JP2015078254A - Resin composition, polyimide resin film using the same, color filter, tft substrate and display device including the same, and their production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyimide precursor resin composition which realizes a polyimide resin film with a low haze value.SOLUTION: A resin composition comprises: (a) a polyimide precursor having a structural unit represented by general formula (1); and (b) a compound having at least two monovalent organic groups represented by formula (2) or (3).

Description

  The present invention relates to a polyimide precursor resin composition containing an epoxy compound, a polyimide resin film using the same, a TFT substrate containing the same, a display device, and methods for producing them. More specifically, the present invention relates to a resin composition suitably used for a circuit board such as a flexible substrate and a flexible printed circuit board applicable to a flat panel display, a touch panel, electronic paper, a color filter, a TFT substrate, a solar cell and the like.

  Organic films are more flexible than glass, and are not easily broken and light. Recently, studies have been actively made to reduce the weight and flexibility of displays by forming substrates of display devices and light receiving devices using organic films. A display device refers to a liquid crystal panel, an organic EL panel, electronic paper, or the like. The light receiving device refers to a touch panel, a color filter, and the like. In general, examples of the resin used for the organic film include polyester, polyamide, polyimide, polycarbonate, polyethersulfone, acrylic, and epoxy. In particular, polyimide resin has high mechanical strength such as high mechanical strength, abrasion resistance, dimensional stability, chemical resistance, and excellent electrical properties such as insulation, in addition to high heat resistance. It is attracting attention as an alternative material.

  As a material used for a substrate of a display device or a light receiving device, first, heat resistance and a low coefficient of linear thermal expansion (CTE) are required. For example, in order to form an active matrix driven low-temperature polysilicon thin film transistor (TFT) or oxide TFT used as a TFT substrate for an organic EL panel on a polyimide film, it is generally 300 ° C. to 650 ° C. Heat resistance is necessary. Furthermore, low CTE properties are also required from the viewpoint of dimensional stability during processing.

  Transparency is mentioned as the 2nd characteristic calculated | required by the material used for a board | substrate. For example, a color filter substrate or a transparent circuit substrate requires high light transmittance (colorlessness) and transparency (no cloudiness) in the visible light region. The TFT substrate is also preferably transparent. In general, a photolithography method is used for processing TFTs. In this case, the processing accuracy of the device strongly depends on the alignment accuracy of the base material and the mask. In general, alignment marks are used for alignment, and when a resin film is formed on the alignment marks, if the resin is clouded, it becomes difficult to recognize the alignment marks, and devices are fabricated on the resin substrate. Or the processing accuracy of the element is lowered. Furthermore, from the viewpoint of improving the sensitivity of the defect inspection of the formed resin film, the resin film is preferably free of white turbidity.

  As a polyimide having heat resistance and low CTE property, a polyimide containing 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as an acid dianhydride component is disclosed (for example, Patent Documents 1 to 4). 6), for example, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and p-phenylenediamine, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis Polyimides obtained from (trifluoromethyl) benzidine and the like are disclosed.

JP 2012-184281 A JP 2012-144603 A JP2013-082774A JP 2010-202729 A JP 2005-314630 A JP 2012-051995 A

  As described above, although a material having heat resistance has been proposed, as described in Patent Document 6, the polyimide film has a problem that haze occurs due to crystallization of molecular chains depending on the conditions of the thermal imidization process. There is. Furthermore, Patent Document 6 discloses a method for reducing the haze value of a polyimide film, but the haze value of a polyimide film (10 micron thickness) obtained by using this method is about 2 to 4%. The appearance is cloudy and is insufficient from the viewpoint of transparency. Therefore, a material satisfying all of heat resistance, low CTE property and transparency has not been obtained.

  In view of the above problems, the present invention includes a polyimide precursor resin composition that gives a polyimide resin film having a low haze value, a polyimide resin film obtained by heat-treating the resin composition, and the polyimide resin film as a base material. An object is to provide a display device, a light receiving device, and a circuit board.

  The inventors of the present invention have studied the above problems, and have reached the configuration of the present invention by working on solving the problems from the viewpoint of suppressing crystallization, which is a cause of cloudiness of the film.

  That is, the present invention provides (a) a polyimide precursor having a structural unit represented by the general formula (1) and (b) at least two monovalent organic groups represented by the formula (2) or (3). It is a resin composition containing the compound which has.

(In the general formula (1), X ¹ and X ² are each independently a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, A is a tetravalent organic group, and B is a divalent organic group. Group.)

  ADVANTAGE OF THE INVENTION According to this invention, the polyimide precursor resin composition which gives the polyimide resin film of a low haze value can be obtained. This enables, for example, processing of a display device, a light receiving device, and a circuit board with high accuracy on the polyimide resin film, and leads to improvement of processing accuracy.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

<Resin composition>
The resin composition of the present invention comprises (a) a polyimide precursor having a structural unit represented by the general formula (1), and (b) a monovalent organic group represented by the formula (2) or (3). Including at least two compounds

In the general formula (1), X ¹ and X ² are each independently a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, A is a tetravalent organic group, and B is a divalent organic group. It is.

[(A) Polyimide precursor having a structural unit represented by the general formula (1)]
In the general formula (1), X ¹ and X ² each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. Examples of the case where X ¹ and X ² in the general formula (1) are a monovalent organic group having 1 to 10 carbon atoms include a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic group, and an alkylsilyl group. Etc. Examples of the saturated hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, and a tert-butyl group. Examples of the unsaturated hydrocarbon group include a vinyl group, an ethynyl group, a biphenyl group, and a phenylethynyl group. The saturated hydrocarbon group may be further substituted with a halogen atom. Examples of the aromatic group include a phenyl group. The aromatic group may be further substituted with a saturated hydrocarbon group, an unsaturated hydrocarbon group or a halogen atom. Examples of the alkylsilyl group include a trimethylsilyl group.

  In general formula (1), A represents a tetravalent organic group, which is an acid dianhydride and a derivative residue thereof. A preferably has 1 to 40 carbon atoms. Examples of A include a tetravalent aromatic group, an alicyclic aliphatic group, and a chain aliphatic group.

  As aromatic dianhydrides, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-terphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-oxyphthalate Acid dianhydride, 2,3,3 ′, 4′-oxyphthalic dianhydride, 2,3,2 ′, 3′-oxyphthalic 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, 1,4- (3,4-dicarboxyphenoxy) benzene dianhydride, p-phenylenebis (trimellitic acid monoester acid anhydride), 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, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 2,3 5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2 , 2-bis (4- (3,4-dicarboxybenzoyloxy) 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, 2,2 ′ -Bis [(dicarboxyphenoxy) phenyl] propane dianhydride, 2,2'-bis [(dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride Or acid dianhydride compounds in which these aromatic rings are substituted with an alkyl group, an alkoxy group, a halogen atom, or the like, but are not limited thereto.

  Examples of the alicyclic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5. -Cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride Anhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2 , 3,4-cycloheptanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 2,3 5-tori Ruboxycyclopentyl acetic acid 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-tetracarboxylic dianhydride, bicyclo [2,2,2] oct -7-ene-2,3,5,6-tetracarboxylic dianhydride, bi Chlo [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-dicarboxylicsan anhydride, and “Licacid” ® BT-100 (above, trade name, New Nippon Rika Co., Ltd.) and derivatives thereof, or acid dianhydride compounds in which these alicyclic rings are substituted with an alkyl group, an alkoxy group, a halogen atom, or the like, are not limited thereto.

  Examples of the aliphatic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and derivatives thereof. It is not limited to these.

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

  Among these, it is preferable that A is a tetravalent organic group selected from the following formulas (4) to (6) from the viewpoints of heat resistance, low CTE properties, and commercial availability. That is, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, p-phenylenebis (trimellitic acid monoester acid anhydride) is used as the acid dianhydride. Is preferred.

  Among these, the formula (6) having an ester structure is inferior to the other two acid dianhydrides from the viewpoint of heat resistance. Therefore, when the heat resistance is particularly important, A is the formula (4) or It is preferable that it is a tetravalent organic group selected from (5). That is, pyromellitic dianhydride and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride are particularly preferable as the acid dianhydride.

  In general formula (1), B represents a divalent organic group and is a diamine residue. B preferably has 1 to 40 carbon atoms. Examples of B include an aromatic group, an alicyclic aliphatic group, and a chain aliphatic group.

  As aromatic diamine compounds, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylsulfone, 3, 4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, benzidine 2,2'-bis (trifluoromethyl) benzidine, 3,3'-bis (trifluoromethyl) benzidine, 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 2,2'3,3 '-Tetramethylbenzidine, 2,2'-dichlorobenzidine, 3,3'-di Lolobenzidine, 2,2′3,3′-tetrachlorobenzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, Bis (3-aminophenoxyphenyl) sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 1,4 -Bis (4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2'-bis [3- (3-aminobenzamido) -4-hydroxyphenyl] hexafluoropropane, 4- Aminophenyl-4'-aminobenzoate, 4,4'-diaminobenzani De or an alkyl group in these aromatic ring, an alkoxy group, and a diamine compound substituted with a halogen atom, but is not limited thereto.

  Examples of the alicyclic diamine compound include cyclobutane diamine, isophorone diamine, bicyclo [2,2,1] heptane bismethylamine, tricyclo [3,3,1,13,7] decane-1,3-diamine, 1,2 -Cyclohexyldiamine, 1,3-cyclohexyldiamine, 1,4-diaminocyclohexane, trans-1,4-diaminocyclohexane, cis-1,4-diaminocyclohexane, 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'-diaminodicyclohexyl Rumethane, 3,5-diethyl-3 ′, 5′-dimethyl-4,4′-diaminodicyclohexylmethane, 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) propane, 2,2-bis (3,5-diethyl-4-aminocyclohexyl) propane, 2,2- (3,5- Diethyl-3 ′, 5′-dimethyl-4,4′-diaminodicyclohexyl) propane, or diamine compounds in which these alicyclic rings are substituted with an alkyl group, an alkoxy group, a halogen atom, or the like, are limited thereto. It is not a thing.

  Examples of the aliphatic diamine compound include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, and 1,8-diaminooctane. Alkylene glycols such as 1,9-diaminononane and 1,10-diaminodecane, ethylene glycol diamines such as bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, And 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, and α, ω-bis (3-aminopropyl) polydimethylsiloxane Although diamine is mentioned, it is not limited to these.

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

  Among these, it is preferable that B is a divalent organic group selected from the following formulas (7) to (12) from the viewpoint of being commercially available and easy to obtain, heat resistance, and low CTE properties. That is, p-phenylenediamine, 2,2′-dimethylbenzidine, 2,2′-bis (trifluoromethyl) benzidine, 4-aminophenyl-4′-aminobenzoate, 4,4′-diaminobenzanilide as a diamine, It is preferable to use trans-1,4-diaminocyclohexane. Among these, trans-1,4-diaminocyclohexane has an alicyclic structure and has low heat resistance. Therefore, for applications that require a high temperature of 400 ° C. or higher, such as a low-temperature polycrystalline polysilicon TFT, B is preferably an aromatic divalent organic group.

  Furthermore, although ester groups and amide groups are highly effective in reducing CTE, heat resistance is not high. Therefore, when the heat resistance is more important, it is preferable that B is a divalent organic group selected from the formula (7), (8) or (9). That is, as the diamine, p-phenylenediamine, 2,2'-dimethylbenzidine, or 2,2'-bis (trifluoromethyl) benzidine is preferable.

  Among these, when 2,2'-bis (trifluoromethyl) benzidine is used, the CTE is higher than that of polyimide using the other two diamines due to the bulky trifluoromethyl group. Therefore, when heat resistance, low CTE property, and white turbidity suppression are satisfied at a high level, B is preferably a divalent organic group selected from the formula (7) or (8). That is, p-phenylenediamine or 2,2'-dimethylbenzidine is preferable as the diamine.

  From the above, polyimides satisfying heat resistance, low CTE property, and white turbidity suppression at a high level include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid as acid dianhydride. Polyimide using acid dianhydride and p-phenylenediamine or 2,2′-dimethylbenzidine as diamine is preferable. By using these polyimide films as the substrate of the TFT substrate, gas barrier films and TFTs can be manufactured under high temperature conditions of 400 ° C. or higher, and the warpage of the TFT substrate using the obtained polyimide resin film is suppressed. can do.

  Further, since siloxane diamines can improve the adhesion between the polyimide resin film and the substrate, it is possible to suppress the peeling of the resin film and the occurrence of cracks in the manufacturing process of the polyimide resin film and the display device. The copolymerization ratio is not particularly limited as long as heat resistance and optical characteristics are not impaired, but a range of 0.1 to 10 mol% is preferable.

  In addition, the ratio of the structural unit of a polymer can be measured by the mass analysis of a polyimide precursor or a polyimide, pyrolysis gas chromatography (GC), NMR, and IR measurement.

  Although the molecular weight of the polyimide precursor of this invention is not specifically limited, The range of 5000-200000 is preferable from a viewpoint of mechanical strength and the applicability | paintability of a varnish. The molecular weight of the polyimide precursor can be measured by gel permeation chromatography (GPC) measurement.

  The polyimide precursor of the present invention may be sealed at both ends with a terminal blocking agent in order to adjust the molecular weight to a preferred range. 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 glycol Cole 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 mono Examples include, but are not limited to, methylol, tricyclodecane monomethylol, norbonol, terpineol, and the like.

  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. Isocyanates such as chloroformates, butyl isocyanate, 1-naphthyl isocyanate, octadecyl isocyanate, phenyl isocyanate, butyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, 2-ethylhexyl vinyl ether, isobutyl vinyl ether, isopropyl vinyl ether, n -Propyl vinyl ether, tert-butyl vinyl ether, benzyl vinyl ether and the like.

  Examples of other compounds used as 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 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 5 to 90 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 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 and ¹³ C NMR spectrum measurement.

[(B) Compound having at least two monovalent organic groups represented by formula (2) or (3)]
As described above, whitening of the polyimide film is considered to be caused by crystallization of polyimide molecular chains. In general, since crystallization of a polymer compound requires rearrangement of molecular chains, crystallization occurs when molecular chain mobility is high to some extent. Solvent molecules remain in the polyimide precursor film formed by drying the coating film of the polyimide precursor resin composition solution, and the solvent molecules act as a plasticizer, so that the polyimide precursor during the thermal imidization process It is thought that the mobility of the body molecular chain increases and crystallization proceeds. In particular, in General Formula (1), A is a tetravalent organic group selected from Formulas (4) to (6), and B is a divalent organic group selected from Formulas (7) to (9). If so, it is considered that the polyimide precursor and the polyimide molecular chain have high rigidity and are particularly easily crystallized. That is, it is estimated that the polyimide having high heat resistance and low CTE property is likely to become cloudy.

  Although the details of the mechanism in which the component (b) in the present invention suppresses white turbidity has not been clarified, it is presumed to be caused by inhibition of crystallization of two polyimide molecular chains.

(1) Formation of a crosslinked structure (b) Since the component has at least two monovalent organic groups represented by the formula (2) or (3) having high reactivity with a carboxyl group, (a) It is thought that molecular chain mobility is lowered by cross-linking of the polyimide precursor molecular chain by the reaction of the carboxyl group of the component polyimide precursor and the organic group, and as a result, the crystallization of the polyimide film is inhibited. It is done.

(2) Steric hindrance of cross-linked structure Crystallization of polymer chains requires a uniform aggregate structure of the molecular chains. It is considered that the cross-linking structure produced by the reaction between the component (a) and the component (b) becomes a steric hindrance and inhibits the formation of a uniform aggregate structure of polyimide molecular chains, thereby inhibiting crystallization.

  (B) As a component, what contains the diepoxy compound represented by General formula (13) from a viewpoint of white turbidity suppression is preferable.

D is a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, or a divalent organic group having 1 to 40 carbon atoms. Examples of the organic group include a saturated hydrocarbon group, an unsaturated hydrocarbon group, and an aromatic group. Examples of the saturated hydrocarbon group include alkylene groups such as a methylene group, an ethylene group, and a propylene group. The saturated hydrocarbon group may be further substituted with a halogen atom. Examples of the unsaturated hydrocarbon group include —CH═CHCH ₂ — and —CH═CHCH ₂ CH ₂ — groups. Examples of the aromatic group include a phenylene group, a naphthylene group, and bisphenylfluorene. The aromatic group may be further substituted with a halogen atom.

R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. Examples of the organic group include a saturated hydrocarbon group, an unsaturated hydrocarbon group, and an aromatic group. Examples of the saturated hydrocarbon group include alkyl groups such as methyl group, ethyl group, and tert-butyl group, and alkoxy groups such as methoxy and ethoxy. The saturated hydrocarbon group may be further substituted with a halogen atom. Examples of the unsaturated hydrocarbon group include a vinyl group, an ethynyl group, a biphenyl group, a phenylethynyl group, and a styryl group. Examples of the aromatic group include a phenyl group. The aromatic group may be further substituted with a halogen atom.

  a and b are each independently an integer of 0 to 4;

  Since the compound represented by the general formula (13) has an aromatic ring, the cross-linked structure formed by the component (a) and the component (b) becomes rigid, and the mobility of the polyimide precursor molecular chain is lowered. Can do. As a result, the white turbidity suppressing effect can be enhanced.

  Specific examples of such compounds are (when D is a single bond) 4,4′-diglycidyloxybiphenyl, 3,3′-dimethyl-4,4′-diglycidyloxybiphenyl, 3,3 ′, 5 , 5′-tetramethyl-4,4′-diglycidyloxybiphenyl, D is a hydrocarbon group: bis (4-glycidyloxyphenyl) methane, bis (2-ethyl-4-glycidyloxyphenyl) methane, bis (5 -Methyl-2-glycidyloxyphenyl) methane, bis (2-glycidyloxyphenyl) methane, 2-glycidyloxyphenyl-4-glycidyloxyphenylmethane, 1,1-bis (4-glycidyloxyphenyl) ethane, 2, 2-bis (4-glycidyloxyphenyl) propane, 2,2-bis (2-methyl-4-glycidyloxyphenyl) Lopan, 2,2-bis (3-methyl-4-glycidyloxyphenyl) propane, 2,2-bis (2-glycidyloxyphenyl) propane, 2- (2-glycidyloxyphenyl) -2- (4-glycidyl) Alkyl or alkenyl substituents such as oxyphenyl) propane, 1,1-bis (4-glycidyloxyphenyl) cyclohexane, 9,9-bis (4-glycidyloxyphenyl) fluorene, and bis (when D is an oxygen atom) Alkyl or alkenyl substituents such as 4-glycidyloxyphenyl) ether and bis (4-glycidyloxy3-methylphenyl) ether, bis (2-glycidyloxyphenyl) ether, and bis (4- Glycidyloxyphenyl) thioether, bis (4-glycidylo) Alkyl or alkenyl substituents such as cis (3-methylphenyl) thioether, or alkyl or alkenyl such as bis (4-glycidyloxyphenyl) sulfone or bis (4-glycidyloxy-3-methylphenyl) sulfone (when D is a sulfonyl group) It is a substitute.

  The above compound can be obtained, for example, by reacting a compound having two or more hydroxy groups with epichlorohydrin. This reaction can be performed in the same manner as a normal epoxidation reaction.

  The reaction between the hydroxy compound and epichlorohydrin is, for example, 50 to 150 in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide after dissolving the hydroxy compound in excess epichlorohydrin. The method of making it react for 1 to 10 hours in the range of ° C, preferably 60 to 120 ° C. In this case, the amount of the alkali metal hydroxide used is in the range of 0.8 to 2 mol, preferably 0.9 to 1.2 mol, relative to 1 mol of the hydroxyl group in the hydroxy compound. Epichlorohydrin is used in excess with respect to the hydroxyl group in the hydroxy compound, but is usually in the range of 1.5 to 25 mol, preferably 2 to 15 mol, relative to 1 mol of the hydroxyl group in the hydroxy compound. It is. After completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the solvent is distilled off. The target compound can be obtained.

  The product of the above reaction may include an oligomer produced by the reaction of the epoxy group of the compound as the component (b) with the hydroxyl group of the hydroxy compound as a starting material. However, the content of the oligomer is preferably 50% by weight or less and more preferably 20% by weight or less with respect to the compound to be the component (b). When the oligomer is 50% by weight or less, the heat resistance can be increased and the haze value can be decreased.

  Suitable examples of hydroxy compounds are (when D is a single bond) 4,4′-dihydroxybiphenyl, 3,3′-dimethyl-4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetra Methyl-4,4′-dihydroxybiphenyl, D is a hydrocarbon group: bis (4-hydroxyphenyl) methane, bis (2-ethyl-4-hydroxyphenyl) methane, bis (5-methyl-2-hydroxyphenyl) methane Bis (2-hydroxyphenyl) methane, 2-hydroxyphenyl-4-hydroxyphenylmethane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2 -Bis (2-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, , 2-bis (2-hydroxyphenyl) propane, 2- (2-hydroxyphenyl) -2- (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 9,9-bis ( Alkyl or alkenyl substituents such as 4-hydroxyphenyl) fluorene, (when D is an oxygen atom) alkyl or alkenyl substituents such as bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3-methylphenyl) ether Alkyl or alkenyl substituents such as bis (2-hydroxyphenyl) ether, (when D is a sulfur atom) bis (4-hydroxyphenyl) thioether, bis (4-hydroxy-3-methylphenyl) thioether, In the case of a sulfonyl group) bis (4-hydroxyphenyl) Hong, alkyl or alkenyl substituents, such as bis (4-hydroxy-3-methylphenyl) sulfone.

  Examples of commercially available products that can be used as the component (b) include JER825, JER827, JER828, JER806, JER807, YX4000, YL6121H (above trade names, manufactured by Mitsubishi Chemical Corporation), Ogusol PG100, EG200 (above trade names, Osaka). Gas Chemical Co., Ltd.), Show Free TMBDG (trade name, Showa Denko Co., Ltd.), Epicron 830, Epicron 835, Epicron 840, Epicron 850, Epicron 152, Epicron 153 (trade name, DIC Corporation) Manufactured). Two or more of these may be used in combination.

  The content of the compound having at least two monovalent organic groups represented by formula (2) or (3) in the resin composition is not particularly limited, but (a) 100 parts by weight of the polyimide precursor On the other hand, it is preferably 5 to 40 parts by weight, and more preferably 5 to 25 parts by weight.

  As the component (b), diepoxy compounds other than the above and polyfunctional epoxy compounds having three or more epoxy groups can be used. For example, phenol novolac-type glycidyl ether compounds, trisphenol-type triglycidyl ether compounds; polyphenol-type epoxy compounds such as cresol novolac-type glycidyl ether compounds; glycidyl amine-type epoxy compounds of aniline derivatives such as aniline, toluidine, methylenediamine, aminophenol; Glycidyl ester type epoxy compounds such as phthalic acid diglycidyl ester, trimellitic acid triglycidyl ester, trimesic acid triglycidyl ester, pyromellitic acid tetraglycidyl ester; 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes, etc. Hydroxy (poly) alkoxyarylfluorene type epoxy compound; 1-cyclohexene-1,2-dicarboxylic acid diglycidyl ester 3-cyclohexene-1,2-dicarboxylic acid diglycidyl ester, 4-cyclohexene-1,2-dicarboxylic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, 3-methylhexahydrophthalic acid diglycidyl ester, 4- Alicyclic polycarboxylic acid glycidyl ester such as methylhexahydrophthalic acid diglycidyl ester, 1,2,4-cyclohexanetricarboxylic acid triglycidyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid tetraglycidyl ester; Glycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol tetraglycidyl ether, polyalkylene glycol diglycidyl ether, sorbitol polyglycidyl ether, etc. Diether ether type epoxy compounds; isocyanuric type epoxy compounds such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; hydrogenated polyphenol type epoxy compounds such as hydrogenated bisphenol A diglycidyl ether and hydrogenated bisphenol F diglycidyl ether; Vinyl-3-cyclohexylene dioxide, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate Bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylhexyl) adipate, tetrakis (3,4-epoxycyclohexylmethyl) butanthate Lacarboxylate, di (3,4-epoxycyclohexylmethyl) -4,5-epoxytetrahydrophthalate), ethylenebis (3,4-epoxycyclohexanecarboxylate), ethylenebis (3,4-epoxy-6-methylcyclohexane) Carboxylate), limonene dioxide, bis (3,4-epoxycyclohexyl) methane, 2,2-bis (3,4-epoxycyclohexyl) propane, bis (3,4-epoxycyclohexyl), 1,2,5, Cycloaliphatic epoxy compounds such as 6-cyclooctadiene dioxide and dicyclopentadiene dioxide; 1,2-ethanediol diglycidyl ether, 1,3-propanediol diglycidyl ether, propylene glycol diglycidyl ether, 1,4 -Butanegio Examples include aliphatic epoxy compounds such as lucidiglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, diethylene glycol diglycidyl ether, and neopentyl glycol diglycidyl ether. However, it is not limited to these. Further, groups other than the glycidyl ether group may be substituted with an alkyl group, an ether group, a halogen group, or the like, and two or more of these diepoxy compounds and polyfunctional epoxy compounds may be contained.

  The epoxy compound in the resin composition can be easily detected by the following method. For example, a polyimide precursor resin composition to which an epoxy compound is added, or the polyimide resin composition can be easily detected by direct pyrolysis gas chromatography (PGC), infrared spectrum and 13C, 15N NMR spectrum measurement. .

  The resin composition of the present invention may contain a monoepoxy compound as long as it contains the component (b) as long as the effects of the present invention are not impaired. Examples of the monoepoxy compound include butyl glycidyl ether, phenyl glycidyl ether, orthocresyl glycidyl ether, metaparacresyl glycidyl ether, allyl glycidyl ether, benzyl glycidyl ether, 1,3-butadiene monoepoxide, tert-butyl glycidyl ether, 1- Chloro-2,3-epoxypropane, 1,2-epoxycyclohexane, 1,4-epoxycyclohexane, 1,2-epoxycyclopentane, 1,2-epoxydecane, 1,2-epoxy-9-decene, 1, 2-epoxydodecane, 1,2-epoxyheptane, 1,2-epoxypentane, 3,4-epoxytetrahydrofuran, 1,2-epoxy-4-vinylcyclohexane, ethyl glycidyl ether, propylene oxide, 2- (3,4 − Poxycyclohexyl) monotrioxy compounds such as ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like. It is not limited. Moreover, groups other than the glycidyl ether group may be substituted with an alkyl group, an ether group, a halogen group, or the like, and two or more of these monoepoxy compounds may be contained.

  If the resin composition of this invention is a range which does not impair the effect of this invention, if it contains (b) component, it may contain the other thermal crosslinking agent. As the thermal crosslinking agent, a compound having at least two oxetane rings, 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.

  Examples of the bifunctional oxetane compound include “Ethanacol” OXBP, “Ethanacol” OXTP, “Ethanacol” OXIPA (trade name, manufactured by Ube Industries, Ltd.), PNOX-1009, OXT-121, OXT-221 (above, Examples of the compound having three or more oxetanyl groups include oxetanilated phenol resin and oxetanyl silicate. Two or more of these may be contained.

  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-TPPHAP (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 thermal crosslinking agent other than the compound having at least two monovalent organic groups represented by the formula (2) or (3) should contain 0.01 to 50 parts by weight with respect to 100 parts by weight of the polyimide precursor resin. Is preferred.

[(C) Solvent]
The resin composition of the present invention is preferably a resin composition containing a solvent. As the solvent, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, gamma butyrolactone, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N, N Polar aprotic solvents such as' -dipropylethylenediamine, N, N'-diisopropylethylenediamine, N, N'-dibutylethylenediamine, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, dioxane , Ethers such as propylene glycol monomethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, esters such as ethyl acetate, propylene glycol monomethyl ether acetate, ethyl lactate, toluene Aromatic hydrocarbons such as xylene and the like may be used alone, or two or more.

  The content of the solvent is preferably 50 parts by weight or more, more preferably 100 parts by weight or more, preferably 2,000 parts by weight or less, more preferably 1,500 parts by weight with respect to 100 parts by weight of the polyimide precursor. It is as follows. If it is the range of 50-2,000 weight part, it will become a viscosity suitable for application | coating and the thickness after application | coating can be adjusted easily.

[Other ingredients]
The resin composition of the present invention may contain a surfactant. Fluorosurfactants such as Florard (trade name, manufactured by Sumitomo 3M Co., Ltd.), Megafuck (trade name, manufactured by DIC Corporation), Sulflon (trade name, manufactured by Asahi Glass Co., Ltd.), etc. Can be given. 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 (Bic Chemie Corporation) )) And other organic siloxane surfactants. Emulmin (Sanyo Kasei Kogyo Co., Ltd., polyoxyalkylene lauryl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether and polyoxyethylene cetyl ether surfactants are included. In addition, polyflow (trade name, Kyoeisha Chemical ( Acrylic polymer surfactants such as those manufactured by KK).

  It is preferable to contain 0.01-10 weight part of surfactant with respect to 100 weight part of resin compositions.

  The resin composition of the present invention may contain an internal release agent. Examples of the internal mold release agent include long chain fatty acids.

  A coupling agent such as a silane coupling agent or a titanium coupling agent can be added to the resin composition of the present invention in order to improve adhesion to the substrate. Examples of the coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyltributoxysilane, γ-aminoethyltriethoxysilane, γ -Aminoethyltrimethoxysilane, γ-aminoethyltripropoxysilane, γ-aminoethyltributoxysilane, γ-aminobutyltriethoxysilane, γ-aminobutyltrimethoxysilane, γ-aminobutyltripropoxysilane, γ-amino Examples of the titanium coupling agent include γ-aminopropyltriethoxytitanium, γ-aminopropyltrimethoxytitanium, γ-aminopropyltripropoxytitanium, and γ-aminopropylene. Tributoxytitanium, γ-aminoethyltriethoxytitanium, γ-aminoethyltrimethoxytitanium, γ-aminoethyltripropoxytitanium, γ-aminoethyltributoxytitanium, γ-aminobutyltriethoxytitanium, γ-aminobutyltrimethoxy Titanium, γ-aminobutyltripropoxytitanium, γ-aminobutyltributoxytitanium, etc. Two or more of these may be used in combination. The amount used at this time is preferably 0.1% by weight or more and 3% by weight or less with respect to the polyimide precursor.

  In addition, it is also possible to mix | blend various additives as needed.

  The resin composition of the present invention may contain a colorant. By adding a colorant, the color of the heat-treated film of the resin composition can be adjusted. For example, the color can be brought close to white by adding a blue pigment to a yellowish polyimide film.

  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 blue (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.

  The resin composition 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 contained inorganic filler preferably has a small particle size in order to prevent light scattering. The average particle size is 0.5 to 100 nm, preferably in the range of 0.5 to 30 nm.

  The content of the inorganic filler is preferably 1 to 50 parts by weight, more preferably 10 to 30 parts by weight with respect to 100 parts by weight of the polyimide precursor. As the content increases, flexibility and folding resistance decrease.

  Various known methods can be used as a method of incorporating an inorganic filler into the resin composition. For example, an organoinorganic filler sol can be mixed with a polyimide precursor. Organo inorganic filler sol is an organic solvent in which an inorganic filler is dispersed at a ratio of about 30% by weight. Examples of organic solvents include methanol, isopropanol, normal butanol, ethylene glycol, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl acetate, Examples include propylene glycol monomethyl ether, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, and gamma butyrolactone.

  In order to improve the dispersibility of the inorganic filler with respect to the polyimide precursor, the organoinorganic filler sol may be treated with a silane coupling agent. When the terminal functional group of the silane coupling agent has an epoxy group or an amino group, the affinity with the polyimide precursor is increased by bonding with the carboxylic acid of the polyimide precursor, and more effective dispersion is performed. be able to.

  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.

  The resin composition of the present invention may contain a photoacid generator. By containing a photoacid generator, when light is irradiated through a mask on which an exposure pattern is drawn, an acid is generated in the exposed portion and the solubility of the exposed portion in an alkaline aqueous solution is increased. It can be used as a composition.

  Examples of the photoacid generator used in the present invention include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts and iodonium salts. Among them, a quinonediazide compound is preferably used from the standpoint that a positive photosensitive resin composition exhibiting an excellent dissolution inhibiting effect and having a high sensitivity and a low film thickness can be obtained. Moreover, you may contain 2 or more types of photo-acid generators. Thereby, the ratio of the dissolution rate of an exposed part and an unexposed part can be enlarged more, and a highly sensitive positive type photosensitive resin composition can be obtained.

  The quinonediazide compound includes a polyhydroxy compound in which a sulfonic acid of quinonediazide is bonded with an ester, a polyamino compound in which a sulfonic acid of quinonediazide is bonded to a sulfonamide, and a sulfonic acid of quinonediazide in an ester bond and / or sulfone. Examples include amide-bonded ones. Although all the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, it is preferable that 50 mol% or more of the entire functional groups are substituted with quinonediazide. By using such a quinonediazide compound, a positive photosensitive resin composition that reacts with i-ray (wavelength 365 nm), h-ray (wavelength 405 nm), and g-ray (wavelength 436 nm) of a mercury lamp, which is a general ultraviolet ray, is obtained. be able to.

  In the present invention, the quinonediazide compound is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group. A compound having both of these groups in the same molecule may be used, or a compound using different groups may be used in combination.

  The quinonediazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, a method of reacting 5-naphthoquinonediazide sulfonyl chloride and a phenol compound in the presence of triethylamine can be mentioned. Examples of the method for synthesizing a phenol compound include a method in which an α- (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acid catalyst.

  The content of the photoacid generator is preferably 3 to 40 parts by weight with respect to 100 parts by weight of the polyimide precursor. By setting the content of the photoacid generator within this range, higher sensitivity can be achieved. Furthermore, you may contain a sensitizer etc. as needed.

  In order to form a pattern of the positive photosensitive resin, a varnish of the positive photosensitive resin is applied onto the substrate, and after exposure, the exposed portion is removed using a developer. Developers include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl An aqueous solution of a compound showing alkalinity such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. In some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, gamma butyrolactone, dimethylacrylamide, methanol, ethanol, isopropanol. Alcohols such as ethyl lactate, esters such as propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added singly or in combination. . After development, it is preferable to rinse with water. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.

  Below, the manufacturing method of the polyimide precursor which has a structural unit represented by General formula (1) is demonstrated. Polyimide precursors 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 can be produced, and a known reaction method can be used.

  As a specific reaction method, a predetermined amount of all diamine components and a solvent are charged and dissolved in a reactor, and then a predetermined amount of acid dianhydride component is charged and stirred at room temperature to 80 ° C. for 0.5 to 30 hours. The method of doing is mentioned.

  Below, the method to manufacture a polyimide resin film using the resin composition of this invention is demonstrated. The polyimide resin film may contain the aforementioned surfactant, internal release agent, thermal crosslinking agent, colorant, inorganic filler, photoacid generator, and the like.

  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, alkali-free glass, or the like is used, but is not limited thereto. Examples of the coating method include a slit 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 these, spin coating or slit coating is preferable.

  Next, the polyimide precursor resin composition applied to the substrate is dried to obtain a polyimide precursor resin composition film. For drying, a hot plate, an oven, an infrared ray, a vacuum chamber or the like is used. When a hot plate is used, the object to be heated is heated by holding it 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 are 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, the resin layer coated on a 300 mm × 350 mm × 0.7 mm glass substrate is heated. In this case, the height of the proxy pin is preferably about 2 to 12 mm.

  Among these, it is preferable to perform vacuum drying using a vacuum chamber, and it is more preferable to perform heating for drying after vacuum drying, or heating for drying while vacuum drying. As a result, the drying process time can be shortened, and a uniform coating film can be obtained. The heating temperature for drying 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 170 ° C for 1 minute to several hours. The room temperature is usually 20 to 30 ° C, preferably 25 ° C. Furthermore, you may perform a drying process in multiple times on the same conditions or different conditions.

  Next, heating for imidization is performed. The polyimide precursor resin composition film is heated in the range of 180 ° C. or more and 650 ° C. or less to be converted into a polyimide resin film. This is called a thermal imidization step. The thermal imidization process may be performed after passing through some process after the drying process.

  The atmosphere of the thermal imidization step is not particularly limited, and may be air or an inert gas such as nitrogen or argon. However, if firing is performed in an atmosphere having a high oxygen concentration, the mechanical properties deteriorate, such as the fired film becoming brittle due to oxidative degradation. In order to suppress such deterioration of mechanical properties, it is preferable to perform thermal imidization by heating in an atmosphere having an oxygen concentration of 5% or less. On the other hand, oxygen concentration management in the ppm order is often difficult at the manufacturing site. The polyimide resin film of the present invention is preferable if the oxygen concentration at the time of heat curing is 5% or less because higher mechanical properties can be maintained.

  In addition, the time required to reach the heating temperature for thermal imidization is not particularly limited, and a temperature raising method that matches the heating type of the production line can be selected. For example, in the oven, the polyimide precursor resin film formed on the substrate may be heated from room temperature to the heating temperature over 5 to 120 minutes, or heated in the range of 200 ° C. to 650 ° C. in advance. The polyimide precursor resin film formed on the base material may be suddenly put into the oven and the heat treatment may be performed. Generally, when the heating rate is increased, white turbidity becomes remarkable. This is because when the polyimide precursor film is rapidly heated, more solvent remains in the film even in the process of thermal imidization than when the temperature is gradually raised. Therefore, it is considered that crystallization is likely to proceed by increasing the mobility of the polyimide precursor molecular chain due to its plasticizing effect. As described above, since the crystallization of the polyimide molecular chain is suppressed by the component (b) in the resin composition of the present invention, a polyimide resin film having a low haze value can be obtained regardless of the conditions of the thermal imidization step. . Therefore, the time required for the heating process can be shortened.

  The polyimide resin film obtained as described above has a low haze value and has flexibility, and can be suitably used as a flexible substrate. As a flexible substrate, the haze value is preferably 1.0% or less. In this case, white turbidity is not seen in the appearance inspection.

  Below, although it describes about the manufacturing method of the display device, light receiving device, circuit board, TFT substrate, etc. which used the polyimide resin film obtained by this invention for the base material, the polyimide resin on the base material obtained as mentioned above is described. Even if the film is peeled off from the base material, a display device, a light receiving device, a circuit, a TFT, or the like may be produced on the resin film as it is without peeling. In the latter case, it is necessary to peel off the display device light receiving device, circuit, TFT, etc. from the substrate together with the polyimide resin film. However, the peeling method is not particularly limited, and is a method of immersing in water, hydrochloric acid or hydrofluoric acid. And a method of irradiating the interface between the polyimide resin film and the substrate with laser light in a wavelength range from ultraviolet light to infrared light. In order to facilitate the peeling operation, a release agent or a sacrificial layer may be applied to the substrate before applying the polyimide precursor resin composition to the substrate. Examples of the release agent include vegetable oils, alkyds, silicones, fluorines, aromatic polymers, alkoxysilanes, and the like. Examples of the sacrificial layer include a metal film, an oxide film, and an amorphous silicon film.

  The polyimide resin film of this invention can be used conveniently for the base material of a TFT substrate. That is, a TFT substrate having an inorganic film and a TFT on the polyimide resin film of the present invention can be obtained.

A TFT substrate using the polyimide resin film of the present invention can be manufactured through at least the following steps.
(1) Step of applying the resin composition of the present invention on the substrate (2) Step of removing the solvent from the applied resin composition (3) Imidating the polyimide precursor in the resin composition to form a polyimide resin film Step of obtaining (4) Step of forming inorganic film on polyimide resin film (5) Step of forming TFT.

  A polyimide precursor resin composition is applied onto a glass substrate. Next, the solvent is removed from the resin composition applied by the drying method. Further, the polyimide precursor in the resin composition is imidized by the thermal imidization to obtain a polyimide resin film. An inorganic film is formed on the polyimide resin film.

  As the inorganic film, it is preferable to form a gas barrier film on at least one surface of the polyimide resin film in order to suppress permeation of gas such as water vapor and oxygen. Preferred gas barrier films 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. Of these, silicon oxide, nitride, or oxynitride is the main component from the viewpoint of gas barrier properties, transparency, surface smoothness, flexibility, film stress, cost, and the like. These inorganic gas barrier films can be produced by a vapor deposition method in which a film is formed by depositing a material in a vapor phase, such as sputtering, vacuum deposition, ion plating, and plasma CVD. Among these, the sputtering method is preferable from the viewpoint that particularly excellent gas barrier properties can be obtained. The thickness of the inorganic gas barrier film is preferably 10 to 300 nm, and more preferably 30 to 200 nm. In order to obtain a high gas barrier property, the film forming temperature of the inorganic film is preferably higher, preferably 300 ° C. or higher, more preferably 400 ° C. or higher, and further preferably 500 ° C. or higher.

  Examples of the semiconductor layer for forming the TFT include an amorphous silicon semiconductor, a polycrystalline silicon semiconductor, an oxide semiconductor typified by IGZO, and an organic semiconductor typified by pentacene and polythiophene. For example, using the polyimide resin film of the present invention as a base material, a gas barrier film, a gate electrode, a gate insulating film, an IGZO semiconductor layer, an etching stopper film, and a source / drain electrode are sequentially formed by a known method to produce a bottom gate type TFT. To do.

  A TFT substrate using a polyimide resin film can be manufactured through the above steps. A bottom gate type TFT comprising: Such a TFT substrate can be used as a driving substrate for a liquid crystal device or an organic EL element. In particular, as a TFT substrate for an organic EL element, a polycrystalline silicon TFT or an oxide TFT is preferable from the viewpoint of charge mobility. For the production of these TFTs, the film forming temperature is preferably 350 ° C., more preferably 400 ° C. or higher, and more preferably 450 ° C. or higher.

  For example, since a user of a bottom emission type organic EL panel senses light transmitted through a TFT substrate, a display image is blurred if white turbidity is seen on the substrate. On the other hand, since a substrate having a low haze value can be obtained by using the polyimide resin film of the present invention, a clear display image can be obtained. Further, in the manufacture of TFT substrates, the polyimide resin film of the present invention has a low haze value, so that the alignment of each pattern when forming the gate electrode, gate insulating film, IGZO semiconductor layer, etching stopper film, and source / drain electrodes The visibility of the alignment mark to be used is good, and the TFT can be manufactured with high accuracy. As a result, a TFT substrate with good driving performance can be obtained.

  Polyimides using pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride as acid dianhydride, p-phenylenediamine, 2,2'-dimethylbenzidine as diamine are heat resistant Because of its excellent properties, it becomes possible to form a TFT under a high temperature condition of 400 ° C. or higher. Furthermore, since these polyimides have low CTE properties, warping of the TFT substrate after peeling can be suppressed.

  Among the polyimide resin films of the present invention, those having a high transmittance in the visible light region can be suitably used for a color filter substrate. That is, a color filter having a black matrix and colored pixels on the polyimide resin film of the present invention can be obtained. Since the user of the display panel senses the light transmitted through the color filter, the display image becomes blurred if a resin substrate with white turbidity is used. On the other hand, since the polyimide resin film of the present invention has a low haze, by using a color filter using the polyimide resin film, a clear display image without blurring can be obtained for a user who senses light transmitted through the color filter. A good display device that can be provided is obtained.

A color filter using the polyimide resin film of the present invention can be produced through at least the following steps.
(1) Step of applying the resin composition of the present invention on the substrate (2) Step of removing the solvent from the applied resin composition (3) Imidating the polyimide precursor in the resin composition to form a polyimide resin film Obtaining step (4) forming a black matrix and colored pixels;

  An example of the manufacturing method will be described. A polyimide resin film is applied on a glass substrate. Next, the solvent is removed from the resin composition applied by the drying method. Further, the polyimide precursor in the resin composition is imidized by the thermal imidization to obtain a polyimide resin film. The gas barrier layer is preferably formed on the polyimide resin film.

  On the polyimide resin film, a black matrix paste made of polyamic acid in which a black pigment made of carbon black or titanium black is dispersed is applied by a method such as spin coater or die coater so that the film thickness after curing becomes 1 μm. After drying under reduced pressure to 60 Pa or less, semi-cure is performed in a hot air oven or hot plate at 110 to 140 ° C.

  After applying the positive resist by spin coater or die coater so that the film thickness after pre-baking is 1.2 μm, it is dried under reduced pressure to 80 Pa and pre-baked in a hot air oven or hot plate at 80 to 110 ° C. And a resist film is formed. Then, after selectively exposing with ultraviolet rays through a photomask by a proximity exposure machine or a projection exposure machine, alkali development such as 1.5 to 3% by weight of potassium hydroxide or tetramethylammonium hydroxide The exposed portion is removed by immersing in the solution for 20 to 300 seconds. Resin in which a black pigment is dispersed in a polyimide resin by removing the positive resist using a stripping solution and then heating it in a hot air oven or hot plate at 200 to 300 ° C. for 10 to 60 minutes to convert the polyamic acid to polyimide. Form a black matrix.

  The colored pixel is formed using a colorant and a resin. When a pigment is used as the colorant, the pigment is mixed with a polymer dispersant and a solvent and subjected to a dispersion treatment, and then added with an alkali-soluble resin, a monomer, a photopolymerization initiator, and the like. On the other hand, when a dye is used as the colorant, the dye is prepared by adding a solvent, an alkali-soluble resin, a monomer, a photopolymerization initiator, and the like. The total solid content in this case is the total of the polymer dispersant, the alkali-soluble resin, the monomer and the colorant, which are resin components.

  The obtained colorant composition is applied to a target film thickness of 0.8 to 3.0 μm after heat treatment by a method such as a spin coater or a die coater on a transparent substrate on which a resin black matrix is formed. After coating, the film is dried under reduced pressure up to 80 Pa and 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 with ultraviolet rays or the like 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 0.02-1% by mass of potassium hydroxide or tetramethylammonium hydroxide for 20-300 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.

  Then, after applying acrylic resin by a method such as a spin coater or die coater, vacuum drying, prebaking in a hot air oven or hot plate at 80 to 110 ° C., and 5 to 40 in a hot air oven or hot plate at 150 to 250 ° C. A flattening film is formed by partial heating.

  A color filter using a polyimide resin film can be manufactured through the above steps. The order of patterning the colored pixels is not particularly limited.

  Since the polyimide resin film of the present invention has a low haze value, the use of a color filter using the polyimide resin film provides a clear display image without blurring for the user who senses the light transmitted through the color filter. An excellent display device that can be obtained is obtained.

  The polyimide resin film of the present invention can form a transparent conductive film on at least one side and can be suitably used as a touch panel substrate. As the transparent conductive film, a known metal film, metal oxide film, or the like can be applied. Among them, it is preferable to apply a metal oxide film from the viewpoint of transparency, conductivity, and mechanical properties. Examples of the metal oxide film include indium oxide, cadmium oxide and tin oxide to which tin, tellurium, cadmium, molybdenum, tungsten, fluorine, zinc, germanium and the like are added as impurities, zinc oxide to which aluminum is added as an impurity, and oxide. Examples thereof include metal oxide films such as titanium. 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 transparent conductive film can be formed by any method as long as the target thin film can be formed. For example, from the gas phase such as sputtering, vacuum deposition, ion plating, and plasma CVD. A vapor deposition method or the like in which a material is deposited to form a film 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. Further, the thickness of the transparent conductive film is preferably 20 to 500 nm, and more preferably 50 to 300 nm.

  The polyimide resin film of this invention can be used conveniently for the base material of a flexible circuit board. There is no limitation in particular as a flexible circuit board, What formed some circuits on it by using the polyimide resin film of this invention as a base film is mentioned. For example, a photoresist film is formed on a copper-clad polyimide film (CCL) in which the polyimide resin film of the present invention is used as a base film and a copper foil is provided on one or both sides via an adhesive layer, exposure / development, etching, resist peeling Then, a solder resist film is formed, electrolytic gold plating is performed, and a cover lay film serving as a protective layer is pasted thereon to obtain a circuit board.

  The polyimide resin film of the present invention can be used for display devices such as liquid crystal displays, organic EL displays, and electronic paper, light receiving devices such as color filters, touch panels, solar cells, and CMOS. In particular, in utilizing these display devices and light receiving devices as flexible devices that can be bent, the flexible substrate of the present invention is preferably used.

  As an example of a manufacturing process of a flexible device, a circuit necessary for a display device or a light receiving device is formed on a polyimide resin film formed on a substrate, and the polyimide resin film is formed on the substrate using a known method such as laser irradiation. Peeling off.

  For example, taking a flexible organic EL display as an example, an inorganic gas barrier film is first formed on a polyimide resin film formed on a substrate. A TFT made of amorphous silicon, low-temperature polysilicon, oxide semiconductor or the like is formed thereon. Next, an electrode is formed, and organic layers such as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer are stacked. The other electrode is formed thereon, and a gas barrier film is further formed for sealing. Thereafter, the polyimide resin film is peeled off from the substrate using a known method such as laser irradiation.

  The display device and the light receiving device may include a color filter using the flexible substrate of the present invention. For example, a flexible display device for full color display can be obtained by attaching a light emitting device to a color filter using the flexible substrate of the present invention. In particular, it is preferable to combine a light emitting device having a white light emitting function, for example, a white light emitting organic EL element, and a color filter using the flexible substrate of the present invention.

  Hereinafter, the present invention will be described with reference to examples and the like, but the present invention is not limited to these examples.

(1) Production of a polyimide resin film (on a glass substrate) 120 ° C. × 4 minutes using a spin coater MS-A200 manufactured by Mikasa Co., Ltd. on a 50 mm × 50 mm × 1.1 mm thick glass substrate (Tempax) A polyimide precursor composition solution (varnish) was spin-coated so that the thickness after pre-baking was 15 ± 0.5 μm. Then, the prebaking process for 140 degreeC x 10 minutes was performed using the ventilation dryer. After removing the pre-baked film from the blower / dryer and the temperature of the resin film / substrate dropped to room temperature, an inert oven heated to 250 ° C. under a nitrogen stream (oxygen concentration 20 ppm or less) (INH-21CD, manufactured by Koyo Thermo Systems Co., Ltd.) And heated to 400 ° C. in 10 minutes, and subjected to a heat treatment at the ultimate temperature for 30 minutes to produce a polyimide resin film (on a glass substrate). The thickness of the obtained polyimide resin film was 10 μm.

(2) 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 (1) was measured. As each value, a value measured once was used.

(3) Appearance inspection The polyimide resin film on the glass substrate was inspected by visual inspection, and “white turbidity” was observed when white turbidity was observed, and “no white turbidity” was observed when no white turbidity was observed.

(4) Measurement of coefficient of linear thermal expansion (CTE) Measurement was performed under a nitrogen stream using a thermomechanical analyzer (EXSTAR6000 TMA / 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 adsorbed water from the sample, and in the second stage, air cooling was performed to a 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 linear expansion coefficient (CTE) was calculated | required from the average of the linear expansion coefficient of 50-200 degreeC in a 3rd step. For measurement, the polyimide resin film prepared in (1) was immersed in hydrofluoric acid for 1 to 4 minutes, peeled off from the substrate, and an air-dried polyimide resin film was obtained.

(5) Measurement of 1% weight loss temperature (Td1) Measurement was performed under a nitrogen stream using a thermogravimetric apparatus (TGA-50 manufactured by Shimadzu Corporation). The temperature raising method was performed under the following conditions. In the first stage, the temperature of the sample was raised to 350 ° C. at a temperature rise rate of 3.5 ° C./min to remove the adsorbed water of the sample, and in the second stage, the temperature drop rate was 10 ° C./min to room temperature. 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 measurement, the polyimide resin film prepared in (1) was immersed in hydrofluoric acid for 1 to 4 minutes, peeled off from the substrate, and an air-dried polyimide resin film was obtained.

Hereinafter, the abbreviations of the compounds used in the examples are described.
PMDA: pyromellitic dianhydride BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride CRD-H: p-phenylenebis (trimellitic acid monoester anhydride)
PDA: paraphenylenediamine m-TB: 2,2′-dimethylbenzidine TFMB: 2,2′-bis (trifluoromethyl) benzidine NMP: N-methyl-2-pyrrolidone DAE: 4,4′-diaminodiphenyl ether SiDA: Bis (3-aminopropyl) tetramethyldisiloxane additive A: 2,2-bis (4-glycidyloxyphenyl) propane (Mitsubishi Chemical Corporation, JER828)
Additive B: bis (4-glycidyloxyphenyl) methane (Mitsubishi Chemical Corporation, JER807)
Additive C: 9,9-bis (4-glycidyloxyphenyl) fluorene (Osaka Gas Chemical Co., Ltd., Ogsol PG-100).

Synthesis example 1
Under a dry nitrogen stream, PMDA 2.4735 g (11.3 mmol), BPDA 13.3461 g (45.4 mmol), PDA 6.1316 g (56.7 mmol), and NMP 100 g were placed in a 200 mL four-necked flask and heated and stirred at 65 ° C. After 6 hours, it was cooled to obtain a varnish.

Synthesis example 2
Under a dry nitrogen stream, PMDA 1.5981 g (7.3 mmol), BPDA 8.6224 g (29.3 mmol), TFMB 11.7308 g (36.6 mmol), and NMP 100 g were added to a 200 mL four-necked flask and heated and stirred at 65 ° C. After 6 hours, it was cooled to obtain a varnish.

Synthesis example 3
PMDA 1.9492g (8.9mmol), BPDA10.5168g (35.7mmol), m-TB9.48553g (44.6mmol), and NMP100g were put into a 200mL four necked flask under dry nitrogen stream, and it heated and stirred at 65 degreeC. After 6 hours, it was cooled to obtain a varnish.

Synthesis example 4
Under a dry nitrogen stream, PMDA 1.3109 g (6.0 mmol), CRD-H 11.0178 g (24.0 mmol), TFMB 9.6225 g (30.0 mmol), and NMP 100 g were added to a 200 mL four-necked flask and heated and stirred at 65 ° C. After 6 hours, it was cooled to obtain a varnish.

Synthesis example 5
Under a dry nitrogen stream, PMDA 1.5381 g (7.1 mmol), CRD-H 12.2921 g (28.2 mmol), m-TB 7.4850 g (35.3 mmol), and NMP 100 g were put into a 200 mL four-necked flask and heated and stirred at 65 ° C. did. After 6 hours, it was cooled to obtain a varnish.

Production Example 1 Production of Black Resin Composition for Alignment Marks BPDA, DAE, and SiDA were reacted in an NMP solvent to obtain a polyimide precursor (polyamide acid) solution.

  A carbon black mill base having the following composition was dispersed at 7000 rpm for 30 minutes using a homogenizer, and glass beads were filtered to prepare a black resin composition.

Carbon black mill base composition Carbon black (MA100 manufactured by Mitsubishi Kasei Co., Ltd.): 4.6 parts Polyimide precursor solution: 24.0 parts NMP: 61.4 parts Glass beads: 90.0 parts.

Production Example 2 Production of Polyimide Substrate Active Matrix Organic EL Element [1] Production of Polyimide Resin Film Pre-baked on a glass substrate of 300 mm × 400 mm × 0.7 mm thickness (AN100 (Asahi Glass Co., Ltd.)) at 140 ° C. for 10 minutes. The varnish prepared in the examples described later was spin-coated so that the subsequent thickness was 15 ± 0.5 μm. Then, the prebaking process for 140 degreeC x 10 minutes was performed using the ventilation dryer. The prebaked film is directly put into an inert oven heated to 400 ° C, held for 30 minutes under a nitrogen stream (oxygen concentration 20 ppm or less), and cooled to 50 ° C at 5 ° C / min to produce a polyimide resin film (on a glass substrate). did.

[2] Production of TFT substrate An inorganic gas barrier film made of SiO was formed on the polyimide resin film produced above (on a glass substrate) by plasma CVD. 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) connected to the TFT through the contact hole was formed on the insulating film. This wiring is for connecting an organic EL element formed between TFTs or an organic EL element formed in a later process and the TFT. 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, and no wrinkles or cracks were observed in the flattened layer obtained after exposure, development and heat treatment. Further, 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.

[3] Production of Top Emission Type Organic EL Element A top emission type organic EL element was formed on the obtained planarization layer. First, a first electrode made of Al / ITO (Al: reflective electrode) was formed on the planarizing layer by connecting to a wiring through a 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 change in the thickness of the flattening layer was less than 1% after heat dehydration with respect to the treatment before the stripping solution treatment. 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 were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of ITO 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.

Example 1
To 10 g of the varnish obtained in Synthesis Example 1, 0.18 g of additive A (10 parts by weight with respect to 100 parts by weight of the polymer) was added to obtain a resin varnish. Using the obtained varnish, a polyimide resin film was formed on a glass substrate by the above method, and a haze value measurement and an appearance inspection were performed.

Example 2
To 10 g of the varnish obtained in Synthesis Example 2, 0.18 g of additive A (100 parts by weight with respect to 100 parts by weight of the polymer) was added to obtain a resin varnish. Using the obtained varnish, a polyimide resin film was formed on a glass substrate by the above method, and a haze value measurement and an appearance inspection were performed.

Example 3
To 10 g of the varnish obtained in Synthesis Example 3, 0.18 g of additive A (10 parts by weight with respect to 100 parts by weight of the polymer) was added to obtain a resin varnish. Using the obtained varnish, a polyimide resin film was formed on a glass substrate by the above method, and a haze value measurement and an appearance inspection were performed.

Example 4
To 10 g of the varnish obtained in Synthesis Example 4, 0.18 g of additive A (10 parts by weight with respect to 100 parts by weight of the polymer) was added to obtain a resin varnish. Using the obtained varnish, a polyimide resin film was formed on a glass substrate by the above method, and a haze value measurement and an appearance inspection were performed.

Example 5
To 10 g of the varnish obtained in Synthesis Example 5, 0.18 g of additive A (10 parts by weight with respect to 100 parts by weight of the polymer) was added to obtain a resin varnish. Using the obtained varnish, a polyimide resin film was formed on a glass substrate by the above method, and a haze value measurement and an appearance inspection were performed.

Example 6
To 10 g of the varnish obtained in Synthesis Example 1, 0.18 g of additive B (10 parts by weight with respect to 100 parts by weight of the polymer) was added to obtain a resin varnish. Using the obtained varnish, a polyimide resin film was formed on a glass substrate by the above method, and a haze value measurement and an appearance inspection were performed.

Example 7
To 10 g of the varnish obtained in Synthesis Example 1, 0.18 g of additive C (10 parts by weight with respect to 100 parts by weight of the polymer) was added to obtain a resin varnish. Using the obtained varnish, a polyimide resin film was formed on a glass substrate by the above method, and a haze value measurement and an appearance inspection were performed.

Example 8
To 10 g of the varnish obtained in Synthesis Example 2, 0.18 g of additive B (10 parts by weight with respect to 100 parts by weight of the polymer) was added to obtain a resin varnish. Using the obtained varnish, a polyimide resin film was formed on a glass substrate by the above method, and a haze value measurement and an appearance inspection were performed.

Example 9
To 10 g of the varnish obtained in Synthesis Example 2, 0.18 g of additive C (10 parts by weight with respect to 100 parts by weight of the polymer) was added to obtain a resin varnish. Using the obtained varnish, a polyimide resin film was formed on a glass substrate by the above method, and a haze value measurement and an appearance inspection were performed.

Example 10
To 10 g of the varnish obtained in Synthesis Example 3, 0.18 g of additive B (10 parts by weight with respect to 100 parts by weight of the polymer) was added to obtain a resin varnish. Using the obtained varnish, a polyimide resin film was formed on a glass substrate by the above method, and a haze value measurement and an appearance inspection were performed.

Example 11
To 10 g of the varnish obtained in Synthesis Example 3, 0.18 g of additive C (10 parts by weight with respect to 100 parts by weight of the polymer) was added to obtain a resin varnish. Using the obtained varnish, a polyimide resin film was formed on a glass substrate by the above method, and a haze value measurement and an appearance inspection were performed.

Comparative Example 1
Using the varnish obtained in Synthesis Example 1, a polyimide resin film was formed on the glass substrate by the above-described method, and haze value measurement and appearance inspection were performed.

Comparative Example 2
Using the varnish obtained in Synthesis Example 2, a polyimide resin film was formed on a glass substrate by the above method, and a haze value measurement and an appearance inspection were performed.

Comparative Example 3
Using the varnish obtained in Synthesis Example 3, a polyimide resin film was formed on a glass substrate by the above method, and haze value measurement and appearance inspection were performed.

Comparative Example 4
Using the varnish obtained in Synthesis Example 4, a polyimide resin film was formed on a glass substrate by the above method, and haze value measurement and appearance inspection were performed.

Comparative Example 5
Using the varnish obtained in Synthesis Example 5, a polyimide resin film was formed on a glass substrate by the above method, and haze value measurement and appearance inspection were performed.

  Table 1 shows the haze values of Examples 1 to 11 and Comparative Examples 1 to 5, 1% thermal weight loss temperature (Td1), CTE, and appearance inspection results. It can be seen that by adding a specific epoxy compound, high transparency can be obtained without significantly impairing heat resistance and low CTE properties. In particular, Examples 1, 3, 6, 7, 10, and 11 using PMDA, BPDA for acid dianhydride, PDA for diamine, and m-TB satisfy high levels of heat resistance, low CTE property, and transparency. Can be made.

Example 12
The black resin composition prepared in Preparation Example 1 is spin-coated on a 50 mm × 50 mm × 1.1 mm thick glass substrate (Tempax) and dried on a hot plate at 130 ° C. for 10 minutes to form a black resin coating film did. A positive type photoresist (“SRC-100” manufactured by Shipley Co., Ltd.) was spin-coated and prebaked at 120 ° C. for 5 minutes on a hot plate. After exposure to 100 mJ / cm ² ultraviolet rays using an ultra-high pressure mercury lamp and mask exposure, 2.38% tetramethylammonium hydroxide aqueous solution was used to simultaneously develop the photoresist and etch the black resin coating, A pattern was formed. The resist was peeled off with methyl cellosolve acetate and imidized by heating at 280 ° C. for 10 minutes with a hot plate to form alignment marks (cross shape with a side length of 5 mm) on the glass substrate. When the thickness of the alignment mark was measured, it was 1.4 μm.

  A polyimide resin film was produced on the alignment mark substrate produced above using the varnish prepared in Example 1 according to the procedure described in Production Example 2 [1].

  The obtained polyimide resin film did not show white turbidity, and the alignment mark formed on the glass substrate was visible.

  Using the alignment marks described above, top emission type organic EL elements were produced according to the procedures described in Production Examples 2 [2] and [3]. When a voltage was applied to the obtained organic EL element via a drive circuit, good light emission was exhibited. Further, no warpage occurred in the element.

  Example 13 An alignment mark (cross shape having a side length of 5 mm) was formed on a glass substrate (Tempax) having a thickness of 50 mm × 50 mm × 1.1 mm in the same manner as in Example 12.

  A polyimide resin film was produced on the alignment mark substrate produced above using the varnish prepared in Example 2 according to the procedure described in Production Example 2 [1].

  The obtained polyimide resin film did not show white turbidity, and the alignment mark formed on the glass substrate was visible.

  Using the alignment marks described above, top emission type organic EL elements were produced according to the procedures described in Production Examples 2 [2] and [3]. When a voltage was applied to the obtained organic EL element via a drive circuit, good light emission was exhibited. However, some warping occurred in the element.

Example 14
An alignment mark (cross shape with a side length of 5 mm) was formed on a glass substrate (Tempax) having a thickness of 50 mm × 50 mm × 1.1 mm in the same manner as in Example 12.

  A polyimide resin film was produced on the alignment mark substrate produced above using the varnish prepared in Example 3 according to the procedure described in Production Example 2 [1].

  The obtained polyimide resin film did not show white turbidity, and the alignment mark formed on the glass substrate was visible.

  Using the alignment marks described above, top emission type organic EL elements were produced according to the procedures described in Production Examples 2 [2] and [3]. When a voltage was applied to the obtained organic EL element via a drive circuit, good light emission was exhibited. Further, no warpage occurred in the element.

Example 15
An alignment mark (cross shape with a side length of 5 mm) was formed on a glass substrate (Tempax) having a thickness of 50 mm × 50 mm × 1.1 mm in the same manner as in Example 12.

  A polyimide resin film was produced on the alignment mark substrate produced above using the varnish prepared in Example 4 according to the procedure described in Production Example 2 [1].

  The obtained polyimide resin film did not show white turbidity, and the alignment mark formed on the glass substrate was visible.

  Using the alignment marks described above, top emission type organic EL elements were produced according to the procedures described in Production Examples 2 [2] and [3]. When a voltage was applied to the obtained organic EL element via a drive circuit, good light emission was exhibited. However, some warping occurred in the element.

Example 16
An alignment mark (cross shape with a side length of 5 mm) was formed on a glass substrate (Tempax) having a thickness of 50 mm × 50 mm × 1.1 mm in the same manner as in Example 12.

  A polyimide resin film was produced on the alignment mark substrate produced above using the varnish prepared in Example 5 according to the procedure described in Production Example 2 [1].

  The obtained polyimide resin film did not show white turbidity, and the alignment mark formed on the glass substrate was visible.

  Using the alignment marks described above, top emission type organic EL elements were produced according to the procedures described in Production Examples 2 [2] and [3]. When a voltage was applied to the obtained organic EL element via a drive circuit, good light emission was exhibited. However, some warping occurred in the element.

Comparative Example 6 Confirmation of Alignment Mark Visibility An alignment mark was formed on a glass substrate in the same procedure as in Example 16, and the varnish prepared in Comparative Example 1 was used instead of the varnish prepared in Example 1. A polyimide resin film was formed in the same manner as in Example 16.

  The obtained polyimide resin film was cloudy, the alignment mark formed on the glass substrate could not be visually recognized, and the organic EL element could not be produced.

Comparative Example 7 Confirmation of Alignment Mark Visibility An alignment mark was formed on a glass substrate in the same procedure as in Example 16, and the varnish prepared in Comparative Example 2 was used instead of the varnish prepared in Example 1. A polyimide resin film was formed in the same manner as in Example 16.

  The obtained polyimide resin film was cloudy, the alignment mark formed on the glass substrate could not be visually recognized, and the organic EL element could not be produced.

Comparative Example 8 Confirmation of Alignment Mark Visibility An alignment mark was formed on a glass substrate in the same procedure as in Example 16, and the varnish prepared in Comparative Example 3 was used instead of the varnish prepared in Example 1. A polyimide resin film was formed in the same manner as in Example 16.

  The obtained polyimide resin film was cloudy, the alignment mark formed on the glass substrate could not be visually recognized, and the organic EL element could not be produced.

Comparative Example 9 Confirmation of Alignment Mark Visibility An alignment mark was formed on a glass substrate in the same procedure as in Example 16, and the varnish prepared in Comparative Example 4 was used instead of the varnish prepared in Example 1. A polyimide resin film was formed in the same manner as in Example 16.

  The obtained polyimide resin film was cloudy, the alignment mark formed on the glass substrate could not be visually recognized, and the organic EL element could not be produced.

Comparative Example 10 Confirmation of Alignment Mark Visibility An alignment mark was formed on a glass substrate in the same procedure as in Example 16, and the varnish prepared in Comparative Example 5 was used instead of the varnish prepared in Example 1. A polyimide resin film was formed in the same manner as in Example 16.

  The obtained polyimide resin film was cloudy, the alignment mark formed on the glass substrate could not be visually recognized, and the organic EL element could not be produced.

Example 17 Production of Polyimide Substrate Color Filter [1] Production of Polyimide Resin Film Thickness after prebaking at 140 ° C. for 10 minutes on a 300 mm × 400 mm × 0.7 mm thick glass substrate (AN100 (Asahi Glass Co., Ltd.)) The varnish prepared in Example 2 was spin-coated so that the thickness was 15 ± 0.5 μm. Then, the prebaking process for 140 degreeC x 10 minutes was performed using the ventilation dryer. The pre-baked film is directly put into an inert oven heated to 350 ° C., held for 30 minutes under a nitrogen stream (oxygen concentration 20 ppm or less), and cooled to 50 ° C. at 5 ° C./min to produce a polyimide resin film (on a glass substrate). did.

[2] Production of Resin Black Matrix The black resin composition produced in Production Example 1 was spin-coated on the polyimide resin film on the glass substrate produced above, dried on a hot plate at 130 ° C. for 10 minutes, and then coated with black resin. A film was formed. A positive type photoresist (SRP-100, manufactured by Shipley Co., Ltd.) is spin coated, pre-baked on a hot plate at 120 ° C. for 5 minutes, exposed to 100 mJ / cm ² ultraviolet rays using an ultra-high pressure mercury lamp, and exposed to a mask. Using 38% tetramethylammonium hydroxide aqueous solution, simultaneously develop photoresist and etch black resin coating to form pattern, strip resist with methyl cellosolve acetate, 280 ° C on hot plate for 10 minutes By imidizing by heating, a resin black matrix in which carbon black was dispersed in a polyimide resin was formed. When the thickness of the black matrix was measured, it was 1.4 μm.

[3] Preparation of Photosensitive Color Resist Pigment Red PR177, 8.05 g was charged together with 50 g of 3-methyl-3-methoxybutanol, and dispersed at 7000 rpm for 5 hours using a homogenizer, and then the glass beads were filtered and removed. 70.00 g of acrylic copolymer solution (“Cyclomer” P, ACA-250, 43 wt% solution manufactured by Daicel Chemical Industries, Ltd.), 30.00 g of pentaerythritol tetramethacrylate as a polyfunctional monomer, “Irgacure as a photopolymerization initiator” "369. 15.00 g of cyclopentanone 260.00 g and 20 wt% photosensitive acrylic resin solution (AC) 134.75 g were added to obtain a photosensitive red resist. Similarly, a photosensitive green resist composed of Pigment Green PG38 and Pigment Yellow PY138 and a photosensitive blue resist composed of Pigment Blue PB15: 6 were obtained.

[4] Preparation of colored layer The spinner rotation speed is adjusted so that the film thickness at the black matrix opening after heat treatment is adjusted to 2.0 μm on the polyimide resin film on the glass substrate on which the black matrix is patterned. The red coloring layer was obtained by apply | coating a neutral red resist on a polyimide film, and prebaking for 10 minutes at 100 degreeC with a hotplate. Next, using a UV exposure machine “PLA-5011” manufactured by Canon Inc., a black matrix opening and a partial area on the black matrix are passed through a chrome photomask through which light is transmitted in an island shape. / cm ² (ultraviolet intensity of 365 nm). After exposure, the film was dipped in a developer composed of a 0.2% aqueous solution of tetramethylammonium hydroxide and developed. Subsequently, washed with pure water and then heat-treated in an oven at 230 ° C. for 30 minutes to produce red pixels.

  Similarly, a green pixel made of a photosensitive green resist and a blue pixel made of a photosensitive blue resist were produced to obtain a polyimide substrate color filter produced on a glass substrate.

[5] Peeling of the polyimide substrate color filter from the glass substrate The polyimide substrate color filter prepared above on the glass substrate was cut and immersed in water for 12 hours, whereby the polyimide substrate color filter was peeled from the glass substrate. In addition, when the pixel pattern shape was confirmed using the optical microscope, the pattern shape did not change before and after peeling. Further, the color filter was not turbid, and the appearance was not inferior to that of the glass substrate color filter.

Comparative Example 11 Production of Polyimide Substrate Color Filter A polyimide substrate color filter was produced in the same manner as in Example 17 except that the varnish prepared in Comparative Example 2 was used instead of the varnish prepared in Example 2. When the pixel pattern shape was confirmed using an optical microscope, there was no change in the pattern shape before and after peeling. However, the color filter was slightly turbid, and the appearance was inferior to that of the glass substrate color filter.

Claims (14)

(A) a polyimide precursor having a structural unit represented by the general formula (1), and (b) a compound having at least two monovalent organic groups represented by the formula (2) or (3). Resin composition.

(In the general formula (1), X ¹ and X ² are each independently a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, A is a tetravalent organic group, and B is a divalent organic group. Group.) In general formula (1), A is a tetravalent organic group selected from the following formulas (4) to (6), and B is a divalent organic group selected from the following formulas (7) to (9). The resin composition according to claim 1.

The component (b) is a compound having at least two monovalent organic groups represented by the formula (2), and the compound is a compound represented by the general formula (13). Resin composition.

(In General Formula (13), D is a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, or a divalent organic group having 1 to 40 carbon atoms, and R ¹ and R ² are each independently a hydrogen atom, halogen, An atom, a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms, and a and b are each independently an integer of 0 to 4). Furthermore, the resin composition in any one of Claims 1-3 containing a solvent. A polyimide resin film obtained by heating the resin composition according to claim 1. A TFT substrate comprising an inorganic film and a TFT on the polyimide resin film according to claim 5. The TFT substrate according to claim 6, wherein the inorganic film contains silicon oxide, nitride, or oxynitride. The method for manufacturing a TFT substrate according to claim 6 or 7, comprising the following steps.
(1) A step of applying the resin composition according to claim 4 on a substrate (2) A step of removing a solvent from the applied resin composition (3) A polyimide precursor by imidizing a polyimide precursor in the resin composition Step of obtaining resin film (4) Step of forming inorganic film on polyimide resin film (5) Step of forming TFT A color filter comprising a black matrix and colored pixels on the polyimide resin film according to claim 5. The color filter according to claim 9, wherein the black matrix is a resin black matrix in which a black pigment is dispersed in a polyimide resin. The method for producing a color filter according to claim 9 or 10, comprising the following steps.
(1) A step of applying the resin composition according to claim 4 on a substrate (2) A step of removing a solvent from the applied resin composition (3) A polyimide precursor by imidizing a polyimide precursor in the resin composition Step of obtaining a resin film (4) Step of forming a black matrix and colored pixels A display device comprising the TFT substrate according to claim 6. A display device in which a light emitting device is bonded to the color filter according to claim 9. The display device according to claim 12 or 13, wherein the display device is an organic EL element.