° direction were measured. The smaller the color coordinate difference measured in each direction, the smaller the color shift in the oblique visual field, and the determination was made by the following evaluation method.
  • Light resistance test A light resistance test was performed under the following conditions, and the physical properties (transmittance, elongation at break, CTE, haze, laser peelability) before and after the light resistance test were compared.
  • the polyimide resin film on the glass substrate prepared in (3) was used, and light was applied from the resin film side.
  • CBDA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
  • PMDA-HH 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride
  • PMDA-HS 1R, 2S, 4S, 5R- Cyclohexanetetracarboxylic dianhydride
  • BPDA 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride
  • BPF-PA 9,9-bis (4- (3,4-dicarboxyphenoxy) phenyl )
  • HFHA 2,2-bis [3- (3-aminobenzamido) -4-hydroxyphenyl] hexafluoropropane
  • m-TB 2,2′-dimethyl-4,4′-diaminobiphenyl
  • TFMB 2 2,2′-bis (trifluoromethyl) benzidine
  • Example 1 Under a dry nitrogen stream, CBDA 3.34 g (17.0 mmol), TFMB 4.64 g (14.5 mmol), HFHA 1.55 g (2.56 mmol), and NMP 50 g were placed in a 100 mL four-necked flask and heated and stirred at 60 ° C. . After 8 hours, it was cooled to obtain a varnish.
  • Example 2 Under a dry nitrogen stream, CBDA 3.10 g (15.8 mmol), TFMB 3.55 g (11.1 mmol), HFHA 2.87 g (4.75 mmol), and NMP 50 g were placed in a 100 mL four-necked flask and heated and stirred at 60 ° C. . After 8 hours, it was cooled to obtain a varnish.
  • Example 3 Under a dry nitrogen stream, CBDA 3.52 g (18.0 mmol), TFMB 5.46 g, HFHA 0.54 g (0.90 mmol), and NMP 50 g were placed in a 100 mL four-necked flask and heated and stirred at 60 ° C. After 8 hours, it was cooled to obtain a varnish.
  • Example 4 Under a dry nitrogen stream, CBDA 4.00 g (20.4 mmol), m-TB 3.68 g (17.3 mmol), HFHA 1.85 g (3.06 mmol), and NMP 50 g were placed in a 100 mL four-necked flask and heated at 60 ° C. Stir. After 8 hours, it was cooled to obtain a varnish.
  • Example 5 In a 100 mL four-necked flask under a dry nitrogen stream, CBDA 3.53 g (18.0 mmol), TFMB 4.61 g (14.4 mmol), HFHA 0.54 g (0.90 mmol), 4-ABS-3AP 0.71 g (2 .70 mmol) and NMP (50 g) were added, and the mixture was heated and stirred at 60 ° C. After 8 hours, it was cooled to obtain a varnish.
  • Example 6 Under a dry nitrogen stream, CBDA 3.18 g (16.2 mmol), BPF-PA 1.16 g (1.80 mmol), TFMB 5.48 g (17.1 mmol), HFHA 0.54 g (0.90 mmol) in a 100 mL four-necked flask. ) And NMP (50 g) were added and heated and stirred at 60 ° C. After 8 hours, it was cooled to obtain a varnish.
  • Example 7 0.4 g of Tinuvin 405 (manufactured by BASF) (5 parts by mass with respect to 100 parts by mass of the polyimide precursor resin) was added to 50 g (concentration 16%) of the varnish obtained in Example 1, and the mixture was stirred at 30 ° C. for 30 minutes. A varnish was prepared.
  • Example 8 0.4 g of RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.) (5 parts by mass with respect to 100 parts by mass of the polyimide precursor resin) was added to 50 g (concentration: 16%) of the varnish obtained in Example 1, and 30 ° C. The varnish was prepared by stirring for a minute.
  • Example 9 50 g of varnish obtained in Example 1 (concentration 16%), 0.4 g of ULS-935 (molecular weight over 1000, manufactured by Lion Specialty Chemicals) (5 parts by mass with respect to 100 parts by mass of polyimide precursor resin) The varnish was prepared by adding and stirring at 30 ° C. for 30 minutes.
  • Example 10 Under a dry nitrogen stream, PMDA-HS 4.20 g (18.7 mmol), DABA 3.62 g (15.9 mmol), HFHA 1.70 g (2.81 mmol), and NMP 50 g were placed in a 100 mL four-necked flask and heated at 60 ° C. Stir. After 8 hours, it was cooled to obtain a varnish.
  • Example 11 Under a dry nitrogen stream, PMDA-HS 4.21 g (18.8 mmol), DABA 3.62 g (17.8 mmol), HFHA 0.57 g (0.94 mmol), and NMP 50 g were placed in a 100 mL four-necked flask and heated at 60 ° C. Stir. After 8 hours, it was cooled to obtain a varnish.
  • Example 12 Under a dry nitrogen stream, PMDA-HH 4.20 g (18.7 mmol), DABA 3.62 g (15.9 mmol), HFHA 1.70 g (2.81 mmol), and NMP 50 g were placed in a 100 mL four-necked flask and heated at 60 ° C. Stir. After 8 hours, it was cooled to obtain a varnish.
  • Example 13 Under a dry nitrogen stream, CBDA 3.85 g (19.6 mmol), TFMB 6.16 g (19.2 mmol), HFHA 0.24 g (0.39 mmol), and NMP 50 g were put into a 100 mL four-necked flask and heated and stirred at 60 ° C. . After 8 hours, it was cooled to obtain a varnish.
  • Example 14 Under a dry nitrogen flow, CBDA 6.06 g (30.9 mmol), 4,4′-DDS 3.84 g (15.4 mmol), TFMB 4.45 g (13.9 mmol), HFHA 0.93 g (100 mL four-necked flask) 1.55 mmol) and 50 g of NMP were added and heated and stirred at 60 ° C. After 8 hours, it was cooled to obtain a varnish.
  • Example 15 Under a dry nitrogen stream, CBDA 6.06 g (30.9 mmol), TFMB 8.41 g (26.3 mmol), HFHA 2.62 g (4.33 mmol), X-22-1660B-3 1.36 g in a 100 mL four-necked flask (0.31 mmol, compound represented by the general formula (25)) and NMP (50 g) were added, and the mixture was heated and stirred at 60 ° C. After 8 hours, it was cooled to obtain a varnish.
  • Example 16 Under a dry nitrogen stream, CBDA 6.06 g (30.9 mmol), TFMB 7.92 g (24.7 mmol), 4-ABS-3AP 1.48 g (4.33 mmol), HFHA 0.93 g (1) .55 mmol), X-22-1660B-3 1.36 g (0.31 mmol) and NMP 50 g were added, and the mixture was heated and stirred at 60 ° C. After 8 hours, it was cooled to obtain a varnish.
  • Tables 1 and 2 show the compositions of the varnishes synthesized in Examples 1 to 16 and Comparative Examples 1 to 4. Further, by using these varnishes, the light transmittance (T), in-plane / out-of-plane birefringence, haze value, 1% thermogravimetric reduction temperature (Td1) of the polyimide resin films obtained in (1) to (4). ), Linear thermal expansion coefficient (CTE), glass transition temperature (Tg), residual stress, peeling energy at the time of laser irradiation, touch panel evaluation, BM position accuracy, angle dependence of organic EL element color coordinates, The evaluation results are shown in Tables 1 and 2.
  • High transparency which is a characteristic necessary for a support substrate for a display, when the polyimide resin contains the structural unit of the general formula (1) as a main component and contains the structure of the general formula (2) in a range of 2 mol% to 30 mol%. It can be seen that all of low CTE, low birefringence, high Tg, and laser peelability are satisfied. Since all these characteristics are satisfied, good characteristics can be confirmed when a touch panel, a color filter, a liquid crystal element, and an organic EL element are produced using the polyimide resin according to the embodiment of the present invention. In Comparative Example 1, the organic EL element could not be evaluated because the laser could not be peeled from the glass substrate.
  • Example 17 Implementation of Light Resistance Test Using the varnish prepared in Example 1, a light resistance test was performed using the polyimide resin film prepared in (3). The light resistance test was performed according to the method described in (16).
  • Example 18 A light resistance test was conducted in the same manner as in Example 18 except that the varnish prepared in Example 7 was used.
  • Example 19 A light resistance test was carried out in the same manner as in Example 18 except that the varnish prepared in Example 8 was used.
  • Example 20 A light resistance test was carried out in the same manner as in Example 18 except that the varnish prepared in Example 9 was used.
  • Table 3 shows the results of light transmittance (T), haze, linear thermal expansion coefficient (CTE), elongation at break, and laser peelability using the films before and after the light resistance test described in Examples 17 to 20. It can be seen that since the polyimide resins of Examples 7 to 9 contain an ultraviolet absorber, deterioration of the film before and after the light resistance test is suppressed. Among these, the polyimide resin films of Examples 7 and 8 use a UV absorber having a more preferable structure and a more preferable molecular weight, so that it can be seen that the film characteristics are good even after the light resistance test.

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