JP6292351B1 - POLYIMIDE RESIN, POLYIMIDE RESIN COMPOSITION, TOUCH PANEL USING SAME AND ITS MANUFACTURING METHOD, COLOR FILTER AND ITS MANUFACTURING METHOD, LIQUID CRYSTAL ELEMENT AND ITS MANUFACTURING METHOD, ORGANIC EL ELEMENT AND ITS MANUFACTURING METHOD - Google Patents

Abstract

A polyimide resin having excellent light transmittance, low birefringence, low linear thermal expansibility, and laser releasability, comprising the structural unit of formula 1 as a main component and 2-30 mol% of the structural unit of formula 2 as a whole. Offer.
R ¹ : a group having 4 to 40 carbon atoms (however, a group having a monocyclic / condensed polycyclic alicyclic ring, or a group having a monocyclic / alicyclic ring directly or via a cross-linked structure); R ² : Formula 3; R ³ : Formula 4, Formula 5; R ⁴ -R ¹¹ : Hydrogen, halogen, (halogen-substituted) group having 1 to 3 carbon atoms; X ¹ : Bond, oxygen, sulfur, sulfonyl, (halogen-substituted) C 1-3 groups, esters, amides, sulfides

Description

  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 films are more flexible than glass, and are not easily broken and light. Recently, the movement to make the display flexible by replacing the substrate of the flat panel display with an organic film has been activated.

  Examples of the resin used for the organic film include polyester, polyamide, polyimide, polycarbonate, polyethersulfone, acrylic, and epoxy. Of these, polyimide is a highly heat-resistant resin and is suitable as a display substrate.

  Among polyimides, 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 a property of coloring yellow to brown, and a property of high birefringence. Due to these properties, the wholly aromatic polyimide cannot be used as a display substrate that requires high transparency and low birefringence.

  Examples of a method for suppressing the charge transfer interaction of polyimide and improving the light transmittance include a method of using an alicyclic monomer as at least one component of acid dianhydride and diamine.

  For example, Patent Document 1 discloses that a polyimide obtained from an alicyclic acid dianhydride and various aromatic or alicyclic diamines has high transparency and low birefringence.

  In Patent Document 2, polyimide obtained from 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 2,2′-bis (trifluoromethyl) benzidine (TFMB) is highly transparent. 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.

  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.

JP 11-080350 A JP 2010-059992 International Publication No. 2013/24849 JP 2006-204569 A

  In the case of producing a display on an organic film, a process in which an organic film is formed on a supporting substrate, a device is produced thereon, and then the organic film is peeled off from the supporting substrate. When this peeling process was examined, the polyimides described in Patent Documents 1, 2, and 4 had a problem that the irradiation energy required for peeling was high or peeling with a laser was difficult.

  Moreover, although the polyimide of patent document 3 has the indication that a laser peeling is possible, there existed a problem that CTE was high.

  Thus, there is no known polyimide material that satisfies all the required characteristics of high transparency, low birefringence, low CTE, and laser peelability.

  An object of this invention is to provide the polyimide resin which has the outstanding light transmittance, low birefringence, low linear thermal expansibility, and laser peelability in view of the said subject.

  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. 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 or an oxygen atom. And a divalent cross-linked 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.

  ADVANTAGE OF THE INVENTION According to this invention, the polyimide resin film which has the outstanding light transmittance, low birefringence, low linear thermal expansibility, and laser peelability can be provided. 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. By using the polyimide resin of the present invention as a support substrate for a display, it is possible to create a high-definition display.

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

  DESCRIPTION OF EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following embodiments, and can be implemented with various modifications according to the purpose and application. Each drawing referred to in the following description only schematically shows the shape, size, and positional relationship so that the contents of the present invention can be understood. That is, the present invention is not limited only to the shape, size, and positional relationship exemplified in each drawing.

<Polyimide resin>
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. A tetravalent organic group having 4 to 40 carbon atoms linked to each other. 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 represent 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.

  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”.

  Here, the main component means that the structural unit represented by the general formula (1) has 50 mol% or more of all the structural units of the polymer. By containing 50 mol% or more of the structure represented by the general formula (1) with respect to all the structural units of the polymer, the CTE of the polyimide resin is lowered. Thereby, the curvature at the time of forming the film | membrane using the polyimide resin on a support substrate can be reduced.

  In addition, 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). However, when 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 more preferably 70 mol% or more of all the structural units of the polymer.

  Further, by including the repeating structural unit represented by the general formula (2) in an amount of 2 mol% or more and 30 mol% or less of the total structural units, the CTE of the 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. Here, in the alicyclic structure, some hydrogen atoms may be substituted with halogen. Moreover, you may use these acid components individually or in combination as an acid component.

  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 -Tetrahi Drofuran tetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 2,3,5-tricarboxycyclopentyl acetic dianhydride, 3,4-dicarboxy-1,2, 3,4-tetrahydro-1-naphthalene succinic dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride, bicyclo [4.3.0] nonane 2,4,7,9-tetracarboxylic dianhydride, bicyclo [4.4.0] decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo [4.4.0] decane- 2,4,8,10-tetracarboxylic dianhydride, tricyclo [6.3.0.0 <2,6>] undecane-3,5,9,11-tetracarboxylic dianhydride, bicyclo [2 2.2] Octane-2,3,5,6- Tracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.1] heptanetetracarboxylic dianhydride Bicyclo [2.2.1] heptane-5-carboxymethyl-2,3,6-tricarboxylic dianhydride, 7-oxabicyclo [2.2.1] heptane-2,4,6,8- Tetracarboxylic dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic dianhydride, tetradecahydroanthracene-1,2,8,9-tetracarboxylic dianhydride, 3,3 ′ 4,4′-dicyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-oxydicyclohexanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl ) -3-methyl 3-cyclohexene-1,2 Jikarubonsan anhydride, and "RIKACID" (TM) BT-100 (trade names, manufactured by New Japan Chemical Co., Ltd.) and the like and derivatives thereof are exemplified.

R ¹ in 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 represent 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.

Among these, 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 the 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. The acid dianhydride that gives the structure represented by the chemical formula (11) is a product name “PMDA-HH” from Wako Pure Chemical Industries, Ltd. The acid dianhydride that gives the structure represented by the chemical formula (12) is “ It is commercially available as “PMDA-HS”. In addition, 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).

  Although it does not specifically limit as diamine which gives the structure represented by General formula (3), 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 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-diaminobenzanilide 4-aminobenzoic acid 4-aminophenyl, 4,4-diamino benzophenone or an alkyl group in these aromatic rings, an alkoxy group, such as diamine compounds substituted with a halogen atom.

R ² is preferably at least one selected from, for example, structures represented by chemical formulas (14) to (17) from the viewpoints of availability, transparency of polyimide resin, and low CTE properties. .

R ^{56 to} R ⁸⁷ each independently represent 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.

Of these, it is preferred that R ² is a diamine to provide a structure represented by the following chemical formula (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.

  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.

  Among them, 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).

  In addition, the oxazole ring of General formula (5) produces | generates by dehydration ring closure from the structure represented by 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. Examples of other structural units include polyimide, which is a polycyclic amide dehydration ring, polybenzoxazole, a polyhydroxyamide dehydration ring closure, and the like.

  Examples of acid dianhydrides used for other structural units include aromatic acid dianhydrides and aliphatic acid dianhydrides.

  For example, 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 (2,3-dicarboxyphenyl) ) Propane dianhydride, 1 1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride Bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (1,3-dioxo-1,3-dihydroisobenzfuran-5 Carboxylic acid) 1,4-phenylene, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7 -Naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis (3,4 -Zical Xylphenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxy) Benzoyloxy) phenyl) hexafluoropropane dianhydride, 1,6-difluoropromellitic dianhydride, 1-trifluoromethylpyromellitic dianhydride, 1,6-ditrifluoromethylpyromellitic dianhydride, 2,2′-bis (trifluoromethyl) -4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl Fluorene dianhydride, 4,4 ′-((9H-fluorenyl) bis (4,1-phenyleneoxycarbonyl)) diphthalic dianhydride, RIKACID "(registered trademark) TMEG-100 (trade name, manufactured by New Japan Chemical Co., Ltd.) an aromatic tetracarboxylic dianhydride and derivatives thereof, such as.

  Examples of the aliphatic dianhydride include, but are not limited to, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and derivatives thereof. Is mentioned.

  Moreover, these other acid dianhydrides can be used individually or in combination of 2 or more types.

  Examples of diamine compounds used for other structural units include aromatic diamine compounds, alicyclic diamine compounds, and aliphatic diamine compounds.

  For example, 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 Emissions Zen sulfonate or alkyl groups in these aromatic ring, an alkoxy group, such as diamine compounds substituted with a halogen atom.

  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-diethyl-3 ', 5'-dimethyl-4,4'-di Minodicyclohexyl methane, 4,4'-diaminodicyclohexyl ether, 3,3'-dimethyl-4,4'-diaminodicyclohexyl ether, 3,3'-diethyl-4,4'-diaminodicyclohexyl ether, 3,3 ', 5,5′-tetramethyl-4,4′-diaminodicyclohexyl ether, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodicyclohexyl ether, 3,5-diethyl-3 ′, 5′- Dimethyl-4,4′-diaminodicyclohexyl ether, 2,2-bis (4-aminocyclohexyl) propane, 2,2-bis (3-methyl-4-aminocyclohexyl) propane, 2,2-bis (3-ethyl) -4-aminocyclohexyl) propane, 2,2-bis (3,5-dimethyl-4-aminocyclohexyl) Syl) propane, 2,2-bis (3,5-diethyl-4-aminocyclohexyl) propane, 2,2- (3,5-diethyl-3 ′, 5′-dimethyl-4,4′-diaminodicyclohexyl) Propane, 2,2′-bis (4-aminocyclohexyl) hexafluoropropane, 2,2′-dimethyl-4,4′-diaminobicyclohexane, 2,2′-bis (trifluoromethyl) -4,4 Examples include '-diaminobicyclohexane, or diamine compounds in which these alicyclic rings are substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

  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, α, ω-bis (3-aminopropyl) poly Examples include siloxane diamines such as dimethylsiloxane.

  These aromatic diamine compounds, alicyclic diamine compounds, or aliphatic diamine compounds can be used alone or in combination of two or more.

  Among these, it is preferable to use a diamine having a sulfonate ester in the molecule because transparency can be improved while maintaining the mechanical properties and heat resistance of the polyimide. That is, it is preferable that 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). Thereby, the transparency of a polyimide resin can be improved and the glass transition temperature can be greatly increased. 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. A tetravalent organic group having 4 to 40 carbon atoms linked to each other.

  It is preferable that 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. By containing 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.

  It is preferable that the polyimide resin which concerns on embodiment of this invention has a structure represented by General formula (24) in the acid dianhydride residue and / or diamine residue which comprise a polyimide. When 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. Further, the transparency of the polyimide resin film can be further increased and the birefringence can be further decreased.

In the formula (24), R ⁸⁸ and R ⁸⁹ each independently represent a monovalent organic group having 1 to 20 carbon atoms. m shows the integer of 3-200.

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. Here, the monovalent aliphatic hydrocarbon having 1 to 3 carbon atoms is preferably a methyl group, and the aromatic group having 6 to 10 carbon atoms is preferably a phenyl group.

  M in General formula (24) is an integer of 3-200, Preferably it is 10-200, More preferably, it is 20-150, More preferably, it is an integer of 30-100, Most preferably, it is an integer of 30-60. When 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.

  The polyimide resin having the structure represented by the general formula (24) is obtained by using a silicone compound represented by the following general formula (25) as a monomer component.

In formula (25), a plurality of R ⁹⁰ are each independently a single bond or a divalent organic group having 1 to 20 carbon atoms, and 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, and o is an integer of 0 to 197.

In the general formula (25), 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. As a C6-C20 arylene group, a C3-C20 aromatic group is preferable and a phenylene group, a naphthylene group, etc. are mentioned. Among them, 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.

Preferable specific examples of each group in R ^{91 to} R ⁹³ include 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. Examples of 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. Number average molecular weight 4,400), X22-9409 (manufactured by Shin-Etsu Chemical Co., number average molecular weight 1,300), both ends amino-modified dimethyl silicone, X22-161A (manufactured by Shin-Etsu Chemical Co., number average molecular weight 1) , 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. Examples of 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) Molecular weight 4,200), DMS-Z21 (manufactured by Gerest, number average molecular weight 600 to 800), and the like.

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. The compound having a hydroxy group is considered to react with another tetracarboxylic dianhydride monomer.

Specific examples of the compound represented by the general formula (25) when L ¹ , L ² and L ³ are epoxy groups include X22-163 (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight) which is an epoxy type at both ends. 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). The compound having the epoxy group is considered to react with another diamine monomer.

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. In view of avoiding white turbidity of a varnish composed of a polyimide precursor and a solvent, or from the viewpoint of cost, it is more preferable that 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). .

In general formulas (26) and (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. Show. 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. A tetravalent organic group having 4 to 40 carbon atoms linked to each other. R ² represents a divalent organic group represented by the above general formula (3). R ³ represents the above general formula (4) or (5).

  It does not specifically limit as a method of imidation, Thermal imidation and chemical imidation are mentioned. 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. Examples of 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. And a structure esterified with a group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and the like. 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.

  As a specific reaction method, a predetermined amount of all diamine components and solvents are charged into a reactor and dissolved, and then a predetermined amount of acid dianhydride component is charged, and the temperature is from room temperature to 150 ° C. for 0.5 to 30 hours. Examples include a stirring method.

  In order for the polyimide resin and polyimide precursor resin which concern on embodiment of this invention to adjust molecular weight to a preferable range, you may seal both ends with a terminal blocker. Examples of the terminal blocking agent that reacts with the acid dianhydride include monoamines and monohydric alcohols. Examples of 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. Moreover, various organic groups can be introduce | transduced as a terminal group by making terminal blocker react.

  Monoamines used as the acid anhydride group terminal blocking agent include 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-amino. Naphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino -7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene 1-amino-2-hydroxynaphthalene, 1-cal Xyl-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-amino Naphthalene, 1-carboxy-2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy -4-aminonaphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4- Aminosalicylic acid, 5-aminosalicylic acid, 6-amino Lithic acid, Amelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4, 6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8-aminonaphthalene, 1-mercapto -7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto-2-aminonaphthalene 1-amino-7-mercaptonaphthalene, 2-mer Capto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino-2-mercapto Naphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 2,4 -Diethynylaniline, 2,5-diethynylaniline, 2,6-diethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline, 1-ethynyl-2-aminonaphthalene, 1-ethynyl- 3-aminonaphthalene, 1-ethynyl-4-aminonaphthalene, 1-ethini -5-aminonaphthalene, 1-ethynyl-6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 2-ethynyl-1-aminonaphthalene, 2-ethynyl-3-aminonaphthalene 2-ethynyl-4-aminonaphthalene, 2-ethynyl-5-aminonaphthalene, 2-ethynyl-6-aminonaphthalene, 2-ethynyl-7-aminonaphthalene, 2-ethynyl-8-aminonaphthalene, 3,5- Diethynyl-1-aminonaphthalene, 3,5-diethynyl-2-aminonaphthalene, 3,6-diethynyl-1-aminonaphthalene, 3,6-diethynyl-2-aminonaphthalene, 3,7-diethynyl-1-aminonaphthalene 3,7-diethynyl-2-aminonaphthalene, 4,8-diethynyl-1-amino Naphthalene, 4,8-diethynyl-2-amino-naphthalene, and the like, but is not limited thereto.

  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- Xadecanol, 1-heptadecanol, 2-heptadecanol, 1-octadecanol, 2-octadecanol, 1-nonadecanol, 2-nonadecanol, 1-icosanol, 2-methyl-1-propanol, 2-methyl-2 -Propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2-propyl-1-pentanol, 2-ethyl-1- Hexanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol, 2,4,4-trimethyl-1-hexanol, 2,6-dimethyl-4-heptanol, isononyl alcohol, 3,7-dimethyl- 3-octanol, 2,4-dimethyl-1-heptanol, 2-heptylundecanol, ethylene Recall monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol 1-methyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, cyclopentanol, cyclohexanol, cyclopentane monomethylol, dicyclopentane Examples thereof include, but are not limited to, monomethylol, tricyclodecane monomethylol, norboneol, and terpineol.

  Examples of the acid anhydride, monocarboxylic acid, monoacid chloride compound, and monoactive ester compound used as the 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- Droxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxy Naphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzoic acid, 3-ethynyl Benzoic acid, 4-ethynylbenzoic acid, 2,4-diethynylbenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynylbenzoic acid, 2 -Ethynyl-1-naphtho 3-ethynyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid, 8-ethynyl- 1-naphthoic acid, 2-ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid, Monocarboxylic acids such as 7-ethynyl-2-naphthoic acid and 8-ethynyl-2-naphthoic acid, monoacid chloride compounds in which these carboxyl groups are acid chloride, and terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxyna Phthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, Monoacid chloride compounds in which only the monocarboxyl group of dicarboxylic acids such as 2,6-dicarboxynaphthalene and 2,7-dicarboxynaphthalene is acid chloride, monoacid chloride compounds and N-hydroxybenzotriazole and N-hydroxy-5 -Active ester compounds obtained by reaction with norbornene-2,3-dicarboximide.

  Examples of the dicarbonate compound used as the amino group terminal blocking agent include di-tert-butyl dicarbonate, dibenzyl dicarbonate, dimethyl dicarbonate, and diethyl dicarbonate.

  Examples of the vinyl ether compound used as the amino group terminal blocking agent include tert-butyl chloroformate, n-butyl chloroformate, isobutyl chloroformate, benzyl chloroformate, allyl chloroformate, ethyl chloroformate and isopropyl chloroformate. Chloroformates, isocyanates such as 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 an amino group terminal 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. Moreover, the introduction ratio of the amino group terminal sealing 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. In addition, the polymer in which the end-capping agent is introduced can be easily detected directly by pyrolysis gas chromatograph (PGC), infrared spectrum, ¹ H-NMR spectrum measurement and ¹³ C-NMR spectrum measurement.

<Polyimide resin composition>
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.

(UV absorber)
The polyimide resin composition according to the embodiment of the present invention preferably contains an ultraviolet absorber. When the polyimide resin composition contains 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.

  There is no limitation in particular as a ultraviolet absorber, A well-known thing 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. When 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. . Moreover, since 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 Co.), LA-31 (molecular weight: 659, manufactured by ADEKA).

  It is preferable that content of the ultraviolet absorber in a polyimide resin composition is 0.5-10 weight part with respect to 100 weight part of polyimide resins. When the polyimide resin composition contains an ultraviolet absorber within the above range, light resistance (resistance to light, particularly ultraviolet light) can be improved without impairing the transparency of the resin.

(Thermal crosslinking agent)
The polyimide resin composition according to the embodiment of the present invention may contain a thermal crosslinking agent. As the 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. Specifically, 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, Rica Resin DME-100 (above trade name, manufactured by Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S (above trade name, manufactured by ADEKA CORPORATION), 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 Kayaku Co., Ltd.), EPOX-MK R508, EPOX- MK R540, EPOX-MK R710, EPOX-MK R1710, VG3101L, VG3101M80 (above trade names, manufactured by Printec Co., Ltd.), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085 (above trade names, Daicel Chemical Industries, Ltd.) ))).

  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. -PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM -PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM -BPE, TMO -BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKACALAC MX-279, NIKACAL MW-100LM, NIKACALAC MX-750LM (trade name, manufactured by Sanwa Chemical Co., Ltd.). Two or more of these may be contained.

  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. When 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.

(Coupling agent)
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. It is preferable that content of the coupling agent in a polyimide resin composition is 0.1-10 weight part with respect to 100 weight part of polyimide resins.

(Inorganic filler)
The polyimide resin composition according to the embodiment of the present invention may contain an inorganic filler. Examples of 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. Specifically, the average particle size of the inorganic filler is preferably 0.5 to 100 nm, and 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. When 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.

  In order to improve the dispersibility of the inorganic filler with respect to polyamic acid, polyimide or polyimide oxazole, 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.

  As those having an amino group, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, Examples include 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, and N-phenyl-3-aminopropyltrimethoxysilane.

  Various known methods can be used as a method of treating the organoinorganic filler sol with a silane coupling agent. For example, it can be processed 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.

(Surfactant)
The polyimide resin composition according to the embodiment of the present invention can contain a surfactant. The film thickness uniformity at the time of apply | coating a polyimide resin composition can be improved because a polyimide resin composition contains surfactant. Examples of 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. . In addition, 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. And an organic siloxane surfactant. Furthermore, acrylic polymer surfactants 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.

(Internal release agent)
The polyimide resin composition according to the embodiment of the present invention can contain an internal release agent. When the polyimide resin composition contains an internal release agent, the peelability of the polyimide resin film from the support substrate can be improved. Examples of the internal mold release agent include long chain fatty acids. It is preferable that content of the internal mold release agent in a polyimide resin composition is 0.1-5 weight part with respect to 100 weight part of polyimide resins.

(Coloring agent)
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.

  As the colorant, dyes, organic pigments, inorganic pigments and the like can be used, but 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. When specific examples of typical organic pigments are represented by color index (CI) numbers, the following are preferably used, but they are not limited to these.

  Examples of yellow pigments 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.

  Examples of orange pigments include pigment orange (hereinafter abbreviated as PO) 13, 36, 38, 43, 51, 55, 59, 61, 64, 65, 71, and the like.

  Examples of red pigments 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.

  Examples of purple pigments include pigment violet (hereinafter abbreviated as PV) 19, 23, 29, 30, 32, 37, 40, 50, and the like.

  Examples of blue pigments include Pigment Bull (hereinafter abbreviated as PB) 15, 15: 3, 15: 4, 15: 6, 22, 60, 64, and the like.

  Examples of green pigments 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 and the like, if necessary.

<Production method of polyimide resin film>
Below, the method to manufacture a polyimide resin film using the polyimide resin which concerns on embodiment of this invention, or its composition is demonstrated.

  First, a polyimide precursor resin composition is applied on a substrate. As the substrate, for example, a silicon wafer, ceramics, gallium arsenide, soda lime glass, non-alkali glass, or the like is used. Among these, alkali-free glass is preferable from the viewpoint of surface smoothness and dimensional stability during heating. Examples of 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. Among them, the slit die coating method is preferable from the viewpoint of the surface smoothness and film thickness uniformity of the coating film.

  Next, the board | substrate which apply | coated the polyimide precursor resin composition is dried, and a polyimide precursor resin composition film is obtained. For drying, a hot plate, an oven, an infrared ray, a vacuum chamber, or the like is used. In the case of using a hot plate, 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. As 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. For example, a resin layer coated on a 300 mm × 350 mm × 0.5 mm glass substrate is used. When heating, 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.

  Next, it heats in the range of 180 degreeC or more and 450 degrees C or less, and converts a polyimide precursor resin composition film into a polyimide resin film. And this polyimide resin film is peeled from a board | substrate and a polyimide resin film is obtained. Examples of 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. When peeling is performed after the device is formed on the polyimide resin coating, it is necessary to peel without damaging the device. Therefore, peeling using a laser is preferable.

  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. Regarding transparency, 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.

<Laminate>
The laminated body which concerns on embodiment of this invention has an inorganic film | membrane on the resin film containing the said polyimide resin. 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. In order to suppress deterioration of the electronic device due to moisture or oxygen, it is preferable to provide gas barrier properties by providing a gas barrier layer on the resin film containing the polyimide resin according to the embodiment of the present invention.

  Examples of the material constituting the 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.

  In particular, the gas barrier layer preferably contains at least one of silicon oxide, silicon nitride, silicon oxynitride, and silicon carbonitride. By using these materials, a uniform and dense film can be easily obtained, and the oxygen barrier property of the gas barrier layer is further improved.

   The inorganic film can be manufactured 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.

  There is no restriction | limiting in the number of layers of an inorganic film, Only 1 layer or a multilayer of 2 layers or more may be sufficient. Examples of 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. On the other hand, from the viewpoint of improving the bending resistance of the device, the total thickness of the inorganic film is preferably 1 μm or less, and more preferably 200 nm or less.

<Application>
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 a flexible device includes the process of forming a circuit required for a display device and a light receiving device on a polyimide resin film formed on a substrate. For example, an amorphous silicon TFT can be formed on a flexible substrate. Further, a structure necessary for the device can be formed thereon by a known method. As described above, 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.

(Touch panel)
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.

  On the polyimide resin film 2, a black frame 3, a first transparent wiring 4, and a second transparent wiring 7 are formed. In addition, 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. In this configuration, 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 manufacturing method of the touch panel using the polyimide resin which concerns on embodiment of this invention includes the process of following (1)-(5), for example.
(1) The process of apply | coating a polyimide precursor resin composition on a support substrate.
(2) A step of removing the solvent from the applied polyimide precursor resin composition.
(3) A step of imidizing the polyimide precursor to obtain the polyimide resin film described above.
(4) A step of forming a transparent wiring, an insulating film, and a lead-out wiring on the polyimide resin film.
(5) A step of peeling the polyimide resin film from the support substrate.

  The steps (1) to (3) and (5) can be performed according to the above-described method for producing a polyimide resin film.

  In the step (4), for example, a transparent wiring, an insulating film, and a lead-out wiring are formed as follows.

  First, a conductive film is formed and patterned on a polyimide resin film to form a first transparent wiring. As the conductive film, 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. Among these, from the viewpoint of transparency, conductivity, and mechanical properties, a metal oxide film Is preferably applied. Examples of 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. In addition, a film made of a metal oxide such as one to which aluminum is added as an impurity can be given. Among them, 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. For example, 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. Especially, it is preferable to form into a film using sputtering method from a viewpoint that the outstanding electroconductivity and transparency are acquired. As 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. A method is mentioned. Moreover, it is preferable that the film thickness of a 1st transparent wiring is 20-500 nm, and it is more preferable that it is 50-300 nm.

  Next, an insulating film is formed so as to cover 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.

  Next, 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.

  Next, the lead-out wiring is formed so as to be electrically connected to the first transparent wiring and the second transparent wiring. As 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 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 μm. 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.

  Next, 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 μm. This is dried under reduced pressure at 80 Pa, and then prebaked 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. After stripping the positive resist using a stripping solution, 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, and a black frame in which a black pigment is dispersed in the resin film Form. In the case of forming with a photosensitive resin, exposure and development can be performed without applying a positive resist.

  In order to protect the black frame, an insulating film may be formed on the black frame. At this time, 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.

  Furthermore, you may provide a protective film so that each member which comprises a touchscreen may be coat | covered. 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. By forming a laminate having a gas barrier layer 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. 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.

(Color filter)
The 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. On the polyimide resin film 2, 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. Examples of the black pigment include carbon black, titanium black, titanium oxide, titanium oxynitride, titanium nitride, or iron tetroxide. In particular, carbon black and titanium black are suitable. Moreover, 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 is preferably a polyimide resin 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. As examples of the acid anhydride, diamine and solvent, those mentioned above for the polyimide resin can be used.

  As 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.

  Examples of the alkali-soluble resin include a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid or acid anhydrides.

  Examples of photopolymerizable monomers 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.

  Examples of photopolymerization initiators include benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, α-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, Examples include methoxybutyl acetate or 3-methyl-3-methoxybutyl acetate.

  The colored pixels are generally composed of colored pixels of three colors of red, green, and blue. In addition to the three colored pixels, 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.

  For the colored pixels of the color filter, a resin containing a pigment or a dye as a colorant is used.

  Examples of the pigment used for the red colored pixel include PR254, PR149, PR166, PR177, PR209, PY138, PY150, or PYP139.

  Examples of pigments used for green colored pixels include PG7, PG36, PG58, PG37, PB16, PY129, PY138, PY139, PY150, or PY185.

  Examples of pigments used for blue colored pixels include PB15: 6 or PV23.

  Examples of 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.

  Examples of the resin used for the red, green, and blue colored pixels include acrylic resins, epoxy resins, and polyimide resins, and 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.

  Examples of the alkali-soluble resin include a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid or acid anhydrides.

  Examples of photopolymerizable monomers 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.

  Examples of photopolymerization initiators include benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, α-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.

The manufacturing method of the color filter using the polyimide resin which concerns on embodiment of this invention includes the process of following (1)-(6), for example.
(1) The process of apply | coating a polyimide precursor resin composition on a support substrate.
(2) A step of removing the solvent from the applied polyimide precursor resin composition.
(3) A step of imidizing the polyimide precursor to obtain the polyimide resin film described above.
(4) A step of forming a black matrix on the polyimide resin film.
(5) A step of forming colored pixels on the polyimide resin film.
(6) A step of peeling the polyimide resin film from the support substrate.

  The steps (1) to (3) and (6) can be performed according to the above-described method for producing a polyimide resin film.

  In the step (4), for example, 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 μm. 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.

  Next, 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 μm. This is dried under reduced pressure at 80 Pa, and then prebaked 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. Resin black matrix in which 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 after the positive resist is stripped using a stripping solution, and a black pigment is dispersed in the resin film Form. In the case of forming with a photosensitive resin, exposure and development can be performed without applying a positive resist.

  In the 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. When 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. On the other hand, when 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 coated 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 μm. Apply as follows. This is dried under reduced pressure at 80 Pa, and then prebaked in a hot air oven or hot plate at 80 to 110 ° C. to form a coating film of the colorant.

  Next, exposure is selectively performed through a photomask by a proximity exposure machine or a projection exposure machine. Thereafter, the unexposed portion is removed by immersing in an alkaline developer such as a 0.02-1.0 wt% aqueous potassium hydroxide solution or an aqueous tetramethylammonium hydroxide solution for 20 to 300 seconds. A colored pixel is formed by heat-processing the obtained coating-film pattern for 5 to 40 minutes with a 180-250 degreeC hot-air oven or a hotplate. Using the colorant composition prepared for each color of the color pixel, 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 planarizing layer may be provided on the color filter. Examples of 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 μm is more preferable, and 1.0 to 3.0 μm is more preferable.

  A gas barrier film may be formed between the polyimide resin film and the black matrix / colored pixel layer. By forming 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. 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.

(Liquid crystal element)
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 which 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) or IZO (Indium Zinc Oxide), and the like. A first alignment film 16 is provided. Thus, by using a laminate having a gas barrier layer on a polyimide resin film, gas barrier properties can be imparted to the polyimide resin film, and deterioration of the electrode due to moisture and oxygen can be suppressed. 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.

The manufacturing method of the liquid crystal element using the polyimide resin which concerns on embodiment of this invention includes the process of following (1)-(5), for example.
(1) The process of apply | coating a polyimide precursor resin composition on a support substrate.
(2) A step of removing the solvent from the applied polyimide precursor resin composition.
(3) A step of imidizing the polyimide precursor to obtain the polyimide resin film of the present invention.
(4) A step of forming a transparent electrode, an alignment film, and a liquid crystal layer on the polyimide resin film.
(5) A step of peeling the polyimide resin film from the support substrate.

  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, for example, as follows. First, 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. Among these, from the viewpoints of gas barrier properties, transparency, surface smoothness, flexibility, film stress, cost, and the like, it is preferable that 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. Among these, the sputtering method is preferable from the viewpoint that particularly excellent gas barrier properties can be obtained.

  Further, the thickness of the gas barrier layer is preferably 10 to 300 nm, and more preferably 30 to 200 nm. In order to obtain high gas barrier properties, the gas barrier layer is preferably formed at a higher temperature, preferably 300 ° C. or higher.

  Next, 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. For example, 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.

  Next, 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.

  Next, a liquid crystal layer is formed. A known method can be used for forming the liquid crystal layer. For example, 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 μm 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. After that, 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.

<Organic EL device>
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. On top of this, a TFT layer 22 made of amorphous, silicon, low-temperature polysilicon, oxide semiconductor, etc., and a planarizing layer 23 are provided. Furthermore, it has the insulating film 25 which coat | 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 manufacturing method of the organic EL element using the polyimide resin which concerns on embodiment of this invention includes the process of following (1)-(5), for example.
(1) The process of apply | coating a polyimide precursor resin composition on a support substrate.
(2) A step of removing the solvent from the applied polyimide precursor resin composition.
(3) A step of imidizing the polyimide precursor to obtain the polyimide resin film described above.
(4) A step of forming an organic EL light emitting circuit on the polyimide resin film.
(5) A step of peeling the polyimide resin film from the support substrate.

  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, for example, as follows. First, 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. By forming a laminate having a gas barrier layer on the polyimide resin film, it is possible to impart gas barrier properties to the polyimide resin film, and deterioration of the organic EL light emitting layer due to moisture or oxygen can be suppressed.

  Next, a TFT is formed on the gas barrier film. Examples of 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.

  Next, a planarization layer is formed on the TFT. Examples of 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. Furthermore, 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.

  After producing an organic EL light emitting circuit through these steps, an organic EL element can be obtained by peeling the resin film from the support substrate.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated, this invention is not limited by these examples.

(1) Production of polyimide resin film Using a coating and developing apparatus Mark-7 manufactured by Tokyo Electron Co., Ltd. on a 6-inch mirror silicon wafer, the film thickness after pre-baking at 140 ° C. × 4 minutes is 15 ± 0.5 μm. The varnish was spin coated so that Thereafter, a prebaking process was performed at 140 ° C. for 4 minutes using the same Mark-7 hot plate. Using an inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.), the pre-baked film was heated to 300 ° C. at 3.5 ° C./min under a nitrogen stream (oxygen concentration 20 ppm or less) and held for 30 minutes. It cooled to 50 degreeC at 5 degreeC / min, and produced the polyimide resin film.

(2) Production of polyimide resin film (on glass substrate-1) Using a spin coater MS-A200 manufactured by Mikasa Co., Ltd. on a glass substrate (Tempax) having a thickness of 50 mm × 50 mm × 1.1 mm, 140 ° C. × 4 The varnish was spin coated so that the film thickness after pre-baking was 15 ± 0.5 μm. Then, the prebaking process for 140 degreeC x 4 minutes was performed using the Dainippon Screen Co., Ltd. hotplate D-SPIN. Using an inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.), the pre-baked film was heated to 300 ° C. at 3.5 ° C./min under a nitrogen stream (oxygen concentration 20 ppm or less) and held for 30 minutes. It cooled to 50 degreeC by 5 degreeC / min, and produced the polyimide resin film (on a glass substrate).

(3) Production of polyimide resin film (on glass substrate-2) A slit coater (manufactured by Toray Engineering Co., Ltd.) was used on a 300 mm × 350 mm × 0.5 mm thick glass substrate (AN-100 manufactured by Asahi Glass Co., Ltd.). Then, the varnish was spin-coated so that the film thickness after prebaking at 140 ° C. × 4 minutes was 15 ± 0.5 μm. Then, the prebaking process for 140 degreeC x 4 minutes was performed using the hotplate. Using a inert oven (INH-21CD manufactured by Koyo Thermo System Co., Ltd.), the prebaked film was heated to 300 ° C. over 70 minutes under a nitrogen stream (oxygen concentration 20 ppm or less), held for 30 minutes, and kept at 5 ° C. The solution was cooled to 50 ° C. at a rate of / min to produce a polyimide resin film (on a glass substrate).

(4) Preparation of polyimide resin film (on silicon substrate) Film thickness after pre-baking at 140 ° C. for 4 minutes using a spin coater MS-A200 manufactured by Mikasa Co., Ltd. on a 4-inch silicon substrate cut into ¼. The varnish was spin-coated so that the thickness was 5 ± 0.5 μm. Then, the prebaking process for 140 degreeC x 4 minutes was performed using the Dainippon Screen Co., Ltd. hotplate D-SPIN. Using an inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.), the pre-baked film was heated to 300 ° C. at 3.5 ° C./min under a nitrogen stream (oxygen concentration 20 ppm or less) and held for 30 minutes. It cooled to 50 degreeC at 5 degreeC / min, and produced the polyimide resin film (on a silicon substrate).

(5) Measurement of light transmittance (T) The light transmittance at wavelengths of 308 nm and 400 nm was measured using an ultraviolet-visible spectrophotometer (MultiSpec 1500 manufactured by Shimadzu Corporation). For the measurement, the polyimide resin film produced in (2) was used.

(6) Measurement of haze value Using a direct reading haze computer (HGM2DP, C light source manufactured by Suga Test Instruments Co., Ltd.), the haze value (%) of the polyimide resin film on the glass substrate prepared in (2) was measured. In addition, the average value of 3 times measurement was used as each value.

(7) Measurement of in-plane / out-of-plane birefringence Measure TE refractive index (n (TE)) and TM refractive index (n (TM)) at a wavelength of 632.8 nm using a prism coupler (PC2010, manufactured by METRICON). did. n (TE) and n (TM) are refractive indexes in parallel and perpendicular directions to the polyimide film surface, respectively. In-plane / out-of-plane birefringence was calculated as the difference between n (TE) and n (TM) (n (TE) -n (TM)). For the measurement, the polyimide resin film produced in (4) was used.

(8) Measurement of glass transition temperature (Tg) and linear thermal expansion coefficient (CTE) Measurement was performed under a nitrogen stream using a thermomechanical analyzer (EXSTAR 6000TMA / SS6000 manufactured by SII Nano Technology Co., Ltd.). 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. Moreover, the average of the linear thermal expansion coefficient (CTE) of 50-200 degreeC in a 3rd step was calculated | required. For the measurement, a film obtained by peeling the polyimide resin film prepared in (1) from a silicon wafer was used.

(9) Measurement of 1% weight loss temperature (Td1) Using a thermogravimetric apparatus (TGA-50 manufactured by Shimadzu Corporation), measurement was performed under a nitrogen stream. 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.

(10) Measurement of elongation at break The measurement was performed using Tensilon (Orientec RTM-100). Ten or more samples were measured for each sample, and the JIS average value was calculated using JIS number average (JIS K-6301). For the measurement, a film obtained by peeling the polyimide resin film prepared in (1) from a silicon wafer was used.

(11) 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.

(12) Laser peeling test The polyimide resin film obtained by the method described in (3) is irradiated with a 308 nm excimer laser (shape: 21 mm × 1.0 mm) from the glass substrate side to conduct a laser peeling test. went. The laser was irradiated while shifting by 0.25 mm in the minor axis direction. When the cut was made along the edge of the irradiation region, the energy at which the film peeled was regarded as the irradiation energy (peeling energy) necessary for peeling, and the laser peelability was evaluated according to the following criteria.
Shu (A): Peeling energy is 230 mJ / cm ² or less.
Excellent (B): The peeling energy exceeds 230 mJ / cm ² and is 270 mJ / cm ² or less.
Good (C): The peeling energy exceeds 270 mJ / cm ² and is 310 mJ / cm ² or less.
Yes (D): Peeling Energy exceeds ^{310mJ / cm 2, 350mJ / cm} 2 or less.
Defect (E): peeling energy exceeds 350 mJ / cm ² .

(13) Production and Evaluation of Touch Panel (FIG. 1A) A touch panel was produced and evaluated by the method described below.

[1] Formation of black frame 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 prebaked on a hot plate. Next, after exposure at an exposure amount of 200 mJ / cm ² (ultraviolet intensity at 365 nm) using an ultra-high pressure mercury lamp through a mask, 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. Furthermore, after peeling off the photoresist with methyl cellosolve acetate, 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.

[2] Formation of first transparent wiring A 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.

[3] Formation of Insulating Film Subsequently, 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.

[4] Formation of Second Transparent Electrode Subsequently, a second transparent electrode was formed on the polyimide resin film by the same method as the first transparent wiring.

[5] Formation of Lead Wiring (Metal Wiring) Subsequently, 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.

[6] Formation of Transparent Protective Film Subsequently, an acrylic transparent protective film for covering each formed member was formed.

  Finally, the polyimide resin film was peeled from the glass substrate by irradiating an excimer laser (wavelength 308 nm) from the glass substrate side, and the touch panel (FIG. 1A) was obtained. The obtained touch panel was affixed to an organic EL light emitting panel and evaluated for visibility and operability.

<Visibility>
The color when the organic EL panel was displayed in white was visually observed, and the visibility was determined as follows.
Excellent (A): Appears white (B): Appears to be slightly colored, but appears white to the extent that it does not matter.
Defect (C): It is clearly colored and cannot be said to be white.

<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.

(14) Fabrication of color filter (FIG. 2A) and measurement of BM positional accuracy Color filters were fabricated and BM positional accuracy was measured by the methods described below.

[1] Preparation of black matrix 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 prebaked on a hot plate. Next, after exposure at an exposure amount of 200 mJ / cm ² (ultraviolet intensity at 365 nm) using an ultra-high pressure mercury lamp through a mask, 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. Furthermore, after peeling the photoresist with methyl cellosolve acetate, 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 μm.

[2] Preparation of colored pixels A photosensitive red resist was applied on a polyimide resin film on a glass substrate on which a black matrix was patterned. At this time, the rotational speed of the spinner was adjusted so that the resist thickness at the black matrix opening after the heat treatment was 2.0 μm. Next, red-colored pixels were obtained by pre-baking at 100 ° C. for 10 minutes on a hot plate. Next, using a UV exposure machine “PLA-5011” manufactured by Canon Inc., a black matrix opening and a part of the area on the black matrix are passed through a chrome photomask through which light is transmitted in an island shape. , 100 mJ / cm ² (ultraviolet intensity at 365 nm). After exposure, 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.

  Similarly, a green pixel made of a photosensitive green resist and a blue pixel made of a photosensitive blue resist were produced. Subsequently, the rotation speed of the spinner was adjusted so that the thickness of the colored pixel portion after the heat treatment was 2.5 μm, and the resin composition was applied. Then, it heat-processed for 30 minutes in 230 degreeC oven, and produced the overcoat layer.

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.
Excellent (A): BM positional deviation amount is 1.8 μm or less.
Good (B): BM positional deviation amount is more than 1.8 μm and 2.4 μm or less.
Defect (C): BM positional deviation amount exceeds 2.4 μm.

(15) Preparation of organic EL element and measurement of angle dependency of color coordinate (x, y) Creation of organic EL element and measurement of angle dependency of color coordinate (x, y) are performed by the method described below. went.

[1] Production of 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 μm, 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.

  Further, in order to flatten the unevenness due to the formation of the wiring, 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 μm square was formed in the produced planarization layer, and the thickness was about 2 μm.

[2] Production of Bottom Emission Organic EL Element The following portions were formed on the obtained planarization layer to produce a bottom emission organic EL element. First, the first electrode 17 made of ITO was formed on the planarizing layer by connecting to the wiring through the contact hole. Thereafter, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, patterning of the first electrode was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped using a resist stripping solution (mixed solution of monoethanolamine and diethylene glycol monobutyl ether). The substrate after peeling was washed with water and dehydrated by heating at 200 ° C. for 30 minutes to obtain an electrode substrate with a planarizing layer. The thickness change of the planarizing layer was less than 1% after heat dehydration with respect to the thickness before the treatment with the stripping solution. The first electrode thus obtained corresponds to the anode of the organic EL element.

  Next, an insulating layer having a shape covering the end portion of the first electrode was formed. The photosensitive polyimide varnish was also used for the insulating layer. By providing this insulating layer, it is possible to prevent a short circuit between the first electrode and the second electrode formed in the subsequent process.

  Furthermore, 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 A layer was provided. Next, 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.

The obtained said board | 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 type organic EL element through a drive circuit to display in red, and the luminance alignment 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.
Excellent (A): | x−x ′ | + | y−y ′ | ≦ 0.3
Good (B): | x−x ′ | + | y−y ′ | ≦ 0.5
Possible (C): | x−x ′ | + | y−y ′ | ≦ 0.7
Defect (D): | x−x ′ | + | y−y ′ |> 0.7.

(16) 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. In the light resistance test, the polyimide resin film on the glass substrate prepared in (3) was used, and light was applied from the resin film side.
Apparatus: Q-Sun Xe-1 (manufactured by Q-Lab Corporation)
Illuminance at a wavelength of 340 nm: 0.4 W / m ²
Black panel temperature: 55 ° C. Irradiation time: 250 hours.

Hereinafter, the abbreviations of the compounds used in the examples are described.
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 ) Fluorene anhydride 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 DABA: 4,4′-diaminobenzanilide 4-ABS-3AP: 3-aminophenyl-4 -Aminobenzenesulfonate NMP: N-methyl-2-pyrrolidone.

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 of varnish obtained in Example 1 (concentration: 16%), and 30 at 30 ° C. The varnish was prepared by stirring for a minute.

Example 9
50 g (concentration 16%) of the varnish obtained in Example 1 was 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 the 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 stream, 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.

Comparative Example 1
Under a dry nitrogen stream, 3.62 g (18.4 mmol) of CBDA, 5.91 g (18.4 mmol) of TFMB, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was heated and stirred at 60 ° C. After 8 hours, it was cooled to obtain a varnish.

Comparative Example 2
Under a dry nitrogen stream, CBDA 2.33 g (11.9 mmol), HFHA 7.19 g (11.9 mmol), and NMP 50 g were added to a 100 mL four-necked flask and heated and stirred at 60 ° C. After 8 hours, it was cooled to obtain a varnish.

Comparative Example 3
Under a dry nitrogen stream, CBDA 3.05 g (15.6 mmol), TFMB 2.49 g (7.78 mmol), HFHA 4.70 g (7.78 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.

Comparative Example 4
Under a dry nitrogen stream, 4.26 g (14.5 mmol) of BPDA, 3.95 g (12.3 mmol) of TFMB, 1.31 g (2.17 mmol) of HFHA, and 50 g of NMP 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.

  The compositions of the varnishes synthesized in Examples 1 to 16 and Comparative Examples 1 to 4 are shown in Tables 1-2. Further, using these varnishes, the light transmittance (T), in-plane / out-of-plane birefringence, haze value, 1% thermogravimetric decrease temperature (Td1) of the polyimide resin film 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 1-2.

  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 17-20. Since the polyimide resin of Examples 7-9 contains the ultraviolet absorber, it turns out that the deterioration of the film | membrane before and after a 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.

DESCRIPTION OF SYMBOLS 1 Touch panel 2 Polyimide resin 3 Black frame 4 1st transparent wiring 5 Insulating film 6 Lead-out wiring 7 Second transparent wiring 8 Transparent protective film 9 Gas barrier layer 10 Color filter 11 Black matrix 12R Red pixel 12G Green pixel 12B Blue pixel 13 Over Coat layer 14 Liquid crystal element 15 Pixel electrode 16 First alignment film 17 Second alignment film 18 Counter electrode 19 Liquid crystal layer 20 Polarizing plate 21 Organic EL element 22 TFT layer 23 Flattening layer 24 First electrode 25 Insulating layer 26R Red organic EL light emission Layer 26G Green organic EL light emitting layer 26B Blue organic EL light emitting layer 27 Second electrode 32 Polyimide resin 42 Polyimide resin

Claims (20)

A polyimide resin comprising a structural unit represented by general formula (1) as a main component and a structural unit represented by general formula (2) in an amount of 2 mol% to 30 mol% of all structural units.
(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. And 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 or an oxygen atom. And a divalent cross-linked 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 structural unit represented by the general formula (1) is a main component, and the structural unit represented by the general formula (2) is included in an amount of 5 mol% to 30 mol% of all structural units. Polyimide resin. The polyimide resin according to claim 1 or 2, wherein R ¹ in the general formulas (1) and (2) is 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 2} in the general formula (1) is at least one member selected from the following general formulas (14) to (17), a polyimide resin according to claim 1.
(R ^{56 to} R ⁸⁷ each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 3 carbon atoms that may be substituted with a halogen atom.) Formula (1) R ² is represented by the following general formula in (18) to at least one selected from structures represented by (21), a polyimide resin according to claim 1.
Furthermore, the polyimide resin in any one of Claims 1-5 containing the structural unit represented by General formula (22).
(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. And a tetravalent organic group having 4 to 40 carbon atoms connected to each other through X. X ² and X ³ may be the same or different, and may be an aromatic ring, an aliphatic ring, a chain hydrocarbon group, Or a structure composed of a combination thereof, or a structure composed of a combination of these and one or more groups selected from the group consisting of an amide group, an ester group, an ether group, an alkylene group, an oxyalkylene group, a vinylene group and a haloalkylene group. is there.) The polyimide resin in any one of Claims 1-6 which has a structure represented by General formula (24) in the acid dianhydride residue and / or diamine residue which comprise a polyimide.
(In General Formula (24), 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.) The polyimide resin composition containing the polyimide resin in any one of Claims 1-7, and a ultraviolet absorber. The polyimide resin composition according to claim 8, wherein the ultraviolet absorber is a compound having a molecular weight of 1000 or less. The polyimide resin composition of Claim 8 or 9 whose said ultraviolet absorber is a compound represented by General formula (28) or General formula (29).
(In General Formulas (28) and (29), 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. ) The polyimide resin composition in any one of Claims 8-10 whose content of the said ultraviolet absorber is 0.5-10 mass parts with respect to 100 mass parts of polyimide resins. The laminated body which has an inorganic film on the resin film containing the polyimide resin in any one of Claims 1-7. The touch panel provided with the resin film containing the polyimide resin in any one of Claims 1-7. A method for manufacturing a touch panel including the following steps;
(1) The process of apply | coating a polyimide precursor resin composition on a support substrate;
(2) a step of removing the solvent from the applied polyimide precursor resin composition;
(3) Imidating a polyimide precursor and obtaining the polyimide resin film in any one of Claims 1-7;
(4) forming a transparent wiring, an insulating film and a lead-out wiring on the polyimide resin film;
(5) A step of peeling the polyimide resin film from the support substrate. The color filter provided with the resin film containing the polyimide resin in any one of Claims 1-7. A method for producing a color filter including the following steps;
(1) The process of apply | coating a polyimide precursor resin composition on a support substrate;
(2) a step of removing the solvent from the applied polyimide precursor resin composition;
(3) Imidating a polyimide precursor and obtaining the polyimide resin film in any one of Claims 1-7;
(4) A step of forming a black matrix on the polyimide resin film;
(5) forming a colored pixel on the polyimide resin film;
(6) A step of peeling the polyimide resin film from the support substrate. The liquid crystal element provided with the resin film containing the polyimide resin in any one of Claims 1-7. A method for producing a liquid crystal device comprising the following steps;
(1) The process of apply | coating a polyimide precursor resin composition on a support substrate;
(2) a step of removing the solvent from the applied polyimide precursor resin composition;
(3) Imidating a polyimide precursor and obtaining the polyimide resin film in any one of Claims 1-7;
(4) forming a transparent electrode, an alignment film and a liquid crystal layer on the polyimide resin film;
(5) A step of peeling the polyimide resin film from the support substrate. The organic EL element provided with the resin film containing the polyimide resin in any one of Claims 1-7. The manufacturing method of the organic EL element including the following processes;
(1) The process of apply | coating a polyimide precursor resin composition on a support substrate;
(2) a step of removing the solvent from the applied polyimide precursor resin composition;
(3) Imidating a polyimide precursor and obtaining the polyimide resin film in any one of Claims 1-7;
(4) forming an organic EL light emitting circuit on the polyimide resin film;
(5) A step of peeling the polyimide resin film from the support substrate.