TWI710584B - Polyimide resin, polyimide resin composition, touch panel using the same and manufacturing method thereof, color filter and manufacturing method thereof, liquid crystal element and manufacturing method thereof, organic EL element and manufacturing method thereof - Google Patents

Abstract

The present invention is a polyimide resin, which is characterized in that: the structural unit represented by the general formula (1) is used as the main component, and the general formula (2) containing 2 mol% or more and 30 mol% or less of all the structural units The structural unit has excellent light transmittance, low birefringence, low linear thermal expansion, and laser releasability.

[化1]

(In the formula, multiple R ¹ may be the same or different, and represent a tetravalent organic group with 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or a monocyclic alicyclic structure A tetravalent organic group with 4 to 40 carbon atoms formed by connecting organic groups directly or through a cross-linking structure. R ² represents a specific aromatic group. R ³ represents a specific bisphenol structure or a specific bisbenzoxazole structure.

Description

Polyimide resin, polyimide resin composition, use thereof Touch panel and manufacturing method thereof, color filter and manufacturing method thereof, liquid crystal element and manufacturing method thereof, organic EL element and manufacturing method thereof

The present invention relates to a polyimide resin, a polyimide resin composition, a touch panel using the same, a manufacturing method thereof, a color filter and a manufacturing method thereof, a liquid crystal element and a manufacturing method thereof, an organic electro Electroluminescence (EL) element and its manufacturing method.

Compared with glass, organic film has the advantages of flexibility, resistance to breakage and light weight. Recently, by replacing the substrate of the flat panel display with an organic film, research on the flexibility of the display has become more active.

Examples of the resin used in the organic film include polyester, polyamide, polyimide, polycarbonate, polyether sulfide, acrylic, and epoxy. Among these, polyimide is a resin with high heat resistance and is suitable as a display substrate.

Among polyimines, wholly aromatic polyimines having particularly excellent heat resistance are derived from aromatic acid dianhydrides and aromatic diamines. A wholly aromatic polyimide has an absorption band in the visible light wavelength range derived from an intramolecular or intermolecular charge transfer complex. Therefore, the film containing a wholly aromatic polyimide has the property of coloring from yellow to brown, or the property of large birefringence. Due to these properties, wholly aromatic polyimide cannot be used as a display substrate that requires high transparency and low birefringence.

As a method of suppressing the charge transfer interaction of the polyimide and improving the light transmittance, a method of using an alicyclic monomer as a component of at least any one of an acid dianhydride and a diamine can be cited.

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

Patent Document 2 discloses that 1S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride and 2,2'-bis(trifluoromethyl)benzidine (2,2'-Bis(trifluoromethyl)benzidine, TFMB) obtained polyimide has high transparency, high glass transition temperature (Glass Transition Temperature, Tg).

Patent Document 3 describes a combination of alicyclic dianhydride and an amine having a hydroxyl group, specifically 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]hexafluoro Polyimine obtained from propane (2,2-Bis[3-(3-aminobenzamide)-4-hydroxyphenyl]hexafluoropropane, HFHA) has heat resistance, light transmittance, and low birefringence.

In addition, Patent Document 4 describes that a polyimide obtained from a tetracarboxylic acid and a diamine, which contains an aromatic fluorine compound and an alicyclic compound, respectively, has high transparency, high heat resistance, and low birefringence, and The coefficient of thermal expansion (Coefficient Of Thermal Expansion, CTE) is low. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 11-080350 [Patent Document 2] Japanese Patent Laid-Open No. 2010-085992 [Patent Document 3] International Publication No. 2013/24849 [Patent Document 4] Japanese Patent Laid-Open 2016 -204569 newspaper

[Problem to be solved by the invention] In the case of fabricating a display on an organic film, the process is usually as follows: the organic film is formed on a support substrate, and after the device is fabricated thereon, the organic mold is peeled off from the support substrate . Research in the peeling process has resulted in the following problems: In the polyimide described in Patent Document 1, Patent Document 2, and Patent Document 4, the irradiation energy required for peeling is high, or peeling by laser is difficult .

In addition, it is disclosed that the polyimide described in Patent Document 3 can perform laser peeling, but there is a problem of high CTE.

As such, polyimide materials that satisfy all the required characteristics of high transparency, low birefringence, low CTE, and laser releasability are not yet known.

In view of the above-mentioned problems, the present invention aims to provide a polyimide resin having excellent light transmittance, low birefringence, low linear thermal expansion, and laser releasability. [Means to solve the problem]

The present invention is a polyimide resin characterized in that: the structural unit represented by the general formula (1) is used as the main component, and the general formula (2) contains 2 mol% or more and 30 mol% or less of all the structural units Indicates the structural unit.

[化1]

(R ¹ represents a tetravalent organic group with 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure directly or through a cross-linked structure. A tetravalent organic group having 4 to 40 carbon atoms. R ² represents a divalent organic group represented by the general formula (3). R ³ represents the following general formula (4) or general formula (5))

[化2]

(R ⁴ to R ¹¹ each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group of 1 to 3 carbons which may be substituted by a halogen atom. X ¹ is selected from a direct bond, an oxygen atom, a sulfur atom, and a sulfonyl group , Divalent cross-linked structure in a C1-C3 divalent organic group, ester bond, amide bond or sulfide bond that can be substituted by halogen atoms)

[發明的效果][化3]

[Effects of the invention]

According to the present invention, it is possible to provide a polyimide resin film having excellent light transmittance, low birefringence, low linear thermal expansion, and laser releasability. The polyimide resin of the present invention can be preferably used as a support substrate for displays such as touch panels, color filters, liquid crystal elements, and organic EL elements. By using the polyimide resin of the present invention as a support substrate for displays, a high-definition display can be produced.

Hereinafter, the preferred embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following embodiments, and can be implemented with various changes depending on the purpose or application. In addition, the drawings referred to in the following description only schematically show the shape, size, and positional relationship to the extent that the content of the present invention can be understood. That is, the present invention is not limited to only the shape, size, and positional relationship illustrated in the drawings.

<Polyimide resin> The polyimide resin of the embodiment of the present invention has a structural unit represented by the general formula (1) as a main component, and contains 2 mol% to 30 mol% of all the structural units. The structural unit represented by formula (2).

[化4]

R ¹ represents a tetravalent organic group with 4 to 40 carbons having a monocyclic or condensed polycyclic alicyclic structure, or a carbon in which organic groups having a monocyclic alicyclic structure are directly or through a cross-linked structure. A tetravalent organic group of 4-40. R ² represents a divalent organic group represented by the general formula (3). R ³ represents the following general formula (4) or general formula (5).

[化5]

R ⁴ to R ¹¹ each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 3 carbon atoms which may be substituted with a halogen atom. X ¹ is a divalent bond selected from a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group of 1 to 3 carbons which may be substituted by a halogen atom, an ester bond, an amide bond or a thioether bond. Joint structure.

[化6]

The structural units represented by general formula (1) and general formula (2) are repeating structural units in the polyimide resin of the embodiment of the present invention. Hereinafter, these structural units are sometimes referred to as "repeating structural units" "Or simply "repeating unit".

Here, the main component refers to a structural unit represented by general formula (1) having 50 mol% or more of all structural units of the polymer. With the structure represented by general formula (1) containing 50 mol% or more of all structural units of the polymer, the CTE of the polyimide resin becomes low. Thereby, the warpage at the time of forming a film using the polyimide resin on a support substrate can be reduced.

In addition, the term "all structural units" means all structural units constituting the polyimide having repeating units represented by general formula (1) and general formula (2). Specifically, it refers to the total amount (mol basis) of the repeating units represented by general formula (1) and general formula (2). Wherein, when polyimine also includes structures other than the repeating units represented by general formula (1) and general formula (2), it refers to the repeating units represented by general formula (1) and general formula (2) , And the total amount (mol basis) of structures other than the repeating unit represented by the general formula (1) and (2).

The content of the structural unit represented by the general formula (1) is more preferably 70 mol% or more of all the structural units of the polymer.

In addition, by including the repeating structural unit represented by the general formula (2) at 2 mol% or more and 30 mol% or less of all the structural units, good laser releasability can be imparted, and the CTE of the polyimide can be maintained. low. The content of the repeating structural unit represented by the general formula (2) is more preferably 5 mol% or more and 30 mol% or less.

R ¹ in the general formula (1) and general formula (2) represents the structure of the acid component, and represents a tetravalent organic group having 4 to 40 carbon atoms with a monocyclic or condensed polycyclic alicyclic structure, or having a single A tetravalent organic group having 4 to 40 carbon atoms is formed by connecting the organic groups of the cycloalicyclic structure directly or via a crosslinked structure. Here, the alicyclic structure may substitute a part of hydrogen atoms with halogen. Moreover, as an acid component, these acid components may be used individually or in combination of multiple types.

The acid dianhydride having an alicyclic structure that can be used in the present invention is not particularly limited, and examples include: 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-ring Pentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, 1,2,3,4- Tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3- Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,2,3,4-cycloheptanetetracarboxylic acid Dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,4-Dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic 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, tricyclic [6.3.0.0<2,6>] undecane-3,5,9,11-tetracarboxylic dianhydride, bicyclic [2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]octa-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[ 2.2.1]Heptanetetracarboxylic dianhydride, bicyclo[2.2.1]heptane-5-carboxymethyl-2,3,6-tricarboxylic dianhydride, 7-oxabicyclo[2.2.1]heptan Alkane-2,4,6,8-tetracarboxylic dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic dianhydride, tetradecahydroanthracene-1,2,8,9-tetracarboxylic acid 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-dicarboxylic anhydride and "Rikacid" (registered trademark) BT-100 (above Is a trade name, manufactured by New Japan Rika Co., Ltd.) and these derivatives.

R ^{1 in} general formula (1) and general formula (2) is preferably one or more selected from the structure represented by the following general formula (6) to general formula (10).

[化7]

R ¹² to R ⁵⁵ each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 3 carbon atoms which may be substituted with a halogen atom.

Among these, from the viewpoint of being commercially available, easy to obtain, and the viewpoint of reactivity with a diamine compound, it is preferable that R ¹ exhibits the structure represented by the following chemical formula (11) to (13) Acid dianhydride of 1S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride, 1R,2S,4S,5R-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride Carboxylic dianhydride. The acid dianhydride exhibiting the structure represented by the chemical formula (11) is commercially available under the trade name "PMDA-HH" by Wako Pure Chemical Industries, Ltd., and the acid dianhydride exhibiting the structure represented by the chemical formula (12) is marketed under the trade name "PMDA-HH". PMDA-HS" is commercially available. In addition, these acid dianhydrides can be used individually or in combination of 2 or more types.

[化8]

R ² in the general formula (1) represents the structure of the diamine component, and is represented by the general formula (3).

The diamine exhibiting the structure represented by the general formula (3) is not particularly limited, and examples include 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, and 4 ,4'-Diaminodiphenyl sulfide, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane , 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-diaminodiphenyl sulfide, benzidine, 2,2'-bis(trifluoromethyl) ) Benzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 2,2',3,3' -Tetramethylbenzidine, 4,4-diaminobenzidine, 4-aminobenzoic acid-4-aminophenyl, 4,4-diaminobenzophenone, or these aromatics A diamine compound in which the ring is substituted with an alkyl group, an alkoxy group, a halogen atom, etc.

From the viewpoints of ease of availability, transparency of the polyimide resin, and low CTE, R ^{2 is} preferably one or more selected from the structure represented by the chemical formula (14) to the chemical formula (17), for example.

[化9]

R ⁵⁶ to R ⁸⁷ each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 3 carbon atoms which may be substituted with a halogen atom.

Among these, R ² is preferably a diamine having a structure represented by the following chemical formula (18) to chemical formula (21).

[化10]

The diamine represented by the chemical formula (18) is 2,2'-dimethylbenzidine (m-TB). It can increase the Tg of polyimide and can reduce CTE, so it is preferred.

The diamine showing the structure represented by the chemical formula (19) is 2,2'-bis(trifluoromethyl)benzidine (TFMB). It can improve the transparency of polyimide, can reduce birefringence, and in turn can reduce CTE, so it is preferred.

The diamine showing the structure represented by the chemical formula (20) is 4,4'-Diamino Diphenyl Sulfide (4,4'-DDS). It can increase the Tg of polyimine, so it is preferred.

The diamine showing the structure represented by the chemical formula (21) is 4,4'-diamino benzanilide (DABA). It can reduce the residual stress generated between the polyimide film and the inorganic film, and can suppress the warpage of the substrate, so it is preferred.

Among them, TFMB can better meet all the characteristics of high transparency, low birefringence, and low CTE required by the transparent support substrate, and therefore is particularly preferred.

R ³ in the general formula (2) represents the structure of the diamine component, and is represented by the general formula (4) or (5).

In addition, the oxazole ring of the general formula (5) is generated by dehydrating and ring-closing the structure represented by the general formula (4).

The polyimide resin of the embodiment of the present invention may contain other structural units within a range that does not inhibit the effects of the present invention. Examples of other structural units include polyimide which is a dehydrated ring-closing body of polyamide acid, and polybenzoxazole which is a dehydrated ring-closing body of polyhydroxy amide.

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

For example, the aromatic acid dianhydride is not particularly limited, and examples include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4 '-Biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-terphenyltetracarboxylic dianhydride, 4,4' -Oxydiphthalic dianhydride, 3,4'-oxydiphthalic dianhydride, 3,3'-oxydiphthalic dianhydride, diphenyl benzene-3,3' ,4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane Anhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3 -Dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxybenzene) Base) ether dianhydride, bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) 1,4-phenylene, 2,2-bis(4-(4 -Aminophenoxy)phenyl)propane, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6- Pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(4 -(3,4-Dicarboxyphenoxy)phenyl)hexafluoropropane dianhydride, 2,2-bis(4-(3,4-dicarboxybenzyloxy)phenyl)hexafluoropropane dianhydride , 1,6-Difluoropyromellitic dianhydride, 1-trifluoromethylpyromellitic dianhydride, 1,6-di-trifluoromethylpyromellitic dianhydride, 2,2'-bis (Trifluoromethyl)-4,4'-bis(3,4-dicarboxyphenoxy)biphthalic anhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl ] Dianhydride, 4,4'-((9H-phenoxycarbonyl)bis(4,1-phenoxycarbonyl))diphthalic dianhydride, "Rikacid" (registered trademark) Aromatic tetracarboxylic dianhydrides such as TMEG-100 (trade name, manufactured by New Japan Chemical Co., Ltd.) and their derivatives.

The aliphatic acid dianhydride is not particularly limited, and examples include 1,2,3,4-butane tetracarboxylic dianhydride, 1,2,3,4-pentane tetracarboxylic dianhydride, and these Derivatives, etc.

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

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

For example, the aromatic diamine compound is not particularly limited, and examples include 1,4-bis(4-aminophenoxy)benzene, m-phenylenediamine, p-phenylenediamine, and 1,5-naphthalenediamine , 2,6-Naphthalenediamine, bis{4-(4-aminophenoxyphenyl)} chrysene, bis{4-(3-aminophenoxyphenyl)} chrysene, bis(4-amine Phenyloxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 9,9-bis(4-aminophenyl)pyridium, 2,2-bis[4-( 4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 3-aminophenyl-4-aminobenzenesulfonate An acid ester, 4-aminophenyl-4-aminobenzenesulfonate, or a diamine compound in which the aromatic ring may be substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

The alicyclic diamine compound is not particularly limited, and examples thereof include cyclobutane diamine, isophorone diamine, bicyclo[2.2.1]heptane dimethylamine, tricyclo[3.3.1.13,7 ]Decane-1,3-diamine, 1,2-cyclohexyldiamine, 1,3-cyclohexyldiamine, 1,4-cyclohexyldiamine, 4,4'-diaminodicyclohexylmethane , 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodicyclohexylmethane, 3,3', 5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodicyclohexylmethane, 3 ,5-Diethyl-3',5'-dimethyl-4,4'-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, 2,2'-bis(4-aminocyclohexyl)hexafluoropropane, 2,2'-dimethyl-4,4'-diaminobicyclohexane, 2 , 2'-bis(trifluoromethyl)-4,4'-diaminobicyclohexane, or diamine compounds in which these alicyclic rings are substituted with alkyl groups, alkoxy groups, halogen atoms, etc.

The aliphatic diamine compound is not particularly limited, and examples include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1, 6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, etc. Diamines, bis(aminomethyl)ether, bis(2-aminoethyl)ether, bis(3-aminopropyl)ether and other glycol diamines, and 1,3-bis( 3-aminopropyl) tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane, α,ω-bis(3-aminopropyl)poly Silicone diamines such as dimethylsiloxane.

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

Among these, by using a diamine having a sulfonate in the molecule, transparency can be improved while maintaining the mechanical properties and heat resistance of polyimide, which is preferable. That is, the polyimide resin of the embodiment of the present invention preferably further has a structural unit represented by the general formula (22).

[化11]

R ¹ is as described above. X ² and X ³ may be the same or different, and are a structure containing an aromatic ring, aliphatic ring, a chain hydrocarbon group, or a combination of these, or containing these and a structure selected from the group consisting of amino group, ester group, ether group and extension. A structure of a combination of one or more groups in the group consisting of an alkyl group, an oxyalkylene group, an ethylene group, and a halogenated alkylene group.

The structural unit represented by the general formula (22) preferably contains a structural unit represented by the following general formula (23). Thereby, the transparency of the polyimide resin can be improved, and the glass transition temperature can be significantly increased. The diamine exhibiting the structure is 3-aminophenyl-4-aminobenzenesulfonate.

[化12]

R ¹ represents a tetravalent organic group with 4 to 40 carbons having a monocyclic or condensed polycyclic alicyclic structure, or a carbon in which organic groups having a monocyclic alicyclic structure are directly or through a cross-linked structure. A tetravalent organic group of 4-40.

The polyimide resin of the embodiment of the present invention is preferably in the range of 1 mol% or more and 25 mol% or less, more preferably in the range of 3 mol% or more and 20 mol% or less including the general formula (23). The structural unit. By containing the structural unit represented by the general formula (23) in the above-mentioned range, transparency and glass transition temperature can be improved while maintaining the mechanical properties and flexibility of the polyimide resin.

The polyimide resin of the embodiment of the present invention preferably has a structure represented by general formula (24) in the acid dianhydride residue and/or diamine residue constituting the polyimide. Since the polyimide resin has the structure represented by the general formula (24), the residual stress generated between the polyimide resin and the inorganic film can be reduced, and the warpage of the substrate can be suppressed. In addition, the transparency of the polyimide resin can be further improved, and the birefringence can be further reduced.

[化13]

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

Examples of the monovalent organic group having 1 to 20 carbon atoms in R ⁸⁸ and R ⁸⁹ include a hydrocarbon group, an amino group, an alkoxy group, and an epoxy group. Examples of the hydrocarbon group in R ⁸⁸ and R ⁸⁹ include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.

The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, and specific examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and third Butyl, pentyl, hexyl, etc. The cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms, and specific examples thereof include cyclopentyl and cyclohexyl. The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and specific examples include phenyl, tolyl, and naphthyl.

Examples of the alkoxy group in R ⁸⁸ and R ⁸⁹ include methoxy, ethoxy, propoxy, isopropoxy, butoxy, phenoxy, propyleneoxy, and cyclohexyloxy.

R ⁸⁸ and R ⁸⁹ in the general formula (24) are preferably a monovalent aliphatic hydrocarbon group having 1 to 3 carbons or an aromatic group having 6 to 10 carbons. The reason is that the obtained polyimide film has both high heat resistance and low residual stress. Here, the monovalent aliphatic hydrocarbon having 1 to 3 carbon atoms is preferably a methyl group, and the aromatic group having 6 to 10 carbon atoms is preferably a phenyl group.

In general formula (24), m is an integer of 3 to 200, preferably 10 to 200, more preferably 20 to 150, still more preferably 30 to 100, and particularly preferably 30 to 60. When m is within the above range, the residual stress of polyimide can be reduced. In addition, the polyimide film can be prevented from becoming cloudy or the mechanical strength of the polyimide film is reduced.

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

[化14]

In formula (25), a plurality of R ^90s are each independently a single bond or a divalent organic group having 1 to 20 carbons, and a plurality of R ⁹¹ , R ⁹² and R ^{93 that} are present are independently a carbon number of 1 to 20. The monovalent organic group of 20, L ¹ , L ² and L ³ are each independently a group selected from the group consisting of an amino group, an acid anhydride group, a carboxyl group, a hydroxyl group, an epoxy group, a mercapto group, and R ⁹⁴ . R ⁹⁴ is a monovalent organic group having 1 to 20 carbons. n is an integer of 3 to 200, and o is an integer of 0 to 197.

In general formula (25), examples of the divalent organic group having 1 to 20 carbons in R ⁹⁰ include: alkylene having 1 to 20 carbons, cycloalkylene having 3 to 20 carbons, and 6 carbons. ～20 aryl group and so on. The alkylene having 1 to 20 carbon atoms is preferably an alkylene having 1 to 10 carbon atoms, and examples thereof include methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, Hexamethylene and so on. The cycloalkylene group having 3 to 20 carbon atoms is preferably a cycloalkylene group having 3 to 10 carbon atoms, and examples thereof include cyclobutylene, cyclopentyl, cyclohexyl, and cycloheptyl. As the arylene group having 6 to 20 carbons, an aromatic group having 3 to 20 carbons is preferred, and phenylene, naphthylene, etc. can be mentioned. The divalent organic group having 1 to 20 carbons in R ⁹⁰ is preferably a divalent aliphatic hydrocarbon having 3 to 20 carbons among these.

Preferable specific examples of each group in R ⁹¹ to R ⁹³ include the same ones as those of R ⁸⁸ and R ⁸⁹ described above.

The amine groups in L ¹ , L ² and L ³ include not only the amine group itself but also its reactive derivatives. As a reactive derivative of an amine group, an isocyanate group, a bis(trialkylsilyl) amine group, etc. are mentioned. As a specific example of the compound represented by the general formula (25) when L ¹ , L ² and L ³ are amine groups, there can be cited: X22-1660B-3 ( Made by Shin-Etsu Chemical Co., with a number average molecular weight of 4,400), X22-9409 (manufactured by Shin-Etsu Chemical Co., with a number average molecular weight of 1,300), X22-161A (manufactured by Shin-Etsu Chemical Co., Ltd., modified with dimethyl silicone at both ends) The number average molecular weight is 1,600), X22-161B (manufactured by Shin-Etsu Chemical Co., with a number average molecular weight of 3,000), KF8012 (manufactured by Shin-Etsu Chemical Co., with a number average molecular weight of 4,400), BY16-835U (Toray Dow Corning) Manufacturing; number average molecular weight is 900), Silaplane FM3311 (manufactured by Chisso; number average molecular weight is 1000), etc.

The acid anhydride group in L ¹ , L ² and L ³ not only includes the acid anhydride group itself, but also includes its reactive derivative. Examples of reactive derivatives of the acid anhydride group include acid ester products of the carboxyl group, the chloride of the carboxyl group, and the like. Specific examples in which L ¹ , L ² and L ³ are acid anhydride groups include groups represented by the following formulas.

[化15]

Specific examples of the compound represented by general formula (25) when L ¹ , L ² and L ³ are acid anhydride groups include: X22-168AS (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,000), X22-168A ( Shin-Etsu Chemical Corporation, number average molecular weight is 2,000), X22-168B (Shin-Etsu Chemical Corporation, number average molecular weight is 3,200), X22-168-P5-8 (Shin-Etsu Chemical Corporation, number average molecular weight is 4,200), DMS- Z21 (manufactured by Gelest, with a number average molecular weight of 600 to 800), etc.

Specific examples of the compound represented by the general formula (25) when L ¹ , L ² and L ³ are hydroxyl groups include: KF-6000 (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 900), KF-6001 (Shin-Etsu The number average molecular weight is 1,800 manufactured by a chemical company, KF-6002 (manufactured by Shin-Etsu Chemical Co., the number average molecular weight is 3,200), KF-6003 (manufactured by Shin-Etsu Chemical Co., the number average molecular weight is 5,000), etc. It is considered that the compound having the hydroxyl group reacts with other tetracarboxylic dianhydride monomers.

As a specific example of the compound represented by the general formula (25) when L ¹ , L ² and L ³ are epoxy groups, there can be cited: X22-163 (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 400), KF-105 (manufactured by Shin-Etsu Chemical Co., with a number average molecular weight of 980), X22-163A (manufactured by Shin-Etsu Chemical Co., with a number average molecular weight of 2,000), X22-163B (manufactured by Shin-Etsu Chemical Co., with a number average molecular weight of 3,500 ), X22-163C (manufactured by Shin-Etsu Chemical Company, number average molecular weight of 5,400), X22-169AS (manufactured by Shin-Etsu Chemical Company, number average molecular weight of 1,000), X22-169B (Shin-Etsu Chemical Manufactured by the company, the number average molecular weight is 3,400), etc. It is considered that the compound having the epoxy group reacts with other diamine monomers.

Specific examples of the compound represented by the general formula (25) when L ¹ , L ² and L ³ are mercapto groups include: X22-167B (manufactured by Shin-Etsu Chemical Co., with a number average molecular weight of 3,400), X22-167C (Shin-Etsu Manufactured by a chemical company, the number average molecular weight is 4,600), etc. It is considered that the compound having the mercapto group reacts with other tetracarboxylic dianhydride monomers.

From the viewpoint of increasing the molecular weight of the polyimide precursor or the viewpoint of the heat resistance of the obtained polyimide, L ¹ , L ² and L ^{3 are} preferably independently selected from the group consisting of amino groups and acid anhydrides. group and a base group consisting of R ^94, thereby avoiding clouding varnish containing polyimide precursor and the solvent view viewpoint of cost or, more preferably each independently an amine.

The polyimide resin of the embodiment of the present invention can be prepared by making a polyimide precursor containing a structural unit represented by the following general formula (26) and a structural unit represented by the general formula (27) Obtained in closed loop.

[化16]

In general formula (26) and general formula (27), Y ¹ to Y ⁴ each independently represent a hydrogen atom, a monovalent organic group having 1 to 10 carbons, or a monovalent alkylsilyl group having 1 to 10 carbons. R ¹ represents a tetravalent organic group with 4 to 40 carbons having a monocyclic or condensed polycyclic alicyclic structure, or a carbon in which organic groups having a monocyclic alicyclic structure are directly or through a cross-linked structure. A tetravalent organic group of 4-40. R ² represents a divalent organic group represented by the general formula (3). R ³ represents the general formula (4) or the general formula (5).

The method of imidization is not particularly limited, and examples include thermal imidization or chemical imidization. Among them, from the viewpoints of the heat resistance of the polyimide resin film and the transparency in the visible light region, thermal imidization is preferred.

Polyimide precursor resins such as polyamide acid, polyamide acid ester, and polyamide silylester can be synthesized by the reaction of a diamine compound and acid dianhydride or its derivatives. Examples of derivatives include: the tetracarboxylic acid of the acid dianhydride, the monoester, diester, triester or tetraester of the tetracarboxylic acid, the chlorinated acid, etc., specifically, methyl, ethyl The structure of esterification of butyl group, n-propyl group, isopropyl group, n-butyl group, second butyl group and tertiary butyl group. The reaction method of the polymerization reaction is not particularly limited as long as the target polyimide precursor resin can be produced, and a known reaction method can be used.

As a specific reaction method, the following method can be exemplified: a predetermined amount of all diamine components and solvents are charged in a reaction vessel, and after dissolving, a predetermined amount of acid dianhydride components are charged at room temperature to 150 Stir at 0°C for 0.5 hour to 30 hours.

In order to adjust the molecular weight to a preferable range, the polyimide resin and the polyimide precursor resin of the embodiment of the present invention may be sealed at both ends with a terminal sealant. As a terminal sealing agent which reacts with an acid dianhydride, a monoamine, a monovalent alcohol, etc. are mentioned. In addition, examples of the terminal sealing agent that reacts with the diamine compound include acid anhydrides, monocarboxylic acids, monochlorine compounds, monoactive ester compounds, dicarbonates, vinyl ethers, and the like. In addition, by reacting the terminal sealant, various organic groups can be introduced as terminal groups.

Examples of monoamines used in the sealant at the acid anhydride group terminal include: 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1- Hydroxy-7-aminonaphthalene, 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-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1- Carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 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-aminosalicylic acid, ammelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-amino Benzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminobenzene Phenol, 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-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-Mercapto-3-aminonaphthalene, 1-amino-2-mercaptonaphthalene, 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-diethynyl Aniline, 3,4-diethynylaniline, 3,5-diethynylaniline, 1-ethynyl-2-aminonaphthalene, 1-ethynyl-3-aminonaphthalene, 1-ethynyl-4-amine 1-ethynyl-5-aminonaphthalene, 1-ethynyl-6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 2-acetylene 1-aminonaphthalene, 2-ethynyl-3-aminonaphthalene, 2-ethynyl-4-aminonaphthalene, 2-ethynyl-5-aminonaphthalene, 2-ethynyl-6-aminonaphthalene Naphthalene, 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-aminonaphthalene, 4,8-diethynyl-2-aminonaphthalene, etc., but are not limited to these.

The monovalent alcohol used as the sealant at the acid anhydride group terminal includes 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-undecyl alcohol, 2-undecyl alcohol, 1-dodecanol, 2-dodecanol, 1-tridecanol, 2-Tridecyl alcohol, 1-tetradecanol, 2-tetradecanol, 1-pentadecanol, 2-pentadecanol, 1-hexadecanol, 2-hexadecanol, 1-heptadecanol, 2- Heptadecanol, 1-octadecyl alcohol, 2-octadecyl alcohol, 1-nonadecanol, 2-nonadecanol, 1-eicosanol, 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 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 monomethylol, tricyclodecane monomethylol, norbornyl, terpineol, etc., but not limited to these.

The acid anhydrides, monocarboxylic acids, monochlorine compounds, and monoactive ester compounds used as the sealant at the amino terminal include: phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3 -Hydroxyphthalic anhydride and other acid anhydrides, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy- 8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4 -Carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzoic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 2,4-diethynylbenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4-diethyne Benzoic acid, 3,5-diethynyl benzoic acid, 2-ethynyl-1-naphthoic acid, 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, 7-ethynyl-2-naphthoic acid, 8-ethynyl-2 -Monocarboxylic acids such as naphthoic acid and monochlorine compounds formed by chlorination of the carboxyl groups, as well as terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid Phthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-Dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, 2,7-dicarboxynaphthalene, etc. Monochlorine compounds formed by chlorination of only a single carboxyl group of an acid, and a monochloride compound and N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboxylate Active ester compound obtained by amine reaction.

The dicarbonate compound used as the sealant at the amino terminal includes di-tert-butyl dicarbonate, dibenzyl dicarbonate, dimethyl dicarbonate, and diethyl dicarbonate.

Vinyl ether compounds used as a sealant at the amino terminal include: tert-butyl chloroformate, n-butyl chloroformate, isobutyl chloroformate, benzyl chloroformate, allyl chloroformate, ethyl chloroformate Ester, isopropyl chloroformate and other chloroformates, butyl isocyanate, 1-naphthyl isocyanate, stearyl isocyanate, phenyl isocyanate and other isocyanate compounds, butyl vinyl ether, Cyclohexyl vinyl ether, ethyl vinyl ether, 2-ethylhexyl vinyl ether, isobutyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, tertiary butyl vinyl ether, benzyl vinyl ether, etc.

Other compounds used as a sealant at the amino terminal include: benzyl chloroformate, benzyl chloride, chloroformyl methyl chloroformate, 2,2,2-trichloroethyl chloroformate, and allyl chloroformate , Methanesulfonyl chloride, p-toluenesulfonyl chloride, phenyl isocyanate, etc.

The introduction ratio of the sealant at the end of the acid anhydride group is preferably in the range of 0.1 mol% to 60 mol% with respect to the acid dianhydride component, and more preferably 0.5 mol% to 50 mol%. In addition, with respect to the diamine component, the introduction ratio of the sealant at the amino terminal is preferably in the range of 0.1 mol% to 100 mol%, and particularly preferably 0.5 mol% to 70 mol%. It is also possible to introduce a variety of different terminal groups by reacting a variety of terminal sealants.

The terminal sealant introduced into the polyimide precursor resin or polyimide resin can be easily detected by the following method. For example, the polymer into which the terminal sealant has been introduced is dissolved in an acidic solution and decomposed into the amine component and acid anhydride component as the structural unit of the polymer, and gas chromatography (GC) or nuclear magnetic resonance ( Nuclear Magnetic Resonance, NMR) measurement, whereby the end sealant can be easily detected. In addition, it is easy to directly perform thermal decomposition gas chromatography (Pyrolysis Gas Chromatography, PGC), infrared spectroscopy, ¹ H-NMR spectroscopy, and ¹³ C-NMR spectroscopy on the polymer into which the end sealant has been introduced. detected.

<Polyimide resin composition> The polyimide resin of the embodiment of the present invention is mixed with appropriate components to form a polyimide resin composition. The components contained in the polyimide resin composition are not particularly limited, and examples include ultraviolet absorbers, thermal crosslinking agents, inorganic fillers, surfactants, internal release agents, colorants, and the like.

(Ultraviolet absorber) The polyimide resin composition of the embodiment of the present invention preferably contains an ultraviolet absorber. When the polyimide resin composition contains a UV absorber, it is possible to significantly suppress the deterioration of the transparency or mechanical properties of the polyimide when exposed to sunlight for a long time.

As the ultraviolet absorber, a known one can be used without particular limitation. In terms of transparency and non-coloring properties, benzotriazole-based compounds, benzophenone-based compounds, and triazine-based compounds can be preferably used.

The ultraviolet absorber is preferably a compound having a molecular weight of 1,000 or less. When the ultraviolet absorber is a low molecular compound with a molecular weight of 1000 or less, the light resistance of the resin film can be improved without increasing the haze of the polyimide resin film.

The ultraviolet absorber is preferably a compound represented by general formula (28) or general formula (29). The ultraviolet absorber has a high density of aromatic rings in the molecule, which can increase the affinity with polyimide resins with multiple imine rings and aromatic rings in the molecule, and suppress the haze value of the resin film. rise. In addition, since the heat resistance of the ultraviolet absorber is improved, even if it is heated at a high temperature in the step of imidization of the resin, the sublimation of the ultraviolet absorber can be suppressed.

[化17]

R ⁹⁵ to R ¹⁰⁵ each independently represent a hydrogen atom, a hydroxyl group, a monovalent organic group, or a monovalent organic group bonded via an oxygen atom.

As the ultraviolet absorber represented by the general formula (28), for example, Tinuvin 400 (molecular weight: 640, manufactured by BASF), Tinuvin 405 (molecular weight: 584, BASF (Made by BASF), Tinuvin 460 (molecular weight: 630, manufactured by BASF), etc. In addition, as the ultraviolet absorber represented by the general formula (29), RUVA-93 (molecular weight: 323, manufactured by Otsuka Chemical Co., Ltd.), LA-31 (molecular weight: 659, manufactured by ADEKA Co., Ltd.), etc. .

The content of the ultraviolet absorber in the polyimide resin composition is preferably 0.5 to 10 parts by weight relative to 100 parts by weight of the polyimide resin. When the polyimide resin composition contains the ultraviolet absorber within the above range, the light resistance (resistance to light, particularly ultraviolet light) can be improved without impairing the transparency of the resin.

(Thermal crosslinking agent) The polyimide resin composition of the embodiment of the present invention may contain a thermal crosslinking agent. The thermal crosslinking agent is preferably an epoxy compound or a compound having at least two alkoxymethyl groups or hydroxymethyl groups. By having at least two of these groups, the resin and the same molecule undergo a condensation reaction to form a cross-linked structure, which can improve the mechanical strength or chemical resistance of the cured film after the heat treatment.

As preferred examples of the epoxy compound, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl (glycidyloxy) (Propyl) silicone and other epoxy-containing silicones, etc. However, the present invention is not limited to any of these. Specifically, it can be listed: EPICLON 850-S, EPICLON HP-4032, EPICLON HP-7200, EPICLON HP-820, EPICLON HP-820, and EPICLON HP-4032. (EPICLON) HP-4700, EPICLON EXA-4710, EPICLON HP-4770, EPICLON EXA-859CRP, EPICLON EXA-1514, Epiclon (EPICLON) EXA-4880, EPICLON EXA-4850-150, EPICLON EXA-4850-1000, EPICLON EXA-4816, EPICLON EXA-4822 (The above is the trade name, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), RIKARESIN BEO-60E, RIKARESIN BPO-20E, RIKARESIN HBE-100, RIKARESIN DME-100 (the above are the trade names, manufactured by Nippon Physicochemical Co., Ltd.), EP-4003S, EP-4000S (the above are the trade names, ADEKA (Stock) ) Manufacturing), PG-100, CG-500, EG-200 (the above are trade names, manufactured by Osaka Gas Chemical Co., Ltd.), NC-3000, NC-6000 (the above are trade names, Nippon Kayaku Co., Ltd.) Manufacturing), EPOX-MK R508, EPOX-MK R540, EPOX-MK R710, EPOX-MK R1710, VG3101L, VG3101M80 (the above are trade names, manufactured by PRINTEC (stock)), Cyrosid ( CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDe 2083, CELLOXIDE 2085 (the above are trade names, manufactured by DAICEL Chemical Industry (Stock)), etc.

Examples of compounds having at least two alkoxymethyl groups or hydroxymethyl groups include: DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML -OCHP, 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, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry (Stock)), Nigeria NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW -100LM, NIKALAC MX-750LM (the above are the trade names, manufactured by Sanhe Chemical Co., Ltd.). Two or more of these compounds may be contained.

The content of the thermal crosslinking agent in the polyimide resin composition is preferably 0.01 to 50 parts by weight relative to 100 parts by weight of the polyimide resin. When the polyimide resin composition contains the thermal crosslinking agent within the above-mentioned range, the mechanical properties and chemical resistance of the resin can be improved without impairing the transparency of the resin.

(Coupling agent) In order to improve the adhesion to the substrate, the polyimide resin composition of the embodiment of the present invention may be added with a coupling agent such as a silane coupling agent and a titanium coupling agent. The content of the coupling agent in the polyimide resin composition is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyimide resin.

(Inorganic filler) The polyimide resin composition of the embodiment of the present invention may contain an inorganic filler. Examples of the inorganic filler include silica microparticles, alumina microparticles, titanium dioxide microparticles, and zirconia microparticles. 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 fibrous shape.

In order to prevent light scattering, the inorganic filler preferably has a small particle size. Specifically, the average particle size of the inorganic filler is preferably 0.5 nm to 100 nm, more preferably 0.5 nm to 30 nm.

The content of the inorganic filler in the polyimide resin composition is preferably 1 part by weight to 100 parts by weight with respect to 100 parts by weight of the polyimide resin. Since the polyimide resin composition contains an inorganic filler in the above-mentioned range, the CTE or birefringence of the polyimide resin can be reduced without impairing flexibility.

In order to improve the dispersibility of the inorganic filler with respect to polyamide acid, polyimide or polyimide oxazole, the organic-inorganic filler sol can also be treated with a silane coupling agent. If the terminal functional group of the silane coupling agent has an epoxy group or an amine group, it will have affinity with polyamide acid, polyimide or polyimide oxazole by bonding with the carboxylic acid of polyamide acid Improved performance, enabling more effective dispersion.

Examples of those having an epoxy group include: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxy Propyl propyl trimethoxy silane, 3-glycidoxy propyl methyl diethoxy silane, 3-glycidoxy propyl triethoxy silane, etc.

Examples of those having an amino group include: N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyl Trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butene Group) propylamine, N-phenyl-3-aminopropyl trimethoxysilane, etc.

As a treatment method of the organic-inorganic filler sol with a silane coupling agent, various known methods can be used. For example, it can be processed by adding a silane coupling agent to the organic-inorganic filler sol whose concentration is adjusted, and stirring at room temperature to 80°C for 0.5 to 2 hours.

(Surfactant) The polyimide resin composition of the embodiment of the present invention may contain a surfactant. When the polyimide resin composition contains a surfactant, the film thickness uniformity when the polyimide resin composition is applied can be improved. Examples of surfactants include: FLUORAD (trade name, manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (trade name, manufactured by DIC Co., Ltd.), SULFLON ( Trade name, manufactured by Asahi Glass Co., Ltd.) and other fluorine-based surfactants. Other examples include: KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Co., Ltd.), POLYFLOW, and GLANOL (commodity Name, Kyoeisha Chemical Co., Ltd.), BYK (BYK-Chemie Co., Ltd.) and other organosiloxane surfactants. Furthermore, acrylic polymer surfactants such as POLYFLOW (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) can be cited.

The content of the surfactant in the polyimide resin composition is preferably 0.01 to 10 parts by weight relative to 100 parts by weight of the polyimide resin.

(Internal mold release agent) The polyimide resin composition of the embodiment of the present invention may contain an internal mold release agent. When the polyimide resin composition contains an internal mold release agent, the peelability of the polyimide resin film from the supporting substrate can be improved. As an internal mold release agent, long-chain fatty acid etc. are mentioned. The content of the internal release agent in the polyimide resin composition is preferably 0.1 to 5 parts by weight relative to 100 parts by weight of the polyimide resin.

(Coloring agent) The polyimide resin composition of the embodiment of the present invention may contain a coloring agent. By adding a colorant to the polyimide resin composition, the color of the polyimide resin film can be adjusted.

As the coloring agent, dyes, organic pigments, inorganic pigments, etc. can be used, but in terms of heat resistance and transparency, organic pigments are preferred. Among them, those having high transparency, light resistance, heat resistance, and chemical resistance are preferred. If the color index (Color Index, CI) number is used to indicate specific examples of representative organic pigments, the following pigments can be preferably used, but they are not limited to these.

As an example of a yellow pigment, Pigment Yellow (hereinafter referred to 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.

As an example of an orange pigment, Pigment Orange (hereinafter referred to as PO) 13, 36, 38, 43, 51, 55, 59, 61, 64, 65, 71, etc. can be used.

As an example of the red pigment, Pigment Red (hereinafter referred to 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.

As an example of a purple pigment, Pigment Violet (hereinafter referred to as PV) 19, 23, 29, 30, 32, 37, 40, 50, etc. can be used.

As an example of a blue pigment, Pigment Blue (hereinafter referred to as PB) 15, 15:3, 15:4, 15:6, 22, 60, 64, etc. can be used.

As an example of a green pigment, Pigment Green (hereinafter referred to as PG) 7, 10, 36, 58, etc. can be used.

These pigments can also be subjected to surface treatments such as rosin treatment, acid base treatment, and alkaline treatment as needed.

<The manufacturing method of a polyimide resin film> Hereinafter, the method of manufacturing a polyimide resin film using the polyimide resin of embodiment of this invention or its composition is demonstrated.

First, the polyimide precursor resin composition is coated on the substrate. As the substrate, for example, silicon wafers, ceramics, gallium arsenide, soda lime glass, and alkali-free glass can be used. Among them, from the viewpoint of surface smoothness and dimensional stability during heating, alkali-free glass is preferred. The coating method is, for example, a narrow die coating method, a spin coating method, a spray coating method, a roll coating method, a bar coating method, etc., and these methods may be combined for coating. Among them, the narrow die coating method is preferred from the viewpoints of the surface smoothness and film thickness uniformity of the coating film.

Next, the substrate coated with the polyimide precursor resin composition is dried to obtain a polyimide precursor resin composition film. Drying uses hot plates, ovens, infrared rays, vacuum chambers, etc. In the case of using a heating plate, the heated body is held directly on the plate or on a jig such as a proximity pin provided on the plate for heating. As the material of the proximity pin, there are metal materials such as aluminum or stainless steel, or synthetic resin such as polyimide resin or "Teflon" (registered trademark). Proximity pins of any material can be used. The height of the proximity pin varies according to the size of the substrate, the type of the resin layer as the heated body, and the purpose of heating. For example, when heating the resin layer coated on a glass substrate of 300 mm×350 mm×0.5 mm Next, the height of the proximity pin is preferably about 2 mm to 12 mm. The heating temperature varies depending on the type or purpose of the heated object, but it is preferably in the range of room temperature to 180°C for 1 minute to several hours.

Next, heating is performed in the range of 180° C. or higher and 450° C. or lower to convert the polyimide precursor resin composition film into a polyimide resin film. Then, the polyimide resin film was peeled off from the substrate to obtain a polyimide resin film. Examples of the method include a method of immersing in a chemical solution such as hydrofluoric acid, or a method of irradiating a laser at the interface between the polyimide resin film and the substrate. In the case of peeling after forming a device on a polyimide resin film, it is necessary to peel off without damaging the device, and therefore it is preferable to use laser peeling.

The polyimide resin film obtained in the above manner has high transparency, high heat resistance, low birefringence, low linear thermal expansion, flexibility and good laser peelability, and can be preferably used as flexibility Substrate. Regarding transparency, the transmittance at a wavelength of 400 nm is preferably 85% or more, more preferably 90% or more, and still more preferably 95% or more. Regarding the glass transition temperature, it is preferably 280°C or higher, more preferably 300°C or higher, and still more preferably 350°C or higher. Regarding the birefringence, it is preferably 0.04 or less, and more preferably 0.03 or less. Regarding the residual stress, it is preferably 35 MPa or less, more preferably 30 MPa or less, and still more preferably 25 MPa or less.

<Layered body> The layered body of the embodiment of the present invention has an inorganic film on the resin film containing the polyimide resin. As an example of the inorganic film, a gas barrier layer can be cited. The laminate can be preferably used as a support substrate in electronic devices such as touch panels, color filters, liquid crystal elements, and organic EL elements.

The gas barrier layer is a layer that prevents the permeation of water vapor, oxygen, etc. In order to suppress the deterioration of the electronic device due to moisture or oxygen, it is preferable to impart gas barrier properties by providing a gas barrier layer on the resin film containing the polyimide resin of the embodiment of the present invention.

Examples of materials constituting the gas barrier layer include metal oxides, metal nitrides, metal oxynitrides, and metal carbonitrides. Examples of the metal elements contained in these materials include aluminum (Al), silicon (Si), titanium (Ti), tin (Sn), zinc (Zn), zirconium (Zr), indium (In), Niobium (Nb), molybdenum (Mo), tantalum (Ta), calcium (Ca), etc.

In particular, it is preferable that the gas barrier layer includes at least one of silicon oxide, silicon nitride, silicon oxynitride, and silicon carbon nitride. The reason is that by using these materials, it is easy to obtain a uniform and dense film, and the oxygen barrier properties of the gas barrier layer are further improved.

The inorganic film can be formed by, for example, a sputtering method, a vacuum vapor deposition method, an ion plating method, a plasma chemical vapor deposition (Chemical Vapor Deposition, CVD) method, etc., which deposits materials in the vapor phase to form a film. Make it. Among them, since a more uniform and high oxygen barrier film can be obtained, it is preferable to use a sputtering method or a plasma CVD method.

The number of layers of the inorganic film is not limited, and it may be only one layer or multiple layers of two or more layers. Examples of the multilayer film include a gas barrier layer composed of SiN as the first layer and SiO as the second layer; or a gas barrier layer composed of SiON as the first layer and SiO as the second layer.

From the viewpoint of improving oxygen barrier properties, the total thickness of the inorganic film is preferably 10 nm or more, and more preferably 50 nm or more. On the other hand, from the viewpoint of improving the bending resistance of the device, the total thickness of the inorganic film is preferably 1 μm or less, and more preferably 200 nm or less.

<Uses> The polyimide resin film of the embodiment of the present invention can be used for liquid crystal displays, organic EL displays, touch panels, electronic paper, color filters, and light-emitting diode (LED) displays In flexible displays such as display devices, solar cells, and complementary metal oxide semiconductor (Complementary Metal Oxide Semiconductor, CMOS) light receiving devices.

The manufacturing steps of the flexible device include the following steps: forming circuits necessary for the display device and the light receiving device on the polyimide resin film formed on the substrate. For example, an amorphous silicon thin film transistor (TFT) can be formed on a flexible substrate. Furthermore, a structure necessary for the device can also be formed thereon by a known method. By operating in this manner, a known method such as laser irradiation can be used to peel a solid polyimide resin film on which a circuit or the like is formed from the substrate to obtain a flexible device.

(Touch Panel) The touch panel of the embodiment of the present invention includes a resin film containing the polyimide resin. The configuration example of the touch panel of the embodiment of the present invention will be described with reference to the drawings. Fig. 1A is a diagram showing a basic configuration of a touch panel 1 including a polyimide resin film according to an embodiment of the present invention.

A black frame 3, a first transparent wiring 4, and a second transparent wiring 7 are formed on the polyimide resin film 2. In addition, lead wires 6 are respectively provided on the black frame 3, and an insulating film 5 is provided to cover the first transparent wires 4, and the first transparent wires 4 and the second transparent wires 7 are connected to the lead wires 6 Way to form. The protective film 8 is formed so as to cover these various members.

In addition, FIG. 1B is a modification of the touch panel having the configuration shown in FIG. 1A. In the above configuration, a gas barrier layer 9 as an inorganic film is further formed between the polyimide resin film 2 and the black frame 3, the first transparent wiring 4, the second transparent wiring 7, and the like.

The manufacturing method of the touch panel using the polyimide resin of embodiment of this invention includes the following steps (1)-(5), for example. (1) The step of coating the polyimide precursor resin composition on the support substrate. (2) The step of removing the solvent from the coated polyimide precursor resin composition. (3) The step of obtaining the polyimide resin film by imidizing the polyimide precursor. (4) A step of forming transparent wiring, insulating film, and drawing wiring on the polyimide resin film. (5) The step of peeling the polyimide resin film from the support substrate.

The steps of (1) to (3) and (5) can be performed based on the manufacturing method of the polyimide resin film.

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

First, a conductive film is formed on a polyimide resin film and patterned to form a first transparent wiring. As the conductive film, well-known metal films, metal oxide films, films containing carbon materials such as carbon nanotubes or graphene, etc. can be used. Among them, from the viewpoints of transparency, conductivity, and mechanical properties, preferably Application of metal oxide film. As the metal oxide film, for example, the following metal oxide film can be mentioned: indium oxide, cadmium oxide or tin oxide and added with tin, tellurium, cadmium, molybdenum, tungsten, fluorine, zinc, germanium, etc. as impurities, or Zinc oxide or titanium oxide with aluminum added as an impurity, etc. Among them, a thin film of indium oxide containing 2% by mass to 15% by mass of tin oxide or zinc oxide is excellent in transparency and conductivity, and therefore can be preferably used.

The method of forming the first transparent wiring may be any method as long as it can form the target film or pattern. For example, a sputtering method, a vacuum vapor deposition method, an ion plating method, a plasma CVD method, or the like, is a vapor deposition method that deposits a metal oxide in a vapor phase to form a film. Among them, from the viewpoint of obtaining particularly excellent conductivity and transparency, it is preferable to use a sputtering method to form a film. As a method of pattern formation, for example, the following method can be cited: after coating a positive resist such as novolac type, drying, exposing, developing, and etching with acid, patterning the metal oxide film, and finally using alkali The positive resist is peeled off. In addition, the film thickness of the first transparent wiring is preferably 20 nm to 500 nm, and more preferably 50 nm to 300 nm.

Next, an insulating film is formed so as to cover the first transparent wiring. The insulating film may be either an organic film or an inorganic film. The organic film as an insulating film can be formed by applying a general acrylic or polyimide resist, drying, exposing, developing, and thermally curing.

Next, a second transparent wiring is formed on the polyimide resin film and the insulating film. The second transparent wiring can be formed by the same method as the first transparent wiring.

Next, lead wires are formed so as to be conductive with the first transparent wires and the second transparent wires. As a method of forming the lead-out wiring, for example, a method of patterning a metal film having a three-layer structure of a Mo layer, an Al layer, and a Mo layer, which are all formed by a sputtering method, is similar to the first transparent wiring.

A black frame can also be formed between the polyimide resin and the lead wires. Since the lead wires are formed on the black frame, the lead wires cannot be visually recognized. The black frame can be formed by the following method, for example. The black resin composition for a black frame containing polyamide acid in which a black pigment is dispersed is coated by a method such as a spin coater or a die coater so that the cured film thickness becomes 1 μm. After drying under reduced pressure at 60 Pa or less, it is semi-cured using a hot air oven or hot plate at 110°C to 140°C.

Next, a spin coater or die coater is used to coat the positive resist so that the film thickness after prebaking becomes 1.2 μm. After drying under reduced pressure at 80 Pa, it is pre-baked in a hot air oven or hot plate at 80°C to 110°C to form a resist film. After that, exposure is selectively performed by a proximity exposure machine, a projection exposure machine, etc., through a photomask. In addition, the exposed portion is removed by immersing in an alkaline developer such as potassium hydroxide or tetramethylammonium hydroxide of 1.5% to 3.0% by weight for 20 to 300 seconds. After peeling off the positive resist with a stripping solution, use a hot air oven or hot plate at 200°C to 300°C to heat for 10 minutes to 60 minutes to convert polyamide acid to polyimide, and apply it to the resin film. A black frame with black pigment dispersed on it is formed. In addition, in the case of forming using a photosensitive resin, exposure and development can be performed without applying a positive resist.

In addition, in order to protect the black frame, an insulating film may be formed on the black frame. In this case, the insulating film on the black frame may be formed simultaneously with the insulating film formed on the first transparent wiring. The insulating film may be either an organic film or an inorganic film. The organic film as an insulating film can be formed by applying a general acrylic or polyimide resist, drying, exposing, developing, and thermally curing.

Furthermore, a protective film may be provided to cover each member constituting the touch panel. The protective film may be either an organic film or an inorganic film. The organic film as the protective film can be formed by applying an acrylic polymer solution, drying and thermal curing, for example.

A gas barrier layer can also be provided on the polyimide resin film. By forming a laminate having a gas barrier layer on the polyimide resin film, gas barrier properties can be imparted to the polyimide resin film, and deterioration of wiring due to moisture or oxygen can be suppressed. The number of layers of the gas barrier layer is not limited, and may be only one layer, or multiple layers of two or more layers. As an example of a multilayer film, a gas barrier layer composed of SiO as the first layer and SiN as the second layer, or a gas barrier layer composed of SiO/AlO/ZnO as the first layer and SiO as the second layer.

(Color filter) The color filter of the embodiment of the present invention includes a resin film containing the polyimide resin. The configuration example of the color filter according to the embodiment of the present invention will be described with reference to the drawings.

2A is a diagram showing the basic configuration of a color filter 10 including a polyimide resin film according to an embodiment of the present invention. A black matrix 11, a red coloring pixel 12R, a green coloring pixel 12G, and a blue coloring pixel 12B are formed on the polyimide resin film 2. The color filter further includes an overcoat layer 13 so as to cover these members. Fig. 2B is a modification of the configuration shown in Fig. 2A. In the above configuration, a gas barrier layer 9 as an inorganic film is further formed between the polyimide resin film 2 and each colored pixel and the black matrix 11.

The black matrix is preferably a resin black matrix in which black pigments are dispersed in resin. Examples of black pigments include carbon black, titanium black, titanium oxide, titanium nitride oxide, titanium nitride, or iron tetroxide. In particular, carbon black and titanium black are preferable. In addition, a red pigment, a green pigment, and a blue pigment may be mixed and used as a black pigment.

As the resin used in the resin black matrix, since it is easy to form a fine pattern, a polyimide resin is preferable. The polyimide resin is preferably a polyimide resin that is formed by thermally curing a polyimide acid synthesized from an acid anhydride and a diamine after pattern processing. As examples of acid anhydrides, diamines, and solvents, those listed in the polyimide resin can be used.

The resin used in the resin black matrix is also preferably a photosensitive acrylic resin. The resin black matrix using this preferably contains an alkali-soluble acrylic resin in which a black pigment is dispersed, a photopolymerizable monomer, a polymer dispersant, and an additive.

As an example of an alkali-soluble resin, the copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound is mentioned. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate, or acid anhydride.

Examples of photopolymerizable monomers include: trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, triacrylformal, and pentaerythritol tetra(meth)acrylate Acrylate, dipentaerythritol hexa(meth)acrylate or dipentaerythritol penta(meth)acrylate.

Examples of photopolymerization initiators include benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethyl Aminobenzophenone, 2,2-diethoxyacetophenone, α-hydroxyisobutyl phenyl ketone, thioxanthone or 2-chlorothioxanthone.

Examples of solvents used to dissolve the photosensitive acrylic resin include: propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl acetone, methyl-3-methoxypropionate, ethyl acetate 3-ethoxypropionate, methoxybutyl acetate or 3-methyl-3-methoxybutyl acetate.

Coloring pixels usually include red, green, and blue coloring pixels. In addition, in addition to the three-color colored pixels, by forming colorless and transparent pixels or extremely thinly attached fourth color pixels, the brightness of the white display of the display device can also be improved.

A resin containing a pigment or dye as a coloring agent is used for the colored pixels of the color filter.

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

Examples of the pigment used in the green coloring pixel include PG7, PG36, PG58, PG37, PB16, PY129, PY138, PY139, PY150, or PY185.

As an example of the pigment used in the blue coloring pixel, PB15:6 or PV23 can be mentioned.

Examples of blue dyes include CI Basic Blue (BB) 5, BB7, BB9, or BB26. Examples of red dyes include CI Acid Red (AR) 51, AR87 or AR289. .

Examples of resins used in the red, green and blue coloring pixels include acrylic resins, epoxy resins, or polyimide resins. Since the color filter can be manufactured at a low cost, it is preferably photosensitive. Acrylic resin. The photosensitive acrylic resin usually contains an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator.

As an example of an alkali-soluble resin, the copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound is mentioned. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate, or acid anhydride.

Examples of photopolymerizable monomers include: trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, triacrylic acid formal, pentaerythritol tetra(meth)acrylate, Dipentaerythritol hexa(meth)acrylate or dipentaerythritol penta(meth)acrylate.

Examples of photopolymerization initiators include benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethyl Aminobenzophenone, 2,2-diethoxyacetophenone, α-hydroxyisobutyl phenyl ketone, thioxanthone or 2-chlorothioxanthone.

Examples of solvents used to dissolve the photosensitive acrylic resin include: propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl acetylacetate, methyl-3-methoxypropionate, Ethyl-3-ethoxypropionate, methoxybutyl acetate or 3-methyl-3-methoxybutyl acetate.

The manufacturing method of the color filter using the polyimide resin of embodiment of this invention includes the following steps (1)-(6), for example. (1) The step of coating the polyimide precursor resin composition on the support substrate. (2) The step of removing the solvent from the coated polyimide precursor resin composition. (3) The step of obtaining the polyimide resin film by imidizing the polyimide precursor. (4) A step of forming a black matrix on the polyimide resin film. (5) A step of forming colored pixels on the polyimide resin film. (6) The step of peeling the polyimide resin film from the support substrate.

The steps of (1) to (3) and (6) can be performed based on the manufacturing method of the polyimide resin film.

In the step (4), for example, a black matrix is formed as follows. Use a spin coater or die coater to coat the polyimide resin film on the polyimide resin film so that the thickness of the cured film becomes 1 μm. Things. After drying under reduced pressure at 60 Pa or less, it is semi-cured using a hot air oven or hot plate at 110°C to 140°C.

Next, a spin coater or die coater is used to coat the positive resist so that the film thickness after prebaking becomes 1.2 μm. After drying under reduced pressure at 80 Pa, it is pre-baked in a hot air oven or hot plate at 80°C to 110°C to form a resist film. After that, a proximity exposure machine or a projection exposure machine is used to selectively expose with ultraviolet rays through a photomask. In addition, the exposed portion is removed by immersing in an alkaline developer such as potassium hydroxide or tetramethylammonium hydroxide of 1.5% to 3.0% by weight for 20 to 300 seconds. After peeling off the positive resist with a stripping solution, use a hot air oven or hot plate at 200°C to 300°C to heat for 10 minutes to 60 minutes to convert polyamide acid to polyimide, and apply it to the resin film. A resin black matrix in which black pigments are dispersed is formed on it. In addition, in the case of forming using a photosensitive resin, exposure and development can be performed without applying a positive resist.

In the step (5), for example, the following method is used to form colored pixels on the polyimide resin film formed with the resin black matrix.

The colored pixels of the color filter are made using colorants and resins. In the case of using a pigment as a colorant, after mixing a polymer dispersant and a solvent with the pigment and performing a dispersion treatment, an alkali-soluble resin, a monomer, a photopolymerization initiator, etc. are added. On the other hand, when a dye is used as a coloring agent, a solvent, an alkali-soluble resin, a monomer, a photopolymerizable initiator, etc. are added to the dye. The total solid content in this case is the total of the polymer dispersant as the resin component, the alkali-soluble resin, the monomer, and the coloring agent.

Using a method such as a spin coater or a die coater, the obtained colorant composition is applied to the transparent substrate on which the resin black matrix is formed so that the film thickness after the heat treatment becomes the target film thickness of 0.8 μm to 3.0 μm. After drying it under reduced pressure at 80 Pa, it is pre-baked in a hot-air oven or hot plate at 80°C to 110°C to form a coating film of a coloring agent.

Secondly, with a proximity exposure machine or a projection exposure machine, etc., the exposure is selectively performed through the mask. After that, the unexposed part is removed by immersing in an alkaline developer such as a 0.02% to 1.0% by weight potassium hydroxide aqueous solution or a tetramethylammonium hydroxide aqueous solution for 20 to 300 seconds. The obtained coating film pattern is heated for 5 minutes to 40 minutes in a hot air oven or hot plate at 180°C to 250°C to form colored pixels. Using the coloring agent composition produced for each color of the colored pixels, the red colored pixels, the green colored pixels, and the blue colored pixels are sequentially patterned as described above. In addition, the order of patterning of colored pixels is not particularly limited.

A planarization layer can also be provided on the color filter. Examples of the resin used in the formation of the planarization layer include epoxy resin, acrylic epoxy resin, acrylic resin, silicone resin, and polyimide resin. The film thickness of the planarization layer is preferably a thickness with a flat surface, specifically, it is more preferably 0.5 μm to 5.0 μm, and still more preferably 1.0 μm to 3.0 μm.

A gas barrier film can also be formed between the polyimide resin film and the black matrix/coloring pixel layer. By forming a laminate with a gas barrier layer on the polyimide resin film, gas barrier properties can be imparted to the polyimide resin film, and deterioration of colored pixels caused by moisture or oxygen can be suppressed. The number of layers of the gas barrier layer is not limited, and may be only one layer, or multiple layers of two or more layers. As an example of a multilayer film, a gas barrier layer composed of SiO as the first layer and SiN as the second layer, or a gas barrier layer composed of SiO/AlO/ZnO as the first layer and SiO as the second layer.

(Liquid crystal element) The liquid crystal element of the embodiment of the present invention includes a resin film containing the polyimide resin. The configuration example of the liquid crystal element according to the embodiment of the present invention will be described with reference to the drawings.

Fig. 3 is a diagram showing the basic configuration of a liquid crystal element 14 including a polyimide resin film according to an embodiment of the present invention. The polyimide resin film 32 as the first base material and the polyimide resin film 42 as the second base material have a gap and are arranged facing each other. A liquid crystal layer 19 is provided between these. A gas barrier layer 9 as an inorganic film is provided on the polyimide resin film 42, and a transparent conductive layer made of indium tin oxide (ITO), indium zinc oxide (Indium Zinc Oxide, IZO), etc. is provided on it. The pixel electrode 15 formed by the film and the first alignment film 16 are formed. In this way, by forming a laminate with a gas barrier layer on the polyimide resin film, gas barrier properties can be imparted to the polyimide resin film, and deterioration of the electrode due to moisture or oxygen can be suppressed. In addition, a gas barrier layer 9 as an inorganic film is provided on the polyimide resin film 42, and a counter electrode 18 is provided thereon so as to face the pixel electrode 15. In addition, a second alignment film 17 is provided on the surface of the counter electrode 18 on the liquid crystal layer side.

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

The steps of (1) to (3) and (5) can be performed based on the manufacturing method of the polyimide resin film.

The step (4) can be performed in the following manner, for example. First, a gas barrier layer is formed on the polyimide resin film (the first supporting base material and the second supporting base material) to suppress the permeation of gas such as water vapor or oxygen. As a preferable gas barrier layer, for example, a metal oxide with one or two or more metals selected from the group consisting of silicon, aluminum, magnesium, zinc, zirconium, titanium, yttrium and tantalum as the main component can be cited Substances, metal nitrides of silicon, aluminum, boron, or a mixture of these. Among them, from the viewpoints of gas barrier properties, transparency, surface smoothness, flexibility, film stress, cost, etc., it is preferable to use silicon oxide, nitride, or oxynitride as the main component.

The gas barrier layer can be produced by, for example, a sputtering method, a vacuum vapor deposition method, an ion plating method, a plasma CVD method, or the like, which deposits a material in a gas phase to form a film. Among them, the sputtering method is preferred from the viewpoint of obtaining particularly excellent gas barrier properties.

In addition, the thickness of the gas barrier layer is preferably 10 nm to 300 nm, and more preferably 30 nm to 200 nm. In order to obtain high gas barrier properties, it is preferable that the film forming temperature of the gas barrier layer is high, and it is preferably 300°C or higher.

Secondly, pixel electrodes are formed on the gas barrier layer formed on the first support substrate, and opposing electrodes are formed on the gas barrier layer formed on the second support substrate. The method of forming the pixel electrode and the counter electrode may be any method as long as it can form the target thin film and pattern. For example, sputtering, vacuum evaporation, ion plating, plasma CVD, etc. are suitable. A vapor deposition method in which a metal oxide is deposited in a vapor phase to form a film. The film thickness of the pixel electrode and the opposite electrode is preferably 20 nm to 500 nm, and more preferably 50 nm to 300 nm.

Secondly, a first alignment film is formed on the pixel electrodes, and a second alignment film is formed on the opposite electrodes. The materials and the forming method used for the formation of the alignment film can be known in the art. For example, an alignment film containing polyimide resin can be coated by a printing method, heated at 250° C. for 10 minutes using a hot plate, and rubbing treatment is performed on the obtained film to form it. The thickness of the first alignment film and the second alignment film only needs to be a thickness that can align the liquid crystal of the liquid crystal layer, and is preferably 20 nm to 150 nm, respectively.

Next, a liquid crystal layer is formed. Regarding the formation of the liquid crystal layer, a known method can be used. For example, the liquid crystal layer can be formed by the following method. First, the sealant was coated on the second alignment film by a dispense method, and heated at 90° C. for 10 minutes using a hot plate. On the other hand, spherical spacers with a diameter of 5.5 μm are dispersed on the first alignment film. This was superimposed on the substrate coated with the sealant, and while pressing in an oven, it was heated at 160° C. for 90 minutes to harden the sealant to obtain a cell. Then, the cell was left at a temperature of 120°C and a pressure of 13.3 Pa for 4 hours, and thereafter, after being left in nitrogen for 0.5 hours, the liquid crystal compound was filled again under vacuum. The filling of the liquid crystal compound is performed by placing the cell in the chamber, and after depressurizing to a pressure of 13.3 Pa at room temperature, immersing the liquid crystal injection port in the liquid crystal, using nitrogen and returning to normal pressure. After filling the liquid crystal, the liquid crystal injection port is sealed with ultraviolet curing resin. After these steps, the polyimide resin film is peeled from the supporting substrate, and polarizing plates are attached to the first supporting substrate and the second supporting substrate, respectively, thereby obtaining a liquid crystal element.

<Organic EL element> The organic EL element of the embodiment of the present invention includes a resin film containing the polyimide resin. A configuration example of the organic EL device according to the embodiment of the present invention will be described with reference to the drawings.

Fig. 4 is a diagram showing the basic configuration of an organic EL element 21 including a polyimide resin film according to an embodiment of the present invention. A gas barrier layer 9 as an inorganic film is further formed on the polyimide resin film 2. A TFT layer 22 including amorphous silicon, low-temperature polysilicon, oxide semiconductor, etc., and a planarization layer 23 are provided thereon. Furthermore, it has a first electrode 24 including Al/ITO, etc., and an insulating film 25 covering the end of the first electrode 24, and is provided with a hole input layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. The organic EL light-emitting layers 26R (red light-emitting layer), 26G (green light-emitting layer), and 26B (blue light-emitting layer) are formed with a second electrode 27 containing ITO and the like, and are sealed with a gas barrier layer 9.

The manufacturing method of the organic electroluminescent element using the polyimide resin of embodiment of this invention includes the following steps (1)-(5), for example. (1) The step of coating the polyimide precursor resin composition on the support substrate. (2) The step of removing the solvent from the coated polyimide precursor resin composition. (3) The step of obtaining the polyimide resin film by imidizing the polyimide precursor. (4) A step of forming an organic EL light-emitting circuit on the polyimide resin film. (5) The step of peeling the polyimide resin film from the support substrate.

The steps of (1) to (3) and (5) can be performed based on the manufacturing method of the polyimide resin film.

The step (4) can be performed in the following manner, for example. First, a gas barrier layer is formed on the polyimide resin film. Examples of preferable gas barrier layers are the same as those described in the section of the liquid crystal element. By forming a laminate having a gas barrier layer on the polyimide resin film, gas barrier properties can be imparted to the polyimide resin film, and the deterioration of the organic EL light-emitting layer caused by moisture or oxygen can be suppressed.

Secondly, a TFT is formed on the gas barrier film. Examples of the semiconductor layer used to form the TFT include amorphous silicon semiconductors, polycrystalline silicon semiconductors, oxide semiconductors represented by InGaZnO, organic semiconductors represented by pentacene or polythiophene, and the like. The specific method of forming the TFT is as follows. For example, using the laminate of the embodiment of the present invention as a base material, a gas barrier film, a gate electrode, a gate insulating film, a polysilicon semiconductor layer, an etching stop layer, and source/drain electrodes are sequentially formed by a known method. And make the bottom gate type TFT.

Secondly, a planarization layer is formed on the TFT. As an example of the resin used for formation of a planarization layer, epoxy resin, acrylic epoxy resin, acrylic resin, polysiloxane resin, or polyimide resin is mentioned. Furthermore, an electrode and an organic layer are formed thereon. Specifically, a first electrode including Al/ITO, etc. is formed, and then an insulating film covering the end of the first electrode is provided and includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer The white organic EL light-emitting layer as the organic layer. Furthermore, a second electrode containing ITO or the like is formed to form a sealing film.

After the organic EL light-emitting circuit is produced through these steps, the resin film is peeled from the supporting substrate, thereby obtaining an organic EL device. [Example]

Examples and the like are listed below to illustrate the present invention, but the present invention is not limited by these examples.

(1) The production of polyimide resin film uses Mark-7, a coating and developing device manufactured by Tokyo Electron Co., Ltd., on a 6-inch mirror silicon wafer and pre-baked at 140°C The varnish was spin-coated so that the film thickness after 4 minutes became 15 μm±0.5 μm. Thereafter, the same heating plate of Mark -7 was used for pre-baking at 140°C for 4 minutes. The pre-baked film was heated in an inert gas oven (INH-21CD manufactured by Koyo Thermos Co., Ltd.) under a nitrogen flow (oxygen concentration of 20 ppm or less) at 3.5°C/min to 300°C and kept for 30 minutes. Cool down to 50°C at 5°C/min to produce a polyimide resin film.

(2) The polyimide resin film (on the glass substrate-1) was made using the spin coater MS-A200 manufactured by Mikasa Co., Ltd. on a 50 mm×50 mm×1.1 mm thick glass substrate (TEMPAX), the varnish is spin-coated so that the film thickness after pre-baking at 140°C for 4 minutes becomes 15 μm±0.5 μm. Thereafter, a pre-baking treatment at 140°C for 4 minutes was performed using a hot plate D-SPIN manufactured by Dainippon Screen Co., Ltd. The pre-baked film was heated in an inert gas oven (INH-21CD manufactured by Koyo Thermos Co., Ltd.) under a nitrogen flow (oxygen concentration of 20 ppm or less) at 3.5°C/min to 300°C and kept for 30 minutes. Cool down to 50°C at 5°C/min to produce a polyimide resin film (on a glass substrate).

(3) The production of polyimide resin film (on the glass substrate-2) uses a slit coater (manufactured by Toray Engineering (stock)) on a 300 mm×350 mm×0.5 mm thick glass On the substrate (AN-100 manufactured by Asahi Glass Co., Ltd.), the varnish is spin-coated so that the film thickness after pre-baking at 140°C for 4 minutes becomes 15 μm ± 0.5 μm. After that, a 140°C pre-baking treatment was performed for 4 minutes using a hot plate. The pre-baked film is heated to 300°C for 70 minutes in an inert gas oven (made by Koyo thermos (stock) INH-21CD) under a nitrogen stream (oxygen concentration below 20 ppm), and kept at 5°C for 30 minutes. /min is cooled to 50°C to produce a polyimide resin film (on a glass substrate).

(4) The polyimide resin film (on the silicon substrate) was made using a spin coater MS-A200 manufactured by Mikasa Co., Ltd. on a 4-inch silicon substrate that was cut into 1/4. The varnish was spin-coated so that the film thickness after pre-baking at 140°C for 4 minutes became 5 μm±0.5 μm. Thereafter, a pre-baking treatment at 140°C for 4 minutes was performed using a hot plate D-SPIN manufactured by Dainippon Screen Co., Ltd. The pre-baked film was heated in an inert gas oven (INH-21CD manufactured by Koyo Thermos Co., Ltd.) under a nitrogen flow (oxygen concentration of 20 ppm or less) at 3.5°C/min to 300°C and kept for 30 minutes. Cool down to 50°C at 5°C/min to produce a polyimide resin film (on a silicon substrate).

(5) Measurement of light transmittance (T) An ultraviolet-visible spectrophotometer (MultiSpec 1500 manufactured by Shimadzu Corporation) was used to measure light transmittance at wavelengths of 308 nm and 400 nm. In addition, the polyimide resin film produced in (2) was used for the measurement.

(6) Measurement of haze value Use direct reading haze computer (HGM2DP manufactured by Suga Tester Co., Ltd., C light source) to measure the haze of the polyimide resin film on the glass substrate made in (2) Degree value (%). In addition, as each value, the average value of 3 measurements was used.

(7) Measurement of in-plane/out-of-plane birefringence. A prism coupling (manufactured by METRICON, PC2010) was used to measure the TE refractive index (n(TE)) and TM refractive index (n( TM)). n(TE) and n(TM) are the refractive indexes in parallel and perpendicular directions with respect to the surface of the polyimide film, respectively. Calculate the difference between n(TE) and n(TM) (n(TE)-n(TM)) as the in-plane/out-of-plane birefringence. In addition, the polyimide resin film produced in (4) was used for the measurement.

(8) The glass transition temperature (Tg) and linear thermal expansion coefficient (CTE) are measured using a thermo-mechanical analysis device (SII NanoTechnology Co., Ltd. manufactured EXSTAR 6000TMA/SS6000) under nitrogen flow. . The heating method is performed under the following conditions. In the first stage, the temperature is increased to 150°C at a heating rate of 5°C/min to remove the adsorbed water from the sample. In the second stage, air-cooled to room temperature at a cooling rate of 5°C/min. In the third stage, a formal measurement was performed at a heating rate of 5°C/min to obtain the glass transition temperature. In addition, the average of the coefficient of linear thermal expansion (CTE) at 50°C to 200°C in the third stage was obtained. In addition, a film obtained by peeling off the polyimide resin film produced in (1) from the silicon wafer was used for the measurement.

(9) Measurement of 1% thermogravimetric reduction temperature (Td1) Use a thermogravimetry device (TGA-50 manufactured by Shimadzu Corporation) to measure under nitrogen flow. The heating method is performed under the following conditions. In the first stage, the temperature is increased to 350 degrees at a heating rate of 3.5°C/min and the adsorbed water of the sample is removed. In the second stage, it is cooled to room temperature at a cooling rate of 10°C/min. In the third stage, a formal measurement is performed at a heating rate of 10°C/min, and the 1% thermal weight loss temperature is obtained. In addition, a film obtained by peeling off the polyimide resin film produced in (1) from the silicon wafer was used for the measurement.

(10) Measurement of elongation at break Tensilon (Orientec Co., Ltd. RTM-100) was used for measurement. Measure more than 10 samples per sample, and calculate the JIS average value using the Japanese Industrial Standards (JIS) number average (JIS K-6301). In addition, a film obtained by peeling off the polyimide resin film produced in (1) from the silicon wafer was used for the measurement.

(11) Measurement of residual stress The measurement was performed using a thin film stress measurement device FLX-3300-T manufactured by KLA-Tencor. The measurement was performed using the polyimide resin film produced in (1), and the polyimide resin film was allowed to stand in a room at a room temperature of 23° C. and a humidity of 55% for 24 hours before the measurement.

(12) Laser peel test The polyimide resin film obtained by the method described in (3) was irradiated with a 308 nm excimer laser (shape: 21 mm×1.0 mm) from the glass substrate side, and the laser Shoot peel test. The laser is irradiated in the direction of the minor axis, staggered by 0.25 mm at a time. When the incision was cut along the edge of the irradiation area, the energy of the peeling film was used as the irradiation energy (peeling energy) required for peeling, and the laser peelability was evaluated using the following criteria. Excellent (A): The peeling energy is 230 mJ/cm ² or less. Good (B): The peeling energy exceeds 230 mJ/cm ² and is 270 mJ/cm ² or less. Good (C): The peeling energy exceeds 270 mJ/cm ² and is 310 mJ/cm ² or less. Pass (D): The peeling energy exceeds 310 mJ/cm ² and is 350 mJ/cm ² or less. Bad (E): The peeling energy exceeds 350 mJ/cm ² .

(13) Production and evaluation of touch panel (FIG. 1A) The production and evaluation of the touch panel were carried out by the method described below.

[1] Formation of the black frame on the surface of the polyimide resin film on the glass substrate produced by the method (3), spin-coated a black resin composition for a black frame containing polyamide acid dispersed with black pigments, It was dried on a hot plate heated at 90°C for 3 minutes to form a black resin coating film. Spin-coating positive photoresist (Shipley (Shipley) company, "SRC-100"), using a hot plate for pre-baking. Secondly, use an ultra-high pressure mercury lamp to expose the mask with an exposure of 200 mJ/cm ² (UV intensity at 365 nm), and then use a 2.38% tetramethylammonium hydroxide aqueous solution to perform photoresist Development of the agent and etching of the black resin coating film to form a pattern. Furthermore, after the photoresist was peeled off with methyl cellulose acetate, the black resin coating film was heated in a hot air oven at 280°C for 30 minutes, thereby reducing the polyamide contained in the black resin coating film. Imidization, forming a black frame.

[2] Formation of the first transparent wiring The first transparent wiring containing ITO was formed on the surface of the polyimide resin film on which the black frame was formed in the following manner. An ITO film is formed on the polyimide resin film by sputtering. After coating a novolak-based positive resist on the ITO film, drying, exposure, development, and etching with an acid are performed to pattern the ITO film, and finally the positive resist is peeled off with an alkali.

[3] Formation of insulating film Next, an insulating film is formed on the first transparent wiring. The insulating film is formed by coating an acrylic negative resist, drying, exposing, developing, and thermally curing.

[4] Formation of the second transparent electrode Next, the second transparent electrode was formed on the polyimide resin film by the same method as the first transparent wiring.

[5] Formation of lead-out wiring (metal wiring) Next, lead-out wiring (metal wiring) that is conductive to the first transparent wiring and the second transparent wiring is formed on the black frame. The lead wiring is formed by patterning a metal film having a three-layer structure of Mo layer, Al layer, and Mo layer formed by the sputtering method in the same manner as the first transparent wiring.

[6] Formation of transparent protective film Next, an acrylic transparent protective film covering the formed members was formed.

Finally, by irradiating an excimer laser (wavelength of 308 nm) from the glass substrate side, and peeling the polyimide resin film from the glass substrate, a touch panel was obtained (Figure 1A). The obtained touch panel was attached to an organic EL light emitting panel, and the visibility and operability were evaluated.

<Visibility> The color tone when the organic EL panel displays white is visually observed, and the visibility is judged as follows. Good (A): White is observed. Good (B): Although a little coloration is observed, white is observed to an unconscious degree. Bad (C): Obviously colored and cannot be called white.

<Operability> Connect the touch panel and the external touch position detection circuit (driver), and touch it with your finger according to the instructions displayed on the screen. The operability at this time is determined as follows. Excellent (A): Can be input without malfunction. Good (B): Some malfunctions are observed, but can be input almost without malfunctions. Bad (C): There are many misoperations and it is impossible to input accurately.

(14) Fabrication of color filter (FIG. 2A) and measurement of BM position accuracy The method described below was used to fabricate color filters and the measurement of BM position accuracy.

[1] Production of black matrix: The surface of the polyimide resin film on the glass substrate prepared by the method (3) was spin-coated on the resin black resin composition for black matrix containing polyamide acid dispersed with black pigment , Use a hot plate to dry to form a black resin coating film. Spin-coating positive photoresist (Shipley (Shipley) company, "SRC-100"), using a hot plate for pre-baking. Secondly, use an ultra-high pressure mercury lamp to expose the mask with an exposure of 200 mJ/cm ² (UV intensity at 365 nm), and then use a 2.38% tetramethylammonium hydroxide aqueous solution to perform photoresist Development of the agent and etching of the resin coating film to form a pattern. Furthermore, after the photoresist was peeled off with methyl cellulose acetate, the black resin coating film was heated in a hot air oven at 280°C for 30 minutes, thereby reducing the polyamide contained in the black resin coating film. Imidization, and the black matrix 4 is formed. The thickness of the black matrix was measured, and the result was 1.4 μm.

[2] Production of colored pixels: A photosensitive red resist is coated on a polyimide resin film on a patterned glass substrate with a black matrix. At this time, the rotation speed of the spinner was adjusted so that the thickness of the resist at the opening of the black matrix after the heat treatment became 2.0 μm. Secondly, using a hot plate, pre-baking at 100°C for 10 minutes, thereby obtaining red colored pixels. Secondly, using the UV exposure machine "PLA-5011" manufactured by Canon (Co., Ltd.), a mask made of chrome (Chrome) that transmits light through islands is used for the openings of the black matrix and part of the area on the black matrix. , Expose at 100 mJ/cm ² (UV intensity at 365 nm). After exposure, it was immersed in a developer solution containing 0.2 wt% of tetramethylammonium hydroxide aqueous solution for development, and then washed with pure water. Thereafter, heat treatment was performed in an oven at 230° C. for 30 minutes to produce red pixels.

Similarly, a green pixel containing a photosensitive green resist and a blue pixel containing a photosensitive blue resist were produced. Then, the rotation speed of the spinner was adjusted so that the thickness of the colored pixel portion after the heat treatment became 2.5 μm, and the resin composition was applied. Thereafter, heat treatment was performed in an oven at 230°C for 30 minutes to produce an overcoat layer.

For the deviation of the black matrix of the color filter on the glass substrate produced by the method from the ideal lattice (ideallattice), SMIC-800 (manufactured by Sokkia Topcon) is used for each belt The glass color filter substrates were measured at 24 points, respectively. The average of the absolute value of the deviation obtained by the measurement is calculated by calculation, and the obtained value is used as the deviation of the black matrix from the ideal lattice at its level. The value of the amount of deviation in each Example and Comparative Example was evaluated. In addition, when the BM pattern is formed on the glass substrate and when the BM pattern is formed on the polyimide resin, the difference in the amount of deviation is evaluated (considered as the "BM position deviation amount" ), use the following evaluation methods to determine. Good (A): BM position deviation is 1.8 μm or less. Good (B): The amount of BM positional deviation exceeds 1.8 μm and is 2.4 μm or less. Bad (C): BM position deviation exceeds 2.4 μm.

(15) Fabrication of organic EL elements and measurement of the angular dependence of color coordinates (x, y) The production of organic EL elements and the measurement of the angular dependence of color coordinates (x, y) were performed by the method described below.

[1] Production of TFT substrate On the surface of the polyimide resin film on the glass substrate produced by the method (3), a gas barrier layer containing SiO was formed using a plasma CVD method. Thereafter, a bottom gate type TFT is formed, and an insulating film containing Si ₃ N ₄ is formed in a state covering the TFT. Next, after forming a contact hole on the insulating film, a wiring (height 1.0 μm, not shown) connected to the TFT via the contact hole is formed on the insulating film. The wiring is used to connect between the TFTs or the organic EL element formed in a subsequent step and the TFT.

Furthermore, in order to flatten the unevenness caused by the formation of the wiring, a flattening layer is formed on the insulating film in a state where the unevenness caused by the wiring is filled. The formation of the planarization layer is carried out as follows: the photosensitive polyimide varnish is spin-coated on the substrate, pre-baked on the hot plate (120℃×3 minutes), and then the mask of the desired pattern is interposed Exposure and development are performed, and heat treatment is performed at 230°C for 60 minutes under air flow. The coatability when applying varnish is good. No wrinkles or cracks were confirmed on the flattened layer obtained after exposure, development, and heat treatment. The average step difference of the wiring is 500 nm, and a 5 μm square contact hole is formed in the produced planarization layer, and the thickness is about 2 μm.

[2] Fabrication of bottom emission type organic EL device The following parts were formed on the obtained planarization layer to fabricate a bottom emission type organic EL device. First, the first electrode 17 containing ITO is connected to the wiring via a contact hole on the planarization layer. After that, the resist is applied, pre-baked, exposed through a mask of a desired pattern, and developed. Using the resist pattern as a mask, pattern processing of the first electrode was performed by wet etching using an ITO etchant. After that, the resist pattern was peeled off using a resist stripping liquid (a mixed liquid of monoethanolamine and diethylene glycol monobutyl ether). The peeled substrate was washed with water and heated and dehydrated at 200°C for 30 minutes to obtain an electrode substrate with a planarization layer. Regarding the thickness change of the planarization layer, after heat dehydration, it was less than 1% relative to the thickness before the peeling liquid treatment. The first electrode thus obtained corresponds to the anode of the organic EL element.

Next, an insulating layer covering the shape of the end of the first electrode is formed. A photosensitive polyimide varnish was similarly used for the insulating layer. By providing the insulating layer, a short circuit between the first electrode and the second electrode formed in the subsequent step can be prevented.

Furthermore, in the vacuum evaporation device, the hole transport layer, the organic light emitting layer, and the electron transport layer are sequentially vapor-deposited through the required pattern mask, and the red organic EL light emitting layer, the green organic EL light emitting layer, and the blue Organic EL light emitting layer. Then, a second electrode including Al/Mg (Al: reflective electrode) is formed on the entire surface above the substrate. Furthermore, a SiON sealing film is formed by CVD film formation.

The obtained substrate was taken out of the vapor deposition machine, and an excimer laser (wavelength: 308 nm) was irradiated from the glass substrate side, thereby peeling the organic EL element from the glass substrate. A voltage was applied to the obtained active matrix organic EL element via a drive circuit to display red. The brightness orientation characteristic measuring device C9920-11 (manufactured by Hamamatsu Photonics Co., Ltd.) was used to measure the color coordinates in the 0° direction. (X, y) and the color coordinates (x', y') in the direction of 70°. The smaller the difference of the color coordinates measured in each direction, the smaller the color difference in the oblique field of view, and it is determined by the following evaluation method. Good (A): |x-x'|+|y-y'|≦0.3 Good (B): |x-x'|+|y-y'|≦0.5 Pass (C): |x-x' |+|y-y'|≦0.7 Bad (D): |x-x'|+|y-y'|>0.7.

(16) Light resistance test The light resistance test was performed under the following conditions, and the physical properties (transmittance, elongation at break, CTE, haze, laser peelability) before and after the light resistance test were compared. In addition, the light resistance test used the polyimide resin film on the glass substrate prepared in (3), and irradiated light from the resin film side.

Device: Q-Sun Xe-1 (manufactured by Q-Lab)

Illuminance at wavelength 340nm: 0.4W/m ²

Black panel temperature: 55℃

Irradiation time: 250 hours.

Hereinafter, the abbreviations of the compounds used in the examples are described.

CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

PMDA-HH: 1S, 2S, 4R, 5R-cyclohexane tetracarboxylic dianhydride

PMDA-HS: 1R, 2S, 4S, 5R-cyclohexane tetracarboxylic dianhydride

BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

BPF-PA: 9,9-bis(4-(3,4-dicarboxyphenoxy)phenyl) anhydride

HFHA: 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]hexafluoropropane

m-TB: 2,2'-dimethyl-4,4'-diaminobiphenyl

TFMB: 2,2'-bis(trifluoromethyl)benzidine

DABA: 4,4'-diaminobenzaniline

4-ABS-3AP: 3-Aminophenyl-4-aminobenzenesulfonate

NMP: N-methyl-2-pyrrolidone.

Example 1

Under a stream of dry nitrogen, CBDA 3.34 g (17.0 mmol), TFMB 4.64 g (14.5 mmol), HFHA 1.55 g (2.56 mmol), and NMP 50 g were added to a 100 mL four-neck flask, and heated and stirred at 60°C. After 8 hours, it was cooled to produce a varnish.

Example 2 Under a stream of dry nitrogen, add CBDA 3.10 g (15.8 mmol), TFMB 3.55 g (11.1 mmol), HFHA 2.87 g (4.75 mmol), and NMP 50 g in a 100 mL four-neck flask, and heat at 60°C Stir. After 8 hours, it was cooled to produce a varnish.

Example 3 Under a dry nitrogen flow, CBDA 3.52 g (18.0 mmol), TFMB 5.46 g, HFHA 0.54 g (0.90 mmol), and NMP 50 g were added to a 100 mL four-necked flask, and heated and stirred at 60°C. After 8 hours, it was cooled to produce a varnish.

Example 4 Under a stream of dry nitrogen, CBDA 4.00 g (20.4 mmol), m-TB 3.68 g (17.3 mmol), HFHA 1.85 g (3.06 mmol), and NMP 50 g were added to a 100 mL four-necked flask at 60°C Heat and stir. After 8 hours, it was cooled to produce a varnish.

Example 5 Under dry nitrogen flow, CBDA 3.53 g (18.0 mmol), TFMB 4.61 g (14.4 mmol), HFHA 0.54 g (0.90 mmol), 4-ABS-3AP 0.71 g (2.70 mmol) were added to a 100 mL four-necked flask ), NMP 50 g, heated and stirred at 60°C. After 8 hours, it was cooled to produce a varnish.

Example 6 Under a stream of dry nitrogen, CBDA 3.18 g (16.2 mmol), BPF-PA 1.16 g (1.80 mmol), TFMB 5.48 g (17.1 mmol), HFHA 0.54 g (0.90 mmol), NMP 50 g, heated and stirred at 60°C. After 8 hours, it was cooled to produce a varnish.

Example 7 To 50 g of the varnish obtained in Example 1 (concentration 16%) was added 0.4 g (5 parts by mass relative to 100 parts by mass of the polyimide precursor resin) Tinuvin 405 (BASF (Manufactured by BASF), stirring was performed at 30°C for 30 minutes to prepare a varnish.

Example 8 To 50 g (concentration 16%) of the varnish obtained in Example 1, 0.4 g (5 parts by mass relative to 100 parts by mass of the polyimide precursor resin) RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.) was added , Stir at 30°C for 30 minutes to prepare a varnish.

Example 9 To 50 g (concentration 16%) of the varnish obtained in Example 1, 0.4 g (5 parts by mass relative to 100 parts by mass of the polyimide precursor resin) ULS-935 (molecular weight exceeding 1000, lion (Manufactured by Lion Specialty Chemicals Co., Ltd.), the varnish is prepared by stirring at 30°C for 30 minutes.

Example 10 Under a stream of dry nitrogen, PMDA-HS 4.20 g (18.7 mmol), DABA 3.62 g (15.9 mmol), HFHA 1.70 g (2.81 mmol), NMP 50 g were added to a 100 mL four-necked flask at 60°C Heat and stir. After 8 hours, it was cooled to produce a varnish.

Example 11 Under dry nitrogen flow, PMDA-HS 4.21 g (18.8 mmol), DABA 3.62 g (17.8 mmol), HFHA 0.57 g (0.94 mmol), and NMP 50 g were added to a 100 mL four-neck flask at 60°C Heat and stir. After 8 hours, it was cooled to produce a varnish.

Example 12 Under a stream of dry nitrogen, PMDA-HH 4.20 g (18.7 mmol), DABA 3.62 g (15.9 mmol), HFHA 1.70 g (2.81 mmol), and NMP 50 g were added to a 100 mL four-necked flask at 60°C Heat and stir. After 8 hours, it was cooled to produce a varnish.

Example 13 Under a stream of dry nitrogen, add CBDA 3.85 g (19.6 mmol), TFMB 6.16 g (19.2 mmol), HFHA 0.24 g (0.39 mmol), and NMP 50 g in a 100 mL four-neck flask, and heat at 60°C Stir. After 8 hours, it was cooled to produce a varnish.

Example 14 Under a stream of dry nitrogen, CBDA 6.06 g (30.9 mmol), 4,4'-DDS 3.84 g (15.4 mmol), TFMB 4.45 g (13.9 mmol), HFHA 0.93 g (1.55) were added to a 100 mL four-necked flask mmol), NMP 50 g, heated and stirred at 60°C. After 8 hours, it was cooled to produce a varnish.

Example 15 Under dry nitrogen flow, CBDA 6.06 g (30.9 mmol), TFMB 8.41 g (26.3 mmol), HFHA 2.62 g (4.33 mmol), X-22-1660B-3 1.36 g ( 0.31 mmol, a compound represented by general formula (25)), 50 g of NMP, and heating and stirring at 60°C. After 8 hours, it was cooled to produce a varnish.

Example 16 Under a stream of dry nitrogen, CBDA 6.06 g (30.9 mmol), TFMB 7.92 g (24.7 mmol), 4-ABS-3AP 1.48 g (4.33 mmol), and HFHA 0.93 g (1.55 mmol) were added to a 100 mL four-necked flask. ), X-22-1660B-3 1.36 g (0.31 mmol), NMP 50 g, heated and stirred at 60°C. After 8 hours, it was cooled to produce a varnish.

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

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

Comparative example 3 Under dry nitrogen flow, add CBDA 3.05 g (15.6 mmol), TFMB 2.49 g (7.78 mmol), HFHA 4.70 g (7.78 mmol), and NMP 50 g in a 100 mL four-neck flask, and heat at 60°C Stir. After 8 hours, it was cooled to produce a varnish.

Comparative Example 4 BPDA 4.26 g (14.5 mmol), TFMB 3.95 g (12.3 mmol), HFHA 1.31 g (2.17 mmol), and NMP 50 g were added to a 100 mL four-neck flask under dry nitrogen flow, and heated at 60°C Stir. After 8 hours, it was cooled to produce a varnish.

The compositions of the varnishes synthesized in Examples 1 to 16 and Comparative Examples 1 to 4 are shown in Tables 1 to 2. In addition, using these varnishes, the light transmittance (T), in-plane/out-of-plane birefringence, haze value, and 1% thermal weight loss of the polyimide resin film obtained in (1) to (4) were measured Temperature (Td1), coefficient of linear thermal expansion (CTE), glass transition temperature (Tg), residual stress, peeling energy during laser irradiation, evaluation of touch panels, position accuracy of BM, angle dependence of color coordinates of organic EL elements The evaluation results are shown in Table 1 to Table 2.

It can be seen that the polyimide resin has the structural unit of the general formula (1) as the main component, and contains the structure of the general formula (2) at 2 mol% or more and 30 mol% or less, which satisfies the necessary requirements for the support substrate for displays Characteristics, namely high transparency, low CTE, low birefringence, high Tg, all characteristics of laser peeling. Since all these characteristics are satisfied, when the polyimide resin of the embodiment of the present invention is used to produce a touch panel, a color filter, a liquid crystal element, and an organic EL element, good characteristics can be confirmed. In Comparative Example 1, peeling from the glass substrate by laser could not be performed, and therefore the evaluation of the organic EL element could not be performed.

[Table 1]

[Table 2]

Example 17 Implementation of a light resistance test Using the varnish prepared in Example 1 and the polyimide resin film prepared in (3), a light resistance test was performed. The light resistance test was performed according to the method described in (16).

Example 18 A light resistance test was carried out in the same manner as in Example 18 except that the varnish prepared in Example 7 was used.

Example 19 Except that the varnish prepared in Example 8 was used, a light resistance test was carried out in the same manner as in Example 18.

Example 20 Except having used the varnish prepared in Example 9, it carried out similarly to Example 18, and implemented the light resistance test.

The results of the light transmittance (T), haze, coefficient of linear thermal expansion (CTE), elongation at break, and laser peelability of the film before and after the light resistance test described in Example 17 to Example 20 are shown in Table 3 in. It is understood that since the polyimide resins of Examples 7 to 9 contain an ultraviolet absorber, the deterioration of the film before and after the light resistance test is suppressed. Among them, it can be seen that since the polyimide resin films of Examples 7 and 8 have a better structure and a better molecular weight UV absorber, they have good film properties even after the light resistance test.

[table 3]

1‧‧‧Touch panel 2, 32, 42‧‧‧Polyimide resin 3‧‧‧Black frame 4‧‧‧First transparent wiring 5‧‧‧Insulating film 6‧‧‧Leading wiring 7‧‧‧ Second transparent wiring 8‧‧‧Transparent protective film9‧‧‧Gas barrier layer 10‧‧‧Color filter 11‧‧‧Black matrix 12R‧‧‧Red pixel 12G‧‧‧Green pixel 12B‧‧‧ Blue pixel 13‧‧‧Overcoat 14‧‧‧Liquid crystal element 15‧‧‧Pixel electrode 16‧‧‧First alignment film 17‧‧‧Second alignment film 18‧‧‧Counter electrode 19‧‧‧ Liquid crystal layer 20‧‧‧Polarizer 21‧‧‧Organic EL element 22‧‧‧TFT layer 23‧‧‧Planarization layer 24‧‧‧First electrode 25‧‧‧Insulation layer 26R‧‧‧Red organic EL light-emitting layer 26G‧‧‧Green organic EL light-emitting layer 26B‧‧‧Blue organic EL light-emitting layer 27‧‧‧Second electrode

Fig. 1A is a cross-sectional view showing an example of a touch panel including a polyimide resin film according to an embodiment of the present invention. Fig. 1B is a cross-sectional view showing an example of a touch panel including a polyimide resin film according to an embodiment of the present invention. Fig. 2A is a cross-sectional view showing an example of a color filter including a polyimide resin film according to an embodiment of the present invention. Fig. 2B is a cross-sectional view showing an example of a color filter including a polyimide resin film according to an embodiment of the present invention. Fig. 3 is a cross-sectional view showing an example of a liquid crystal element including a polyimide resin film according to an embodiment of the present invention. 4 is a cross-sectional view showing an example of an organic EL element including a polyimide resin film according to an embodiment of the present invention.

Claims (20)

A polyimide resin characterized in that: the structural unit represented by the general formula (1) is used as the main component, and the structural unit represented by the general formula (2) is contained at 2 mol% or more and 30 mol% or less of all the structural units ；

(R ¹ represents a tetravalent organic group with a carbon number of 4 to 40 having a monocyclic or condensed polycyclic alicyclic structure, or an organic group with a monocyclic alicyclic structure directly or through a cross-linking structure. A tetravalent organic group with 4 to 40 carbon atoms; R ² represents a divalent organic group represented by the general formula (3); R ³ represents the following general formula (4) or general formula (5))

(R ⁴ to R ¹¹ each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group with 1 to 3 carbon atoms that can be substituted by a halogen atom; X ¹ is selected from a direct bond, an oxygen atom, a sulfur atom, and a sulfonyl group , Divalent cross-linked structure in a C1-C3 divalent organic group, ester bond, amide bond or thioether bond that can be substituted by halogen atoms)

The polyimide resin as described in item 1 of the scope of patent application, which has the structural unit represented by the general formula (1) as the main component, and contains 5 mol% or more and 30 mol% or less of all the structural units of the general formula (2 ) Represents the structural unit. The polyimide resin as described in item 1 or item 2 of the scope of patent application, wherein R ^{1 in} general formula (1) and general formula (2) is selected from the following general formula (6) to general formula ( 10) More than one of the indicated structures;

(R ¹² to R ⁵⁵ each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group with 1 to 3 carbon atoms that may be substituted with a halogen atom). The polyimide resin as described in item 1 or item 2 of the scope of patent application, wherein R ² in the general formula (1) is one or more selected from the following general formulas (14) to (17) ；

(R ⁵⁶ to R ⁸⁷ each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group with 1 to 3 carbon atoms that may be substituted with a halogen atom). The polyimide resin as described in item 1 or item 2 of the scope of patent application, wherein R ² in the general formula (1) is a structure selected from the following general formulas (18) to (21) More than one of

The polyimide resin as described in item 1 or item 2 of the scope of patent application, which further includes a structural unit represented by general formula (22);

(R ¹ represents a tetravalent organic group with a carbon number of 4 to 40 having a monocyclic or condensed polycyclic alicyclic structure, or an organic group with a monocyclic alicyclic structure directly or through a cross-linking structure. A tetravalent organic group with 4-40 carbon atoms; X ² and X ³ may be the same or different, and are a structure containing an aromatic ring, aliphatic ring, a chain hydrocarbon group or a combination of these, or containing these and selected from A structure of a combination of one or more groups in the group consisting of amide group, ester group, ether group, alkylene group, oxyalkylene group, vinylene group, and halogenated alkylene group). The polyimide resin as described in item 1 or item 2 of the scope of the patent application, wherein the acid dianhydride residue and/or diamine residue constituting the polyimine has the formula (24) structure;

(In the general formula (24), R ⁸⁸ and R ⁸⁹ each independently represent a monovalent organic group having 1 to 20 carbon atoms; m represents an integer of 3 to 200). A polyimide resin composition comprising the polyimide resin described in any one of items 1 to 7 in the scope of patent application, and an ultraviolet absorber. The polyimide resin composition described in item 8 of the scope of patent application, wherein the ultraviolet absorber is a compound with a molecular weight of 1000 or less. The polyimide resin composition according to item 8 or item 9 of the scope of patent application, wherein the ultraviolet absorber is a compound represented by general formula (28) or general formula (29);

(In general formula (28) and general formula (29), R ⁹⁵ to R ¹⁰⁵ each independently represent a hydrogen atom, a hydroxyl group, a monovalent organic group, or a monovalent organic group bonded via an oxygen atom). The polyimide resin composition according to item 8 or 9 of the scope of patent application, wherein the content of the ultraviolet absorber is 0.5 to 10 parts by mass relative to 100 parts by mass of the polyimide resin. A laminate having an inorganic film on a resin film containing the polyimide resin described in any one of items 1 to 7 of the scope of patent application. A touch panel is provided with a resin film containing the polyimide resin according to any one of items 1 to 7 of the scope of patent application. A method for manufacturing a touch panel, which includes the following steps: (1) a step of coating a polyimide precursor resin composition on a support substrate; (2) from the coated polyimide precursor resin The step of removing the solvent in the composition; (3) the polyimide precursor is imidized to obtain the polyimide resin film as described in any one of items 1 to 7 in the scope of the patent application Steps; (4) a step of forming transparent wiring, an insulating film and lead wires on the polyimide resin film; (5) a step of peeling the polyimide resin film from the support substrate. A color filter is provided with a resin film containing the polyimide resin described in any one of items 1 to 7 of the scope of patent application. A method for manufacturing a color filter, which includes the following steps; (1) the step of coating the polyimide precursor resin composition on the support substrate; (2) the step of removing the solvent from the coated polyimide precursor resin composition; (3) the polyimide precursor resin composition The step of obtaining the polyimide resin film according to any one of items 1 to 7 in the scope of the patent application by imidizing the imine precursor; (4) applying the polyimide resin film (5) the step of forming colored pixels on the polyimide resin film; (6) the step of peeling the polyimide resin film from the support substrate. A liquid crystal element provided with a resin film containing the polyimide resin described in any one of items 1 to 7 in the scope of patent application. A method for manufacturing a liquid crystal element, which includes the following steps: (1) the step of coating a polyimide precursor resin composition on a support substrate; (2) a resin composition from the coated polyimide precursor (3) The step of imidizing the polyimide precursor to obtain the polyimide resin film according to any one of items 1 to 7 in the scope of the patent application (4) a step of forming a transparent electrode, an alignment film and a liquid crystal layer on the polyimide resin film; (5) a step of peeling the polyimide resin film from the support substrate. An organic electroluminescence element provided with a resin film containing the polyimide resin described in any one of items 1 to 7 of the scope of patent application. An organic electroluminescence element manufacturing method, which includes the following steps Step; (1) the step of coating the polyimide precursor resin composition on the supporting substrate; (2) the step of removing the solvent from the coated polyimine precursor resin composition; (3) The polyimide precursor is imidized to obtain the polyimide resin film as described in any one of the first to seventh items in the scope of the patent application; (4) the polyimide The step of forming an organic electroluminescence circuit on the resin film; (5) the step of peeling the polyimide resin film from the support substrate.

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