TWI734795B - Photosensitive resin composition, photosensitive sheet, cured film, element, organic EL display device, semiconductor electronic part, semiconductor device, and method of manufacturing organic EL display device - Google Patents

Abstract

The present invention provides a photosensitive resin composition having a high residual film rate after development, high bending resistance in a cured film, and high sensitivity. The photosensitive resin composition of the present invention contains (a) an alkali-soluble resin and (b) a photosensitive compound; wherein the aforementioned (a) alkali-soluble resin has a structure represented by the general formula (1) of 95-100 mol% as a repeat Unit, and at least one of the ends of the polymer molecular chain in the aforementioned (a) alkali-soluble resin has an organic group derived from a monoamine or an acid anhydride:

(In the general formula (1), R ¹ represents a divalent organic group. R ² and R ³ each independently represent hydrogen or an organic group having 1 to 20 carbons. X ¹ and X ² each independently represent a carbon number of 2 to 20 Linear or branched alkylene, 1,3-phenylene or 1,4-phenylene. R ¹ , X ¹ and X ² may be different from each other in multiple repeating units. m and n is an integer in the range of 0~100,000, m+n≧3.)

Description

Photosensitive resin composition, photosensitive sheet, cured film, element, organic EL display device, semiconductor electronic component, semiconductor device, and method of manufacturing organic EL display device

The present invention relates to a photosensitive resin composition. In detail, it relates to a photosensitive resin composition suitable for surface protection films and interlayer insulating films of semiconductor elements, insulating films of organic electroluminescence (EL) elements, and those using organic EL elements. Flattening film of Thin Film Transistor (hereinafter referred to as TFT) substrate for driving of display device, wiring protection insulating film of circuit substrate, on-chip microlense of solid-state imaging element, and various displays/ Applications such as flattening films for solid-state imaging devices.

唑等耐熱性樹脂因具有優良的耐熱性、電絕緣性，而含有該等耐熱性樹脂的感光性樹脂組成物，可使用於LSI等半導體元件的表面保護膜、層間絕緣膜、有機電場元件及有機EL顯示元件的絕緣層、顯示裝置用TFT基板的平坦化膜等。 Polyimide and polybenzo

Since heat-resistant resins such as azoles have excellent heat resistance and electrical insulation, photosensitive resin compositions containing such heat-resistant resins can be used for surface protection films, interlayer insulating films, organic electric field elements, and semiconductor devices such as LSIs. An insulating layer of an organic EL display element, a flattening film of a TFT substrate for a display device, etc.

In recent years, high sensitivity has been required for photosensitive resin compositions in order to shorten the exposure time for reasons such as increasing the size of substrates and improving productivity. In addition, recently, research has been actively conducted to make the display flexible by forming a substrate with an organic thin film. Therefore, the insulating film and the flattening film are also required to have flexibility such as bending resistance.

For example, a positive photosensitive heat-resistant composition that can be developed with an alkaline aqueous solution has been proposed. A photosensitive resin composition has been proposed by using a high-transparency polyamide containing tetracarboxylic anhydride with an alicyclic structure. Imines to achieve high sensitivity (for example, refer to Patent Documents 1 and 2).

In order to achieve high sensitivity, a highly transparent polyimide resin using tetracarboxylic anhydride having a fluorine atom like a hexafluoropropyl group has also been proposed (for example, refer to Patent Documents 3 and 4).

In addition, in order to achieve bending resistance, a photosensitive resin composition using a polyimide using an ester group-bearing tetracarboxylic anhydride has been proposed (for example, refer to Patent Document 5).

Advanced technical literature Patent literature

Patent Document 1 International Publication No. 2000/73853

Patent Document 2 JP 2010-196041 A

Patent Document 3 JP 2007-183388 A

Patent Document 4 JP 2011-202059 A

Patent Document 5 International Publication No. 2011/59089

Summary of the invention

However, as described in Patent Documents 1 and 2, the polyimide resin using a tetracarboxylic anhydride with an alicyclic structure has too high solubility in alkaline developer, so the residual film rate may decrease. .

In addition, as described in Patent Documents 3 and 4, polyimide resins using tetracarboxylic anhydrides having fluorine atoms such as hexafluoropropyl groups have a brittle cured film and it is difficult to form cured films with excellent bending resistance. situation.

In addition, as described in Patent Document 5, a polyimide resin using a tetracarboxylic anhydride having an ester group structure has excellent bending resistance, but the sensitivity may be insufficient.

Therefore, an object of the present invention is to provide a photosensitive resin composition with high residual film rate after development, high bending resistance in the cured film, and high sensitivity.

The present invention is a photosensitive resin composition containing: (a) an alkali-soluble resin, (b) a photosensitive compound; and the aforementioned (a) alkali-soluble resin has 95-100 mol% represented by the general formula (1) Structural unit, and in the aforementioned (a) alkali-soluble resin, at least one of the ends of the polymer molecular chain has an organic group derived from a monoamine or an acid anhydride:

(In the general formula (1), R ¹ is a divalent organic group. R ² and R ³ each independently represent hydrogen or an organic group having 1 to 20 carbons. X ¹ and X ² each independently represent a carbon number of 2 to 20 Linear or branched alkylene, 1,3-phenylene or 1,4-phenylene. R ¹ , X ¹ and X ² may be different from each other in multiple repeating units. m and n is an integer from 0 to 100,000, m+n≧3).

According to the present invention, it is possible to obtain a photosensitive resin composition containing an alkali-soluble resin having high solubility in organic solvents and having high sensitivity/residual film rate and flexibility.

1‧‧‧TFT (Thin Film Transistor)

2‧‧‧Wiring

3‧‧‧TFT Insulation Layer

4‧‧‧Planarization layer

5‧‧‧ITO (transparent electrode)

6‧‧‧Substrate

7‧‧‧Contact hole

8‧‧‧Insulation layer

9‧‧‧Glass substrate

10‧‧‧First electrode (non-transparent electrode)

11‧‧‧Auxiliary electrode

12‧‧‧Insulation layer

13‧‧‧Organic EL layer

14‧‧‧Second electrode (transparent electrode)

Fig. 1 is a cross-sectional view of an example of a TFT substrate.

Fig. 2 is a schematic diagram of an organic EL display device.

The form used to implement the invention <(a) Alkali-soluble resin>

The resin of the present invention is an alkali-soluble resin selected from alkali-soluble polyimine or polyimine precursors or copolymers thereof having a structural unit represented by the above-mentioned general formula (1).

The photosensitive resin composition having (a) an alkali-soluble resin can be preferably used in the manufacture of an organic EL display device.

As for the polyimide precursor, for example, it can be exemplified by combining tetracarboxylic acid, corresponding tetracarboxylic dianhydride or tetracarboxylic acid diester dichloride, etc., with diamine, corresponding diisocyanate compound or trimethyl Those obtained from reactions such as silylated diamines have residues of tetracarboxylic acid and/or its derivatives, and residues of diamine and/or its derivatives. As for the polyimide precursor, for example, polyamide acid, polyamide ester, polyamide or polyisoimide can be cited.

Polyimides include, for example, the reaction of the above-mentioned polyamide, polyamide, polyamide, or polyisoimide by heating or using an acid or alkali, and Those obtained by dehydrating and ring-closing them have residues of tetracarboxylic acid and/or derivatives thereof, and residues of diamine and/or derivatives thereof.

In order to obtain a resin having a structural unit represented by the general formula (1) as a repeating unit, a tetracarboxylic dianhydride containing an ester group can be used. Compared with rigid polyimide having only an imine structure, the free rotation of the polymer main chain becomes easier due to the inclusion of an ester structure, whereby a cured film with high solvent solubility and flexibility can be obtained.

The ester group-containing tetracarboxylic dianhydride is not particularly limited, and a commercially available product or one obtained by a conventionally known production method can be used.

In the general formula (1), X ¹ and X ² are linear or branched alkylene, 1,3-phenylene or 1,4-phenylene having 2 to 20 carbon atoms. It is preferably a linear or branched alkylene group with 2 to 20 carbon atoms. Since the alkylene group can take a variety of three-dimensional configurations, the resin has an alkylene group in the molecular chain to further improve the flexibility of the cured film. From the viewpoint of improving the heat resistance of the resin, it is preferably a linear or branched chain alkylene with 2 to 6 carbons, and more preferably a linear or branched chain with 2 to 4 carbons Alkylene, especially ethylene. From the viewpoint of improving the heat resistance of the resin and the viewpoint of improving the solvent solubility of the resin, X ¹ and X ² in the aforementioned general formula (1) are preferably ethylene, propylene, or butylene. The group, as described above, is more preferably an ethylene group. When X ¹ and X ² are ethylene groups, it is possible to provide a cured film having a particularly excellent balance of heat resistance and flexibility.

Specific examples of the tetracarboxylic dianhydride containing an ester group include: 1,2-ethylenebis(anhydrotrimellitate) (1,2-ethylenebis(anhydrotrimellitate)), 1,3-propylene Base bis (dehydrated trimellitate), 1,4-tetramethylene bis (dehydrated trimellitate), 1,5-pentamethylene bis (dehydrated trimellitate), 1,6 -Hexamethylene bis (dehydrated trimellitate), 1,7-heptamethylene bis (dehydrated trimellitate), 1,8-octamethylene bis (dehydrated trimellitate) , 1,9-Namethylene bis(dehydrated trimellitate), 1,10-decamethylene bis(dehydrated trimellitate), 1,12-dodecamethylene bis(dehydrated trimellitate) Trimellitate), 1,3-phenylene bis(dehydrated trimellitate), 1,4-phenylene bis(dehydrated trimellitate), etc. Among them, from the viewpoint of particularly excellent balance of heat resistance and flexibility, it is preferable to use 1,2-ethylenebis(anhydro trimellitate).

(A) Alkali-soluble resin that can be used in the present invention has 95-100 mol% of the structural unit represented by the general formula (1), so that the solubility to organic solvents is improved, and at the same time, the resin composition can be softened. Sexual improvement. The so-called structural unit is a repeating unit, which means the structure represented by the repeating numbers m and n, respectively, and the structure represented by the repeating numbers m and n may be random or block.

Alkali-soluble resins having the structural unit represented by the general formula (1) of 95-100 mol% can be prepared according to the method of producing known polyimide precursors described later, by relative to 100 mol% of diamine The ingredients are obtained by using 95-100 mol% of ester group-containing tetracarboxylic dianhydride. (a) Alkali-soluble resins can provide resins with excellent flexibility and high bending resistance by having the structural unit represented by the general formula (1) having 95 mol% or more. ^{In addition, X 1} and X ² in the general formula (1) are linear or branched alkylene, 1,3-phenylene or 1,4-phenylene having 2 to 20 carbon atoms , Since any one of them exhibits hydrophobicity, it can provide a resin with a high residual film rate after development. In particular, when (a) the alkali-soluble resin has a structural unit represented by the general formula (1) at 95 mol% or more, a resin with a high residual film rate after development can be provided.

In addition, the (a) alkali-soluble resin that can be used in the present invention may contain a structure derived from other acid dianhydrides in addition to the ester group-containing tetracarboxylic dianhydride within the range that does not reduce the aforementioned characteristics.

For other acid dianhydrides, specifically, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'- Biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2' ,3,3'-benzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl) Propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4- Dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid Acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl) dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl} dianhydride , 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2- Aromatic tetracarboxylic dianhydrides such as bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and acid dianhydrides of the structure represented by the following general formulas (3) and (4), and butane tetra Aliphatic tetracarboxylic dianhydrides such as carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, etc. Two or more of these can also be used.

(In the general formulas (3) and (4), R ¹⁰ represents an oxygen atom, C(CF ₃ ) ₂ , or C(CH ₃ ) _2. R ¹¹ and R ¹² represent a hydrogen atom or a hydroxyl group.)

The (a) alkali-soluble resin of the present invention preferably has a fluorine atom. In the general formula (1), R ¹ is a structure derived from diamine. In the general formula (1), R ^{1 is} preferably an organic group having a fluorine atom. Due to the presence of fluorine atoms, it imparts water repellency to the surface of the film during alkaline development and can inhibit penetration from the surface. Therefore, it is possible to obtain a high residue of tack and processing patterns without development residues in the unexposed area. Photosensitive resin film of film rate.

In order to obtain the anti-penetration effect of the interface and a suitable dissolution rate, in the general formula (1), when ^{the total amount of R 1} is set to 100 mol%, the organic group having fluorine atoms is preferably 30 mol% or more . With such a configuration is introduced in the monomer component of R ^1, using more than 30 mole% of a monomer containing a fluorine atom is introduced. In addition, in order to obtain adhesion to the substrate, the monomer containing fluorine atoms is preferably 90 mol% or less.

For diamines with fluorine atoms, specifically, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2'-bis(trifluoromethyl)-4,4'-diamine Aromatic diamines such as aminobiphenyl, 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine, and a part of the hydrogen atoms of these aromatic rings with carbon number 1~ Compounds substituted with 10 alkyl groups, fluoroalkyl groups, halogen atoms, etc. The resin having the structure represented by the general formula (1) is preferably a resin containing a structure derived from these compounds.

In addition, (a) the alkali-soluble resin of the present invention preferably has a phenolic hydroxyl group. In the general formula (1), R ^{1 is} preferably an organic group having a phenolic hydroxyl group. The phenolic hydroxyl group can obtain moderate solubility in an alkaline developer, and it interacts with the sensitizer to suppress the solubility of the unexposed part, so it is possible to increase the residual film rate and increase the sensitivity. In addition, the phenolic hydroxyl group also contributes to the reaction with the crosslinking agent, so it is also preferable from the viewpoint of obtaining high mechanical properties and chemical resistance.

In the general formula (1), in order to obtain proper solubility in an alkaline developer, when ^{the total amount of R 1} is set to 100 mol%, the organic group having a phenolic hydroxyl group is preferably 30 mol. %above. Such structures are among the monomer components by introducing the R ^1, monomers containing more than 30 mole% of the phenolic hydroxyl group is introduced. More preferably, it is 50 mol% or more. Moreover, in order to improve the residual film rate after development, the monomer containing a phenolic hydroxyl group is preferably 90 mol% or less.

As for the diamines with phenolic hydroxyl groups, specific examples include: bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl), bis(3 -Amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene (bis(3-amino-4-hydroxyphenyl)methylene), bis(3-amino-4 -Hydroxyphenyl) ether, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl)pyridium, 2,2'-bis(trifluoromethyl)-5 , 5'-Dihydroxybenzidine and other diamines containing hydroxyl groups, and compounds in which part of the hydrogen atoms of these aromatic rings are substituted with alkyl groups or fluoroalkyl groups with 1 to 10 carbon atoms, halogen atoms, etc. . The resin having the structure represented by the general formula (1) is preferably a resin containing a structure derived from these compounds.

By using the aforementioned ester group-containing tetracarboxylic dianhydride, phenolic hydroxyl group-containing diamine, and fluorine atom-containing diamine within the above range, a high-residue film without adhesive and development residues during development can be obtained Rate/high sensitivity photosensitive resin composition.

^{In addition, R 1} in the general formula (1) of the present invention may have a structure derived from other diamines in addition to the aforementioned diamines.

For other diamines, "JEFFAMINE" (registered trademark) KH-511, "JEFFAMINE" ED-600, "JEFFAMINE" ED-900, "JEFFAMINE" ED-2003, "JEFFAMINE" EDR-148, "JEFFAMINE" EDR can be mentioned -176, Polyoxypropylene diamine D-200, D-400, D-2000, D-4000 (above trade name, manufactured by HUNTSMAN Co., Ltd.) as aliphatic diamine containing polyethylene oxide group. Among them, when an aliphatic alkanediamine is used, since flexibility is imparted, the elongation at the breaking point is increased, and the elastic modulus is lowered, so that the warpage of the wafer is suppressed, which is preferable. These characteristics are effective in multilayer and thick films. At the time of introduction, the residue derived from aliphatic alkanediamine among all diamine residues is preferably 10 mol% or more, and from the viewpoint of improving heat resistance, it is preferably 50 mol% or less.

In addition, in the range where the heat resistance is not lowered, other diamines may have an aliphatic group having a siloxane structure, so that the adhesion to the substrate can be improved. Specifically, it can be made by copolymerizing bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. at 1-15 mol%者 etc.

Further, as other diamines, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfonate, and bis(3-amino- 4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy ) Biphenyl, bis(3-amino-4-hydroxyphenyl) pyrene, 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine and other hydroxy-containing diamines, 3- Sulfonic acid-4,4'-diaminodiphenyl ether and other sulfonic acid-containing diamines, dimercaptophenylenediamine and other thiol group-containing diamines, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl Sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4 -Aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl) Chrysene, bis(3-aminophenoxyphenyl) chrysene, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl) ether, 1,4 -Bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diamino Biphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3, 3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis( Aromatic diamines such as trifluoromethyl)-4,4'-diaminobiphenyl, and part of the hydrogen atoms of these aromatic rings are alkyl groups or fluoroalkyl groups with 1 to 10 carbon atoms, and halogen atoms And other substituted compounds, cyclohexanediamine, methylene biscyclohexylamine and other alicyclic diamines. These diamines can be used directly or as corresponding diisocyanate compounds or trimethylsilylated diamines. Moreover, these two or more types of diamine components can also be used in combination. From the viewpoint of improving heat resistance, it is preferable to use an aromatic diamine at 50 mol% or more of the entire diamine.

Among them, preferred ones include: 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, bis(4-aminophenoxy) Phenyl) ingot, bis(3-aminophenoxyphenyl) ingot, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl) ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)benzene Base]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2 ,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine or compounds in which these aromatic rings are substituted with alkyl groups or halogen atoms, and the following general formulas (5)~( 10) Diamines with amide groups as shown. These can be used individually or in combination of 2 or more types.

(In the general formulae (5) to (10), R ¹³ represents an oxygen atom, C(CF ₃ ) ₂ , or C(CH ₃ ) _2. R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or a hydroxyl group.)

In addition, the resin having the structure represented by the general formula (1) of the present invention can contain a sulfonic acid group, a thiol group, and the like. By using a resin having a sulfonic acid group and a thiol group appropriately, it becomes a photosensitive resin composition having moderate alkali solubility.

The (a) alkali-soluble resin that can be used in the photosensitive resin composition of the present invention has an organic group derived from a monoamine or an acid anhydride in at least one end of the polymer molecular chain. Here, monoamine and acid anhydride are terminal sealants. By using the terminal sealant, it becomes easy to adjust the photosensitive resin composition to a suitable viscosity. In addition, it has the following effects: inhibiting the hydrolysis of the resin caused by the acid end, and inhibiting the deterioration of the photosensitive agent (ie, the quinonediazide compound) caused by the amine end when the positive photosensitive resin composition is made, and the effect of reducing the When the photosensitive resin composition of the invention is used as a planarization layer and/or an insulating layer of an organic EL display device, it has an effect of improving the long-term reliability of the organic EL display device. The terminal sealing agent preferably has a hydroxyl group, a carboxyl group, or a sulfonic acid group as a substituent, and from the viewpoint of improving heat resistance, a hydroxyl group is more preferred. Since the terminal sealant has a hydroxyl group, a carboxyl group or a sulfonic acid group as a substituent, the solubility of the obtained resin to the alkaline aqueous solution is improved, and a highly sensitive resin can be provided. In addition, since the resin has a hydroxyl group, a carboxyl group or a sulfonic acid group at the terminal, when a positive photosensitive resin composition is made, the quinonediazide compound interacts with the hydrogen bond to make the unexposed part less soluble and can provide A resin with a high residual film rate after development.

The monoamine that can be used in the terminal sealant is not particularly limited, but for the reasons listed below, it is preferably a compound represented by the following general formula (2). By containing a saturated hydrocarbon group or an aromatic hydrocarbon group in a terminal group, the hydrophobicity of a resin becomes high, and when making the photosensitive resin composition mentioned later, the film shrinkage amount at the time of alkaline development can be reduced. Furthermore, since it contains at least one type of group selected from hydroxyl, carboxyl, or sulfonic acid group, moderate solubility with respect to alkaline developer can be obtained, and when a positive photosensitive resin composition is made, quinone is permeated The diazide compound interacts with the hydrogen bond, thereby making the unexposed part less soluble, and can provide a resin with a high residual film rate after development. In addition, since the phenolic hydroxyl group also contributes to the reaction with the crosslinking agent, it is also preferable from the viewpoint of obtaining high mechanical properties and chemical resistance.

(In the general formula (2), R ⁴ represents a saturated hydrocarbon group having 1 to 6 carbon atoms, and r represents 0 or 1. A and B may be the same or different, and represent a hydroxyl group, a carboxyl group or a sulfonic acid group. s and t respectively Represents 0 or 1, based on the viewpoint of improving the solubility of the obtained resin in an alkaline aqueous solution, s+t≧1.)

Preferred examples of the monoamine represented by the above general formula (2) include: 2-aminophenol, 3-aminophenol (MAP), 2-amino-m-cresol, 2-amino-p-cresol , 3-amino-o-cresol, 4-amino-o-cresol, 4-amino-m-cresol, 5-amino-o-cresol, 6-amino-m-cresol, 4-amino-2,3-di Cresol, 4-amino-3,5-xylenol, 6-amino-2,4-xylenol, 2-amino-4-ethylphenol, 3-amino-4-ethylphenol , 2-amino-4-tertiary butylphenol, 2-amino-4-phenylphenol, 4-amino-2,6-diphenylphenol, 4-aminosalicylic acid, 5-amine Salicylic acid, 6-amino salicylic acid, 2-amino benzoic acid, 3-amino benzoic acid, 4-amino benzoic acid, 2-amino m-toluic acid, 3-amino o-toluic acid, 3-amino p-toluic acid, 4-amino m-toluic acid, 6-amino o-toluic acid, 6-amino m-toluic acid, 3-amino benzene sulfonic acid, 4-amino benzene sulfonic acid, 4- Aminotoluene-3-sulfonic acid, etc. You may use these 2 or more types, and you may use together other terminal sealants.

Relative to the structural unit represented by the general formula (1) of 100 mol%, the monoamine introduction ratio used as the end sealant is preferably 10-100 mol%, and more preferably 40-80 mol% . By setting it to 10 mol% or more, preferably 40 mol% or more, the solubility of the obtained resin in organic solvents is improved, and at the same time, the obtained resin can be appropriately adjusted and used to make a photosensitive resin composition Viscosity at time. Also, from the viewpoint of the solubility of the obtained resin in an alkaline aqueous solution and the mechanical strength of the cured film, it is preferably 100 mol% or less, more preferably 80 mol% or less, and more preferably 70 mol% or less .

The acid anhydride that can be used in the terminal sealant is not particularly limited, but from the viewpoint of the heat resistance of the cured film of the photosensitive resin composition using the obtained resin, an acid anhydride having a cyclic structure or an acid anhydride having a cyclic structure is preferred. The acid anhydride of the linking group. Examples include phthalic anhydride, maleic anhydride (MA), nadic acid anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, and the like.

Relative to the structural unit represented by the general formula (1) of 100 mol%, the introduction ratio of the acid anhydride used as the terminal sealant is preferably 10-100 mol%, more preferably 50-100 mol% . By setting it to 10 mol% or more, preferably 50 mol% or more, the solubility of the obtained resin in organic solvents is improved, and at the same time, the obtained resin can be appropriately adjusted and used to make a photosensitive resin composition The viscosity of the object. Moreover, from the viewpoint of the solubility of the obtained resin in an alkaline aqueous solution and the mechanical strength of the cured film, it is preferably 100 mol% or less, and more preferably 90 mol% or less.

The terminal sealant introduced into the resin can be easily detected by the following method. For example, by dissolving the resin into which the terminal sealant is introduced in an acidic solution, it is decomposed into the constituent units of the resin, that is, the amine component and the acid component, and they are measured by gas chromatography (GC) or NMR to easily detect the terminal Sealants. In addition, the resin into which the terminal sealant is introduced can be directly detected by pyrolysis gas chromatography (PGC), infrared spectroscopy, and 13CNMR spectroscopy.

In the general formula (1), m and n represent the repeating number of the structural unit of the resin, and represent the range of 0 to 100,000, but m+n≧3. From the viewpoint of improving the elongation of the obtained resin, m+n is preferably 10 or more. On the other hand, from the viewpoint of the solubility of the photosensitive resin composition containing the obtained resin to an alkaline developer, m+n is 200,000 or less, preferably 1,000 or less, and more preferably 100 or less. In addition, from the viewpoint of reducing the shrinkage during curing, m/n>1 is preferable. Preferably m/n>2, more preferably m/n>4.

The weight average molecular weight of the resin having the structural unit represented by the general formula (1), in terms of polystyrene based on gel permeation chromatography, is preferably 3,000 to 80,000, more preferably 8,000 to 50,000.

The (a) alkali-soluble resin of the present invention can be produced in accordance with a known method for producing polyimide precursors. For example, the following method can be mentioned: (I) a method of reacting an ester group-containing tetracarboxylic dianhydride with a ^{diamine compound having an R 1} group and a terminal sealant, that is, a monoamine, under low temperature conditions; (II) A method of obtaining a diester from a tetracarboxylic dianhydride containing an ester group and an alcohol, and then reacting a ^{diamine compound having an R 1} group and a terminal sealant, that is, a monoamine, in the presence of a condensing agent; (III) ) The diester is obtained by tetracarboxylic dianhydride containing an ester group and an alcohol, and then the remaining two carboxyl groups are chlorinated, and a ^{diamine compound having an R 1} group, a terminal sealant, that is, a monoamine , The method of reaction, etc. Preferably, the resin polymerized by the above method is poured into a large amount of water or a methanol/water mixed liquid, etc., and precipitated, filtered, dried, and isolated. This precipitation operation removes unreacted monomers, or oligomer components such as dimers and trimers, and improves the film properties after thermal curing. In addition, the polyimide obtained by performing the imidization of the polyimide precursor and performing ring closure can be synthesized by the method of a known imidization reaction after the polyimide precursor is obtained. .

Hereinafter, as a preferable example of (I), an example of a method for producing a polyimide precursor will be described. First, the diamine compound having an R ¹ group is dissolved in a polymerization solvent. The ester group-containing tetracarboxylic dianhydride is slowly added to the solution in a molar amount substantially equal to the diamine compound. Use a mechanical stirrer to stir at -20~100°C, preferably 10~50°C for 0.5~100 hours, more preferably 2~24 hours. After adding tetracarboxylic dianhydride, the terminal sealing agent may be added gradually after stirring at a predetermined temperature and a predetermined time, or it may be added all at once and reacted.

The polymerization solvent can dissolve the raw material monomers, that is, tetracarboxylic dianhydrides and diamines, and the type is not particularly limited. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone amides, γ-butyrolactone, γ- Cyclic esters such as valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, carbonates such as ethylene carbonate and propylene carbonate, Glycols such as triethylene glycol, phenols such as m-cresol and p-cresol, acetophenone, 1,3-dimethyl-2-imidazolidinone, cyclobutane, dimethylsulfoxide, etc. Relative to 100 parts by mass of the obtained resin, the polymerization solvent is preferably used in the range of 100 to 1900 parts by mass, more preferably 150 to 950 parts by mass.

唑、聚苯并

唑前驅物、聚醯胺、將丙烯酸予以共聚合而成的丙烯酸聚合物、酚醛清漆樹脂、可溶酚醛樹脂(resol resin)、矽氧烷樹脂、聚羥基苯乙烯樹脂、或在該等導入有羥甲基、烷氧基甲基或環氧基等交聯基而成的樹脂、該等的共聚聚合物等。這樣的樹脂會溶解於氫氧化四甲銨、膽鹼、三乙胺、二甲基胺基吡啶、單乙醇胺、二乙胺乙醇、氫氧化鈉、氫氧化鉀、碳酸鈉等鹼性的水溶液。藉由含有該等鹼可溶性樹脂，則能夠一邊保有耐熱性樹脂被膜的密接性及優良的靈敏度，一邊能夠賦予各鹼可溶性樹脂的特性。在本發明之感光性樹脂組成物所含之樹脂之中，較佳為本發明之(a)鹼可溶性樹脂為30質量%以上。 The photosensitive resin composition of the present invention may contain (a) alkali-soluble resin other than alkali-soluble resin. Specifically, include: alkali-soluble polybenzo

Azole, polybenzo

Azole precursors, polyamides, acrylic polymers obtained by copolymerizing acrylic acid, novolac resins, resol resins, silicone resins, polyhydroxystyrene resins, or introduced in these Resins composed of cross-linked groups such as methylol, alkoxymethyl, or epoxy, copolymers of these, and the like. Such resins are dissolved in alkaline aqueous solutions such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylamine ethanol, sodium hydroxide, potassium hydroxide, and sodium carbonate. By containing these alkali-soluble resins, the characteristics of each alkali-soluble resin can be imparted while maintaining the adhesiveness and excellent sensitivity of the heat-resistant resin film. Among the resins contained in the photosensitive resin composition of the present invention, the (a) alkali-soluble resin of the present invention is preferably 30% by mass or more.

<(b) Photosensitive compound>

The photosensitive resin composition of the present invention contains (b) a photosensitive compound. The photosensitive compound includes (b1) a photoacid generator and (b2) a photopolymerization initiator. (b1) A photoacid generator is a compound that generates an acid by light irradiation and gives the light-irradiated part a characteristic that the solubility of the alkaline aqueous solution is increased. The so-called (b2) photopolymerization initiator refers to the effect of exposure A compound that breaks and/or reacts to generate free radicals.

By containing the (b1) photoacid generator, acid is generated in the light-irradiated part, and the solubility of the light-irradiated part in the alkaline aqueous solution is increased, and a positive relief pattern that dissolves in the light-irradiated part can be obtained. In addition, by containing (b1) a photoacid generator and an epoxy compound or a thermal crosslinking agent described later, the acid generated in the light irradiation part promotes the crosslinking reaction of the epoxy compound and the thermal crosslinking agent, and light irradiation can be obtained. Part of the insoluble negative relief pattern. In addition, by containing (b2) a photopolymerization initiator and a radical polymerizable compound described later, radical polymerization proceeds, and the exposed portion of the film of the resin composition is insolubilized with the alkaline developer, and a negative pattern can be formed.

Examples of (b1) photoacid generators include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts.

Examples of quinonediazide compounds include: quinonediazide-based sulfonic acid bonded to a polyhydroxy compound with an ester, quinonediazide-based sulfonic acid bonded to a polyamine-based compound with a sulfonamide, The sulfonic acid of the quinonediazide is one formed by ester bonding and/or sulfonamide bonding to a polyhydroxypolyamine compound. Preferably, more than 50 mol% of the entire functional groups of the polyhydroxy compounds and polyamine compounds are substituted with quinonediazide. Moreover, it is preferable to contain 2 or more types of (b1) photoacid generators, and a highly sensitive photosensitive resin composition can be obtained.

In the present invention, it is preferable to use any one of 5-naphthoquinonediazidesulfonyl and 4-naphthoquinonediazidesulfonyl for quinonediazide. The 4-naphthoquinone diazide sulfonate compound has absorption in the i-line region of the mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazide sulfonate compound absorbs and extends to the g-line region of the mercury lamp, and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonate compound and a 5-naphthoquinone diazide sulfonate compound according to the wavelength of exposure. In addition, it may also contain a naphthoquinone diazide sulfonyl ester compound having 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group in the same molecule, and 4-naphthoquinone diazide sulfonyl ester compound Sulfonyl azide compound and 5-naphthoquinone sulfonyl diazide compound.

The above-mentioned naphthoquinonediazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinonediazidesulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide compounds, the resolution, sensitivity, and residual film rate will be improved.

(b1) Among the photoacid generators, sulfonium salt, phosphonium salt, and diazonium salt are preferable because they appropriately stabilize the acid component generated by exposure. Among them, aqua salt is preferred. Furthermore, sensitizers etc. can also be contained as needed.

In the present invention, from the viewpoint of increasing sensitivity, the content of (b1) photoacid generator is preferably 0.01 to 50 parts by mass relative to 100 parts by mass of (a) alkali-soluble resin. Among them, the quinonediazide compound is preferably 3-40 parts by mass. In addition, the total amount of sulfonium salt, phosphonium salt, and diazonium salt is preferably 0.5 to 20 parts by mass.

As (b2) the photopolymerization initiator, for example, a benzyl ketal-based photopolymerization initiator, an α-hydroxyketone-based photopolymerization initiator, an α-aminoketone-based photopolymerization initiator, Acyl phosphine oxide-based photopolymerization initiator, oxime ester-based photopolymerization initiator, acridine-based photopolymerization initiator, titanocene-based photopolymerization initiator, benzophenone-based A photopolymerization initiator, an acetophenone-based photopolymerization initiator, an aromatic ketone ester-based photopolymerization initiator, or a benzoate-based photopolymerization initiator is more preferable from the viewpoint of improving the sensitivity during exposure It is α-hydroxyketone-based photopolymerization initiator, α-aminoketone-based photopolymerization initiator, phosphine oxide-based photopolymerization initiator, oxime ester-based photopolymerization initiator, and acridine-based photopolymerization. The initiator or the benzophenone-based photopolymerization initiator is more preferably an α-aminoketone-based photopolymerization initiator, an phosphine oxide-based photopolymerization initiator, and an oxime ester-based photopolymerization initiator Agent.

Examples of the benzyl ketal-based photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one.

As for the α-hydroxyketone-based photopolymerization initiator, for example, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 2-hydroxy-2-methyl -1-Phenylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropane-1-one Or 2-hydroxy-1-[4-[4-(2-hydroxy-2-methylpropanyl)benzyl]phenyl]-2-methylpropan-1-one.

啉基)丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-(N-

啉基)苯基)-丁烷-1-酮、2-二甲基胺基-2-(4-甲基苄基)-1-(4-(N-

啉基)苯基)-丁烷-1-酮或者3,6-雙(2-甲基-2-(N-

啉基)丙醯基)-9-辛基-9H-咔唑。 Regarding the α-aminoketone-based photopolymerization initiator, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-(N-

Linyl) propane-1-one, 2-benzyl-2-dimethylamino-1-(4-(N-

(Alkolinyl)phenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-(N-

(Hydroxy)phenyl)-butan-1-one or 3,6-bis(2-methyl-2-(N-

(Hydroxy)propyl)-9-octyl-9H-carbazole.

As for the phosphine oxide-based photopolymerization initiator, for example, 2,4,6-trimethylbenzyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzyl) Yl)-phenylphosphine oxide or bis(2,6-dimethoxybenzyl)-(2,4,4-trimethylpentyl)phosphine oxide.

Examples of oxime ester-based photopolymerization initiators include: 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2- Dione-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)oxime, 1-[4- (Phenylthio)phenyl)octane-1,2-dione-2-(O-benzyl)oxime, 1-[4-[4-(carboxyphenyl)thio]phenyl]propane- 1,2-Dione-2-(O-acetyl)oxime, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethanone- 1-(O-acetyl)oxime, 1-[9-ethyl-6-[2-methyl-4-[1-(2,2-dimethyl-1,3-dioxolane- 4-yl)methyloxy)benzyl)-9H-carbazol-3-yl)ethanone-1-(O-acetyl)oxime or 1-(9-ethyl-6-nitro- 9H-carbazol-3-yl)-1-[2-methyl-4-(1-methoxypropan-2-yloxy)phenyl]methanone-1-(O-acetyl)oxime .

Examples of the acridine-based photopolymerization initiator include 1,7-bis(acridin-9-yl)-n-heptane.

As for the titanocene-based photopolymerization initiator, for example, bis(η5-2,4-cyclopentadien-1-yl)-bis[2,6-difluoro)-3-(1H-pyrrole- 1-yl)phenyl)titanium(IV) or bis(η5-3-methyl-2,4-cyclopentadien-1-yl)-bis(2,6-difluorophenyl)titanium(IV) .

As for the benzophenone-based photopolymerization initiator, for example, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamine) Base) benzophenone, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, 4-hydroxybenzophenone, alkylated benzophenone, 3,3',4, 4'-Four (tertiary butylperoxycarbonyl) benzophenone, 4-methyl benzophenone, dibenzyl ketone or quinone.

Examples of acetophenone-based photopolymerization initiators include: 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, and 4-tertiary butyldichloroacetophenone , Benzylidene acetophenone or 4-azido benzylidene acetophenone.

The aromatic ketone ester photopolymerization initiator includes, for example, methyl 2-phenyl-2-oxyacetate.

Benzoic acid ester-based photopolymerization initiators include, for example, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid (2-ethyl)hexyl ester, 4-diethyl Ethyl aminobenzoate or methyl 2-benzylbenzoate.

In the present invention, when the total of (a) alkali-soluble resin and (d) radical polymerizable compound described later is 100 parts by mass, the content of (b2) photopolymerization initiator is preferably 0.1 parts by mass or more , More preferably 0.5 part by mass or more, still more preferably 0.7 part by mass or more, particularly preferably 1 part by mass or more. If the content is within the above range, the sensitivity during exposure can be improved. On the other hand, the content is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 17 parts by mass or less, and particularly preferably 15 parts by mass or less. If the content is within the above range, the resolution after development can be improved, and at the same time, a low taper pattern shape can be obtained.

<(c) Solvent>

The photosensitive resin composition of the present invention contains (c) a solvent. Examples of solvents include ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether, Ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate and other esters, ethanol, isopropanol, butanol, Alcohols such as amyl alcohol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, Ketones such as cyclopentanone and diacetone alcohol, N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, Polar aprotic solvents such as dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, and aromatic hydrocarbons such as toluene and xylene. Two or more of these may be contained. Relative to 100 parts by mass of (a) alkali-soluble resin, the content of (c) solvent is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, more preferably 2000 parts by mass or less, more preferably 1500 parts by mass the following.

<(d) Radical polymerizable compound>

The photosensitive resin composition of the present invention may further contain (d) a radical polymerizable compound.

The (d) radical polymerizable compound refers to a compound having a plurality of ethylenically unsaturated double bond groups in the molecule. At the time of exposure, due to the radicals generated from the aforementioned (b2) photopolymerization initiator, the (d) radical polymerizable compound undergoes radical polymerization, and the exposed part of the resin composition film is insoluble in the alkaline developer, so A negative pattern can be formed.

By containing the (d) radical polymerizable compound, UV curing during exposure is promoted, and sensitivity during exposure can be improved. In addition, the crosslinking density after thermal curing is increased, and the hardness of the cured film can be increased.

The (d) radical polymerizable compound is preferably a compound having a (meth)acryloyl group that is easily radically polymerized. From the viewpoint of improving the sensitivity during exposure and the hardness of the cured film, a compound having two or more (meth)acryl groups in the molecule is more preferable. From the viewpoint of improving the sensitivity during exposure and the hardness of the cured film, the double bond equivalent of the (d) radical polymerizable compound is preferably 80 to 400 g/mol.

(D) Radical polymerizable compounds, for example, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, Propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane di(meth)acrylic acid Ester, ethoxylated trimethylolpropane tri(meth)acrylate, two trimethylolpropane tri(meth)acrylate, two trimethylolpropane tetra(meth)acrylate, 1,3 -Butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(methyl) )Acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate , Ethoxylated glycerol tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, neopentaerythritol tetra(meth)acrylate, ethoxylated neopentaerythritol tri(meth)acrylate ) Acrylate, ethoxylated neopentyl erythritol tetra (meth) acrylate, dineopentaerythritol penta (meth) acrylate, dineopentaerythritol hexa (meth) acrylate, three neopentyl erythritol Alcohol seven (meth) acrylate, trineopentaerythritol octa (meth) acrylate, tetraneopentaerythritol nona (meth) acrylate, tetraneopentaerythritol deca (meth) acrylate, five new Pentaerythritol undeca(meth)acrylate, pentaerythritol dodeca(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-( 3-(meth)acryloyloxy-2-hydroxypropoxy)phenyl)propane, 1,3,5-ginseng ((meth)acryloyloxyethyl)isocyanuric acid, 1, 3-bis((meth)acryloyloxyethyl) isocyanuric acid, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]茀, 9 ,9-bis[4-(3-(meth)acryloyloxypropoxy)phenyl]sulfone or 9,9-bis(4-(meth)acryloyloxyphenyl)sulfone or the like The acid modified product, ethylene oxide modified product or propylene oxide modified product. From the viewpoints of increasing the sensitivity during exposure and increasing the hardness of the cured film, preferred are: trimethylolpropane tri(meth)acrylate, two trimethylolpropane tri(meth)acrylate, two third Methylolpropane tetra (meth) acrylate, neopentyl erythritol tri (meth) acrylate, neopentyl erythritol tetra (meth) acrylate, dineopentaerythritol penta (meth) acrylate, two Neopentyl erythritol hexa (meth) acrylate, trine pentaerythritol hepta (meth) acrylate, trine pentaerythritol octa (meth) acrylate, 2,2-bis[4-(3-( (Methyl)acryloxy-2-hydroxypropoxy)phenyl)propane, 1,3,5-ginseng ((meth)acryloxyethyl)isocyanuric acid, 1,3-bis ((Meth)acryloyloxyethyl) isocyanuric acid, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]茀, 9,9- Bis[4-(3-(meth)acryloxypropoxy)phenyl]sulfonate or 9,9-bis(4-(meth)acryloxyphenyl)sulfonate or the like The property, ethylene oxide modified product or propylene oxide modified product is more preferably an acid modified product or ethylene oxide modified product from the viewpoint of improvement in resolution after development. In addition, from the viewpoint of improving the resolution after development, the polybasic carboxylic acid or the polybasic carboxylic anhydride is paired with a compound having two or more glycidoxy groups in the molecule and an ethylenically unsaturated compound. The compound obtained by reacting the compound obtained by the ring-opening addition reaction of the unsaturated carboxylic acid of the double bond group is also preferred.

In the present invention, when the total of (a) alkali-soluble resin and (d) radical polymerizable compound is 100 parts by mass, the content of (d) radical polymerizable compound is preferably 15 parts by mass or more, and more It is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, and particularly preferably 30 parts by mass or more. When the content is within the above range, the sensitivity during exposure can be improved, and at the same time, a pattern shape with low push-out can be obtained. On the other hand, the content is preferably 65 parts by mass or less, more preferably 60 parts by mass or less, still more preferably 55 parts by mass or less, and particularly preferably 50 parts by mass or less. When the content is within the above range, the heat resistance of the cured film can be improved, and a pattern shape with low push-out can be obtained. By making the pattern shape into a low push-up, the driving stability of the completed organic EL panel can be improved.

<(e) Thermal crosslinking agent>

The photosensitive resin composition of the present invention may further contain (e) a thermal crosslinking agent. The so-called thermal crosslinking agent refers to a compound having at least two thermally reactive functional groups including an alkoxymethyl group, a hydroxymethyl group, an epoxy group, and an oxetane group in the molecule. The thermal crosslinking agent crosslinks the (a) alkali-soluble resin or other additive components, and can improve the heat resistance, chemical resistance, and hardness of the thermally cured film.

As for preferred examples of compounds having at least two alkoxymethyl or hydroxymethyl groups, for example, 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 (above, trade name, Honshu Chemical Industry Co., Ltd.) System), NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.) , Which can be obtained from the aforementioned companies.

As for the compound having an epoxy group or an oxocyclobutane group, examples of compounds having two epoxy groups in one molecule include: "Epikote" (registered trademark) 807, "Epikote" 828, "Epikote" 1002, "Epikote" "1750, "Epikote" 1007, YX8100-BH30, E1256, E4250, E4275 (the above trade names, manufactured by Japan Epoxy Co., Ltd.), "Epiclon" (registered trademark) EXA-4880, "Epiclon" EXA-4822, " Epiclon" EXA-9583, HP4032 (the above product name, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), "Epolite" (registered trademark) 40E, "Epolite" 100E, "Epolite" 200E, "Epolite" 400E, "Epolite" 70P, "Epolite" 200P, "Epolite" 400P, "Epolite" 1500NP, "Epolite" 80MF, "Epolite" 4000, "Epolite" 3002 (the above product names, manufactured by Kyoeisha Chemical Co., Ltd.), "Denacol" ( Registered trademark) EX-212L, "Denacol" EX-214L, "Denacol" EX-216L, "Denacol" EX-252, "Denacol" EX-850L (the above product names, manufactured by Nagase Chemical Technology Co., Ltd.), GAN , GOT (the above brand name, manufactured by Nippon Kayaku Co., Ltd.), "Celloxide" (registered trademark) 2021P (trade name, manufactured by DAICEL (Stock)), "Rika Resin" (registered trademark) DME-100, "Rika Resin "BEO-60E (the above product name, manufactured by the New Japan Physical and Chemical Co., Ltd.), etc., can be obtained from each company.

In addition, those with more than 3 epoxy groups include: VG3101L (trade name, manufactured by Printec (stock)), "Tepic" (registered trademark) S, "Tepic" G, "Tepic" P (the above trade names, Nissan Chemical Industry Co., Ltd.), "Epiclon" N660, "Epiclon" N695, HP7200 (the above brand names, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), "Denacol" EX-321L (trade name, Nagase Chemical Technology (Stock) system), NC6000, EPPN502H, NC3000 (the above product name, Nippon Kayaku Co., Ltd.), "Epotot" (registered trademark) YH-434L (brand name, Toto Kasei (stock) system), EHPE-3150 (Trade name, manufactured by DAICEL (Stock)); For compounds with more than two oxetane groups, examples include: OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (The above product name, manufactured by Toagosei Co., Ltd.), "Eternacoll" (registered trademark) OXBP, "Eternacoll" OXTP (the above product name, manufactured by Ube Industries Co., Ltd.), etc., can be obtained from each company.

If the content of the (e) thermal crosslinking agent is 5 parts by mass or more with respect to 100 parts by mass of (a) alkali-soluble resin, the crosslinking density is increased and the chemical resistance is improved, which is preferable. Furthermore, if it is 10 parts by mass or more, higher mechanical properties can be obtained. On the other hand, from the viewpoint of storage stability and mechanical strength of the composition, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and still more preferably 30 parts by mass or less.

<(f) Colorant>

The photosensitive resin composition of the present invention may further contain (f) a colorant.

The so-called (f) colorant is a compound that absorbs light of a specific wavelength, and particularly refers to a compound that colors by absorbing light of the wavelength of visible light (380~780nm).

By containing (f) the coloring agent, the film obtained from the resin composition can be colored and can be imparted with coloring properties that allow light to penetrate the film of the resin composition or reflect light from the film of the resin composition Color to the desired color. In addition, it is possible to impart a light-shielding property that blocks light of a wavelength that is absorbed by the (f) colorant from light penetrating the film of the resin composition or light reflected from the film of the resin composition.

As for the coloring agent (f), a compound that absorbs light of the wavelength of visible light and is colored in white, red, orange, yellow, green, blue, or purple can be mentioned. By combining two or more colors, the desired toning property of the resin composition can be improved. The toning property is to color the light that penetrates the film of the resin composition or the light reflected from the film of the resin composition. The desired color coordinates.

The aforementioned (f) colorant is preferably the (f1) pigment and/or (f2) dye described later.

In addition, the aforementioned (f) coloring agent is preferably (f3) a black agent and/or (f4) a coloring agent other than black.

The so-called (f3) black agent refers to a compound that is colored black by absorbing light of the wavelength of visible light. It can be a pigment or a dye.

By containing (f3) black agent, the film of the resin composition can be blackened, so that the light-shielding property can be improved. Shading. Therefore, it is suitable for light-shielding films such as black matrixes of color filters or black column spacers of liquid crystal displays, or applications that require high contrast by suppressing reflection of external light.

As for the (f3) black agent, from the viewpoint of light-shielding properties, it is preferably a compound that absorbs light of the full wavelength of visible light and is colored black. In addition, a mixture of two or more compounds selected from white, red, orange, yellow, green, blue, or purple is also preferable. By combining these two or more colors, it can be colored in a simulated black, and the light-shielding property can be improved.

In the photosensitive resin composition of the present invention, the aforementioned (f3) black agent preferably contains one or more types of dye mixtures selected from black pigments, black dyes, and two or more colors, and from the viewpoint of light-shielding properties, it is more preferably Contains black pigment.

The so-called (f4) coloring agent other than black refers to a compound that is colored by absorbing light of the wavelength of visible light. That is, the coloring is the aforementioned white, red, orange, yellow, green, blue, or purple coloring agent other than black.

By containing (f3) a black agent and (f4) a coloring agent other than black, it is possible to impart light-shielding properties, coloring properties, and toning properties to the film of the resin composition.

In the photosensitive resin composition of the present invention, the coloring agent other than black (f4) preferably contains a pigment other than black and/or a dye other than black. From the viewpoint of light-shielding, heat resistance, or weather resistance, More preferably, it contains pigments other than black.

In addition to the solvent, the content ratio of the (f) colorant to the solid content of the photosensitive resin composition of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more. If the content ratio is within the above range, the light shielding properties, coloring properties, and toning properties can be improved. On the other hand, the content ratio is preferably 70% by mass or less, more preferably 65% by mass or less, and still more preferably 60% by mass or less. If the content ratio is within the above range, the sensitivity at the time of exposure can be improved.

<(f1) Pigment>

In the photosensitive resin composition of the present invention, the (f) colorant preferably contains (f1) a pigment. Regarding the aspect in which the aforementioned (f) colorant contains the (f1) pigment, it is preferable to contain the (f1) pigment as the aforementioned (f3) black agent and/or (f4) a coloring agent other than black.

The so-called (f1) pigment refers to a compound that colors the object by physically adsorbing the (f1) pigment to the surface of the object, or the surface of the object interacts with the (f1) pigment, and so on. Generally speaking, it is a solvent, etc. Is insoluble. In addition, the coloring system by the (f1) pigment has high concealment properties and is less likely to fade due to ultraviolet rays or the like.

By containing the (f1) pigment, it can be colored into a color with excellent concealability, and the light-shielding property and weather resistance of the film of the resin composition can be improved.

(f1) The number average particle diameter of the pigment is preferably 1 to 1,000 nm, more preferably 5 to 500 nm, and still more preferably 10 to 200 nm. (f1) When the number average particle diameter of the pigment is within the above range, the light-shielding property of the film of the resin composition and (f1) the dispersion stability of the pigment can be improved.

Here, (f1) the number average particle size of the pigment can be measured using a submicron particle size distribution measuring device (N4-PLUS; Beckman Coulter (stock)) or a Zeta potential-particle size-molecular weight measuring device (Zetasizer Nano ZSP; Sysmex (Stock), obtained by measuring the laser scattering (dynamic light scattering method) caused by the Brownian motion of the (f1) pigment in the solution. In addition, the number average particle diameter of the (f1) pigment in the cured film obtained from the resin composition can be obtained by measurement using SEM and TEM. Set the magnification to 50,000 to 200,000 times, and directly measure the number average particle size of the (f1) pigment. When the (f1) pigment is a regular sphere, the diameter of the regular sphere is measured and set as the number average particle diameter. When (f1) the pigment is not a sphere, measure the longest diameter (hereinafter, "major axis diameter") and the longest diameter in the direction perpendicular to the long axis diameter (hereafter, "minor axis diameter"), and set the long axis The biaxial average diameter obtained by averaging the diameter and the minor axis diameter is defined as the number average particle diameter.

As for (f1) pigments, for example, organic pigments or inorganic pigments can be cited.

By containing organic pigments, coloring properties or toning properties can be imparted to the film of the resin composition. In addition, because it is an organic substance, through chemical structure change or functional transformation, it is possible to transmit or block light of a desired specific wavelength, adjust the transmission spectrum or absorption spectrum of the resin composition film, and make Improved toning.

系顏料、硫靛系顏料、二酮吡咯并吡咯系顏料、喹啉黃(quinophthalone)系顏料、士林(threne)系顏料、吲哚啉系顏料、異吲哚啉系顏料、異吲哚啉酮系顏料、苯并呋喃酮系顏料、苝系顏料、苯胺系顏料、偶氮系顏料、次甲基偶氮系顏料、縮合偶氮系顏料、碳黑、金屬錯合物系顏料、色澱(lake)顏料、調色劑(toner)顏料或者螢光顏料。從耐熱性的觀點，較佳為蒽醌系顏料、喹吖啶酮系顏料、皮蒽酮系顏料、二酮吡咯并吡咯系顏料、苯并呋喃酮系顏料、苝系顏料、縮合偶氮系顏料及碳黑。 For organic pigments, for example, phthalocyanine-based pigments, anthraquinone-based pigments, quinacridone-based pigments, pyranthrone-based pigments, two

Pigments, thioindigo pigments, diketopyrrolopyrrole pigments, quinophthalone pigments, threne pigments, indoline pigments, isoindoline pigments, isoindoline Ketone pigments, benzofuranone pigments, perylene pigments, aniline pigments, azo pigments, methine azo pigments, condensed azo pigments, carbon black, metal complex pigments, lakes (lake) pigment, toner (toner) pigment or fluorescent pigment. From the viewpoint of heat resistance, anthraquinone-based pigments, quinacridone-based pigments, pyranthrone-based pigments, diketopyrrolopyrrole-based pigments, benzofuranone-based pigments, perylene-based pigments, and condensed azo-based pigments are preferred. Pigments and carbon black.

Examples of phthalocyanine-based pigments include copper phthalocyanine-based compounds, halogenated copper phthalocyanine-based compounds, or metal-free phthalocyanine-based compounds.

The anthraquinone-based pigments include, for example, aminoanthraquinone-based compounds, diaminoanthraquinone-based compounds, anthrapyrimidine-based compounds, flavanthrone-based compounds, anthanthrone-based compounds, anion An indanthrone-based compound, a pyranthrone-based compound, or a violanthrone-based compound.

The azo pigments include, for example, bisazo compounds or polyazo compounds.

By containing inorganic pigments, coloring properties or toning properties can be imparted to the film of the resin composition. In addition, since it is an inorganic substance, it is more excellent in heat resistance and weather resistance, and can improve the heat resistance and weather resistance of the film of the resin composition.

As for inorganic pigments, for example, titanium oxide, barium carbonate, zirconium oxide, zinc bloom, zinc sulfide, lead white, calcium carbonate, barium sulfate, white carbon, alumina white, silica, kaolin clay, talc, bentonite, Iron oxide red, molybdenum red, molybdenum orange, chrome vermilion, chrome yellow, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, chrome green (viridian), titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine blue, cyan, cobalt blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, cobalt violet, graphite or silver-tin alloy, or titanium, copper, iron, manganese, cobalt, Metal particles, oxides, composite oxides, sulfides, sulfates, nitrates, carbonates, nitrides, carbides, or oxynitrides of metals such as chromium, nickel, zinc, calcium, or silver.

In the photosensitive resin composition of the present invention, the aforementioned (f1) pigment is preferably a benzofuranone-based black pigment and/or a perylene-based black pigment.

Except for the solvent, the content ratio of the (f1) pigment in the solid content of the photosensitive resin composition of the present invention is preferably 5 mass% or more, more preferably 10 mass% or more, and still more preferably 15 mass% or more. If the content ratio is within the above range, the light-shielding property, coloring property, or toning property can be improved. On the other hand, the content ratio is preferably 70% by mass or less, more preferably 65% by mass or less, and still more preferably 60% by mass or less. If the content ratio is within the above range, the sensitivity during exposure can be improved.

<(f2) Dye>

In the photosensitive resin composition of the present invention, the aforementioned (f) colorant preferably contains (f2) dye. Regarding the aspect in which the aforementioned (f) coloring agent contains the (f2) dye, it is preferable to contain the (f2) dye as the aforementioned (f3) black agent and/or (f4) a coloring agent other than black.

The so-called (f2) dye refers to a compound in which the ionic group or hydroxyl group in the dye (f2) chemically adsorbs or strongly interacts with the surface structure of the object to color the object. Generally speaking, Soluble in solvents, etc. In addition, the coloration caused by the dye (f2) is because the molecules are adsorbed to the object one by one, so the coloring power is high and the color rendering efficiency is high.

By containing the dye (f2), it can be colored into a color with excellent tinting power, and the coloring and toning properties of the film of the resin composition can be improved.

For (f2) dyes, for example, direct dyes, reactive dyes, sulfur dyes, vat dyes, acid dyes, metal-containing dyes, metal-containing acid dyes, basic dyes, mordant dyes, acid mordant dyes, disperse dyes, cationic dyes Dyes or fluorescent whitening dyes.

系染料、酞菁系染料、次甲基系染料、

系染料、喹啉系染料、靛系染料、靛類系染料、碳陽離子(carbonium)系染料、士林系染料、紫環酮(perinone)系染料、苝系染料、三芳基甲烷系染料或者二苯并哌喃系染料。從對後述之溶劑的溶解性及耐熱性的觀點來看，較佳為蒽醌系染料、偶氮系染料、吖

系染料、次甲基系染料、三芳基甲烷系染料、二苯并哌喃系染料。 For (f2) dyes, examples include: anthraquinone dyes, azo dyes, acridine

Dyes, phthalocyanine dyes, methine dyes,

Dyes, quinoline dyes, indigo dyes, indigo dyes, carbonium dyes, Shilin dyes, perinone dyes, perylene dyes, triarylmethane dyes or two Benzopyran dyes. From the viewpoints of solubility in solvents and heat resistance described later, anthraquinone dyes, azo dyes, and acridine are preferred.

Dyes, methine dyes, triarylmethane dyes, dibenzopyran dyes.

By containing the dye (f2), it is possible to impart colorability or toning properties to the film of the resin composition.

Except for the solvent, the content ratio of the (f2) dye to the solid content of the photosensitive resin composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more. If the content ratio is within the above range, the colorability or toning properties can be improved. On the other hand, the content ratio is preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less. If the content ratio is within the above range, the heat resistance of the cured film can be improved.

<(g) Dispersant>

The photosensitive resin composition of the present invention may further contain (g) a dispersant.

The so-called (g) dispersant refers to a surface affinity group that can interact with the surface of the aforementioned (f1) pigment or disperse dye, and has a dispersion stabilization that improves the dispersion stability of (f1) pigment or disperse dye. Structure of the compound. (G) The dispersion stabilization structure of the dispersant includes a substituent having a polymer chain and/or electrostatic charge.

By containing (g) a dispersant, when the resin composition contains (f1) a pigment or a disperse dye, the dispersion stability of these can be improved, and the resolution after development can be improved. In particular, for example, when the (f1) pigment is broken into particles having a number average particle diameter of 1 μm or less, the surface area of the (f1) pigment particles is increased, and agglomeration of the (f1) pigment particles is likely to occur. On the other hand, when the (f1) pigment is contained, the surface of the broken (f1) pigment interacts with the surface affinity group of the (g) dispersant. At the same time, due to the dispersion stabilization structure of the (g) dispersant The resulting steric hindrance and/or electrostatic repulsion will hinder the aggregation of the (f1) pigment particles and improve the dispersion stability.

As for the (g) dispersant having a surface affinity group, for example: (g) dispersing agent having only amine value, (g) dispersing agent having amine value and acid value, and (g) dispersing agent having only acid value Or (g) dispersant which does not have any of amine value and acid value. From the viewpoint of improving the dispersion stability of the particles of the pigment (f1), the (g) dispersant having only an amine value and the (g) dispersant having an amine value and an acid value are preferable.

The (g) dispersant having a surface affinity group preferably has an amine group and/or an acidic group which is a surface affinity group, and a structure that forms a salt with an acid and/or a base.

For (g) dispersants with only amine valence, for example, "DISPERBYK" (registered trademark)-108, the same-109, the same-160, the same-161, the same-162, the same-163, and the same-164 , Same-166, Same-167, Same-168, Same-182, Same-184, Same-185, Same-2000, Same-2008, Same-2009, Same-2022, Same-2050, Same-2055, Same -2150, same-2155, same-2163, same-2164, or same-2061, "BYK" (registered trademark)-9075, same-9077, same-LP-N6919, same-LP-N21116 or same-LP- N21324 (any of the above are manufactured by BYK Chemical Japan), "EFKA" (registered trademark) 4015, the same 4020, the same 4046, the same 4047, the same 4050, the same 4055, the same 4060, the same 4080, the same 4300, Same as 4330, same 4340, same 4400, same 4401, same 4402, same 4403 or same 4800 (any of the above are made by BASF), "Ajisper" (registered trademark) PB711 (made by Ajinomoto Precision Technology Co., Ltd.) Or "SOLSPERSE" (registered trademark) 13240, the same 13940, the same 20000, the same 71000 or the same 76500 (any of the above are made by Lubrizol).

For (g) dispersants with amine and acid values, for example, "ANTI-TERRA" (registered trademark) -U100 or the same -204, "DISPERBYK" (registered trademark) -106, the same-140, the same- 142, same-145, same-180, same-2001, same-2013, same-2020, same-2025, same-187 or same-191, "BYK" (registered trademark)-9076 (BYK Chemical Japan (shares) System, "Ajisper" (registered trademark) PB821, the same as PB880 or the same as PB881 (any of the above are manufactured by Ajinomoto Precision Technology Co., Ltd.) or "SOLSPERSE" (registered trademark) 9000, the same 11200, the same 13650, the same 24000, same 32000, same 32500, same 32600, same 33000, same 34750, same 35100, same 35200, same 37500, same 39000, same 56000, or same 76500 (any of the above are made by Lubrizol).

For (g) dispersants with only acid value, for example, "DISPERBYK" (registered trademark)-102, the same-110, the same-111, the same-118, the same-170, the same-171, the same-174, Same-2060 or same-2096, "BYK" (registered trademark)-P104, same-P105 or same-220S (any of the above are manufactured by BYK Chemical Japan (stock)) or "SOLSPERSE" (registered trademark) 3000, The same 16000, the same 17000, the same 18000, the same 21000, the same 26000, the same 28000, the same 36000, the same 36600, the same 38500, the same 41000, the same 41090, the same 53095 or the same 55000 (any of the above are made by Lubrizol).

(G) Dispersants that do not have either amine value or acid value, for example, "DISPERBYK" (registered trademark)-103, same-2152, same-2200 or same-192 (any of the above are BYK Chemical Japan (stock)) or "SOLSPERSE" (registered trademark) 27000, the same 54000 or the same X300 (any of the above are made by Lubrizol).

(G) The amine value of the dispersant is preferably 5 mgKOH/g or more, more preferably 8 mgKOH/g or more, and still more preferably 10 mgKOH or more. When the amine value is within the above range, the dispersion stability of the (f1) pigment can be improved. On the other hand, the amine value is preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less, and still more preferably 100 mgKOH/g or less. If the amine value is within the above range, the storage stability of the resin composition can be improved.

The amine valence referred to here refers to the mass of potassium hydroxide equivalent to the acid reacted per 1 g (g) of the dispersant, and the unit is mgKOH/g. It can be obtained by titrating with an aqueous potassium hydroxide solution after neutralizing 1 g (g) of the dispersant with an acid. From the value of the amine value, the mass of the resin per 1 mol of the amine group, that is, the amine equivalent (in g/mol) can be calculated, and the number of amine groups in the (g) dispersant can be calculated.

(G) The acid value of the dispersant is preferably 5 mgKOH/g or more, more preferably 8 mgKOH/g or more, and still more preferably 10 mgKOH or more. If the acid value is within the above range, the dispersion stability of the (f1) pigment can be improved. On the other hand, the acid value is preferably 200 mgKOH/g or less, more preferably 170 mgKOH/g or less, and still more preferably 150 mgKOH/g or less. If the acid value is within the above range, the storage stability of the resin composition can be improved.

The so-called acid value here refers to the mass of potassium hydroxide reacted with 1g (g) of the dispersant, and the unit is mgKOH/g. It can be obtained by titrating 1 g (g) of the dispersant with a potassium hydroxide aqueous solution. From the value of the acid value, it is possible to calculate the resin mass per 1 mol of acidic groups, that is, the acid equivalent (in g/mol), and to obtain (g) the number of acidic groups in the dispersant.

The (g) dispersants having polymer chains include: acrylic resin-based dispersants, polyoxyalkylene ether-based dispersants, polyester-based dispersants, polyurethane-based dispersants, and polyol-based dispersants. Dispersant, polyethyleneimine-based dispersant or polyallylamine-based dispersant. From the viewpoint of pattern processability in an alkaline developer, acrylic resin-based dispersants, polyoxyalkylene ether-based dispersants, polyester-based dispersants, and polyurethane-based dispersants are preferred. Or polyol-based dispersant.

When the photosensitive resin composition of the present invention contains a disperse dye as the (f1) pigment and/or (f2) dye, the content ratio of the (g) dispersant in the photosensitive resin composition of the present invention is determined by (f1) When the total of the pigment and/or (f2) dye and (g) dispersant is 100% by mass, it is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more. When the content ratio is within the above range, the dispersion stability of the (f1) pigment and/or disperse dye can be improved, and the resolution after development can be improved. On the other hand, the content ratio is preferably 60% by mass or less, more preferably 55% by mass or less, and still more preferably 50% by mass or less. If the content ratio is within the above range, the heat resistance of the cured film can be improved.

<Sensitizer>

The photosensitive resin composition of the present invention may further contain a sensitizer.

The so-called sensitizer refers to the one that absorbs the energy caused by exposure and generates excited triplet electrons through internal conversion and intersystem crossing, which can mediate the aforementioned (b2) photopolymerization initiator, etc. Energy moving compound.

By containing a sensitizer, the sensitivity during exposure can be improved. This is presumably because the sensitizer absorbs long-wavelength light that does not absorb light such as (b2) photopolymerization initiator, and transfers the energy from the sensitizer to (b2) photopolymerization initiator, etc. The movement can improve the efficiency of the photoreaction.

As for the sensitizer, a thioxanthone-based sensitizer is preferable. For thioxanthone-based sensitizers, for example, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone Ketone, 2,4-Diethylthioxanthone or 2,4-Dichlorothioxanthone.

The sensitizer accounts for the content of the photosensitive resin composition of the present invention. When the total of (a) alkali-soluble resin and (d) radical polymerizable compound is 100 parts by mass, it is preferably 0.01 parts by mass or more, and more It is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and particularly preferably 1 part by mass or more. If the content is within the above range, the sensitivity during exposure can be improved. On the other hand, the content is preferably 15 parts by mass or less, more preferably 13 parts by mass or less, still more preferably 10 parts by mass or less, and particularly preferably 8 parts by mass or less. When the content is within the above range, the resolution after development can be improved, and a pattern shape with low push-out can be obtained.

<Chain transfer agent>

The photosensitive resin composition of the present invention may further contain a chain transfer agent.

The so-called chain transfer agent refers to a compound that can accept free radicals from the polymer growth end of a polymer chain obtained by radical polymerization during exposure to mediate the movement of free radicals to other polymer chains.

By containing a chain transfer agent, the sensitivity during exposure can be improved. This is presumed to be because the radicals generated by exposure pass through the chain transfer agent and the radicals move to other polymer chains, whereby the radicals are cross-linked to the deep part of the film. In particular, when the resin composition contains (f3) black agent as the aforementioned (f) colorant, light caused by exposure is absorbed by (f3) black agent, and the light may not reach the deep part of the film. On the other hand, when a chain transfer agent is contained, the radical movement caused by the chain transfer agent enables radical cross-linking to the deep part of the film, so that the sensitivity at the time of exposure can be improved.

In addition, by containing a chain transfer agent, a pattern shape with low push-out can be obtained. This is presumably because the radical movement caused by the chain transfer agent can control the molecular weight of the polymer chain obtained by radical polymerization during exposure. That is, by containing the chain transfer agent, the formation of significant high-molecular-weight polymer chains due to excessive radical polymerization during exposure is inhibited, and the increase in the softening point of the obtained film is suppressed. Therefore, it is considered that the reflowability of the pattern during thermal curing is improved, and a pattern shape with low push-out can be obtained.

As for the chain transfer agent, a mercaptan-based chain transfer agent is preferred. As for the thiol chain transfer agent, for example, β-mercaptopropionic acid, β-mercaptopropionic acid methyl ester, β-mercaptopropionic acid ethyl ester, β-mercaptopropionic acid 2-ethylhexyl ester, β-mercaptopropionic acid N-octyl ester, β-mercaptopropionic acid methoxybutyl ester, β-mercaptopropionic acid stearyl ester, β-mercaptopropionic acid isononyl ester, β-mercaptobutyric acid, β-mercaptobutyric acid methyl ester, β-mercaptobutyric acid Ethyl mercaptobutyrate, 2-ethylhexyl β-mercaptobutyrate, n-octyl β-mercaptobutyrate, methoxybutyl β-mercaptobutyrate, stearyl β-mercaptobutyrate, β-mercapto Isononyl butyrate, methyl thioglycolate, n-octyl thioglycolate, methoxybutyl thioglycolate, 1,4-bis(3-mercaptobutanoyloxy)butane, 1,4 -Bis(3-mercaptopropionyloxy)butane, 1,4-bis(thioethanoloxy)butane, ethylene glycol bis(thioglycolate), trimethylolethane Ginseng (3-mercaptopropionate), trimethylolethane ginseng (3-mercaptobutyrate), trimethylolpropane ginseng (3-mercaptopropionate), trimethylolpropane ginseng (3- Mercaptobutyrate), trimethylolpropane ginseng (thioglycolate), 1,3,5-ginseng [(3-mercaptopropionyloxy) ethyl] isocyanuric acid, 1,3 , 5-Gins [(3-Mercaptobutyryloxy) ethyl] isocyanuric acid, neopentyl erythritol 4 (3-mercaptopropionate), neopentyl erythritol 4 (3-mercaptobutyrate), Neopentylerythritol 4 (thioglycolate), dineopentaerythritol (3-mercaptopropionate), or dineopentaerythritol (3-mercaptobutyrate). From the viewpoints of improved sensitivity during exposure and low push-out pattern shape, 1,4-bis(3-mercaptobutanoyloxy)butane and 1,4-bis(3-mercaptopropanoyloxy) Yl)butane, 1,4-bis(thioglycoloxy)butane, ethylene glycol bis(thioglycolate), trimethylolethane ginseng (3-mercaptopropionate), Trimethylolethane ginseng (3-mercaptobutyrate), trimethylolpropane ginseng (3-mercaptopropionate), trimethylolpropane ginseng (3-mercaptobutyrate), trimethylol Propane ginseng (thioglycolate), 1,3,5-gin [(3-mercaptopropionyloxy) ethyl] isocyanuric acid, 1,3,5-gin [(3-mercaptobutyryl) (Oxy) ethyl) isocyanuric acid, neopentyl erythritol 4 (3-mercaptopropionate), neopentyl erythritol 4 (3-mercaptobutyrate), neopentaerythritol 4 (thioglycolic acid Ester), dineopentaerythritol (3-mercaptopropionate) or dineopentaerythritol (3-mercaptobutyrate).

When the total of (a) alkali-soluble resin and (d) radical polymerizable compound is 100 parts by mass, the content of the chain transfer agent in the photosensitive resin composition of the present invention is preferably 0.01 parts by mass or more, and more It is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and particularly preferably 1 part by mass or more. If the content is within the above range, the sensitivity at the time of exposure can be improved, and a pattern shape with low push-out can be obtained. On the other hand, the content is preferably 15 parts by mass or less, more preferably 13 parts by mass or less, still more preferably 10 parts by mass or less, and particularly preferably 8 parts by mass or less. If the content is within the above range, the resolution after development and the heat resistance of the cured film can be improved.

<Polymerization inhibitor>

The photosensitive resin composition of the present invention may further contain a polymerization inhibitor.

The so-called polymerization inhibitor means that by capturing the free radicals generated during exposure, or the free radicals at the polymer growth end of the polymer chain obtained by radical polymerization during exposure, and holding it in the form of stable free radicals, it can stop. Free radically polymerized compounds.

By containing a polymerization inhibitor in an appropriate amount, the generation of residue after development can be suppressed, and the resolution after development can be improved. This is presumably because the polymerization inhibitor captures excessive free radicals generated during exposure or free radicals at the growth end of the high molecular weight polymer chain, thereby suppressing the progress of excessive free radical polymerization.

As for the polymerization inhibitor, a phenol-based polymerization inhibitor is preferred. As for phenolic polymerization inhibitors, for example, 4-methoxyphenol, 1,4-hydroquinone, 1,4-benzoquinone, 2-tertiary butyl-4-methoxyphenol, 3-tertiary Butyl-4-methoxyphenol, 4-tertiary butylcatechol, 2,6-di-tertiary butyl-4-methylphenol, 2,5-di-tertiary butyl-1, 4-hydroquinone or 2,5-di-tertiary pentyl-1,4-hydroquinone or "IRGANOX" (registered trademark) 1010, the same 1035, the same 1076, the same 1098, the same 1135, the same 1330, the same 1726, Same as 1425, same 1520, same 245, same 259, same 3114, same 565 or same 295 (any of the above are made by BASF).

When the total of (a) alkali-soluble resin and (d) radical polymerizable compound is 100 parts by mass, the content of the polymerization inhibitor in the photosensitive resin composition of the present invention is preferably 0.01 parts by mass or more, and more It is preferably 0.03 part by mass or more, more preferably 0.05 part by mass or more, and particularly preferably 0.1 part by mass or more. If the content is within the above range, the resolution after development and the heat resistance of the cured film can be improved. On the other hand, the content is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less. If the content is within the above range, the sensitivity during exposure can be improved.

<Adhesion Improver>

The photosensitive resin composition used in the present invention may contain an adhesion improving agent. Adhesion modifiers include: vinyl trimethoxy silane, vinyl triethoxy silane, epoxycyclohexyl ethyl trimethoxy silane, 3-glycidoxy propyl trimethoxy silane, 3-condensation Glyceryloxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3- Silane coupling agents such as aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents, compounds obtained by reacting aromatic amine compounds with alkoxy-containing silicon compounds, etc. Two or more of these may be contained. By containing these adhesion modifiers, the adhesion with base substrates such as _{silicon wafers, ITO, SiO 2} , and silicon nitride can be improved when the photosensitive resin film is developed. In addition, it is possible to improve the resistance to oxygen plasma and UV ozone treatments used in washing and the like. The content of the adhesion improving agent is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of (a) alkali-soluble resin.

<Surfactant>

The photosensitive resin composition used in the present invention may contain a surfactant for the purpose of improving the wettability with the substrate or improving the uniformity of the film thickness of the coating film as required. As the surfactant, commercially available compounds can be used. Specifically, polysiloxane-based surfactants include: SH series, SD series, ST series of Toray Dow Corning Polysiloxane, and "BYK" of BYK Chemical Japan. ”Series, Shin-Etsu Polysiloxane’s KP series, Nippon Oil & Fats Corporation’s Disfoam series, Toshiba Polysiloxane’s TSF series, etc.; for fluorine-based surfactants, examples include: Dai Nippon Ink Industry Co.’s "Megafac (registered trademark) )" series, Sumitomo 3M's Fluorad series, Asahi Glass's "Surflon (registered trademark)" series, "Asahi Guard (registered trademark)" series, Shin Akita Chemical's EF series, Omnova Solutions' Polyfox series, etc.; Surfactants containing acrylic and/or methacrylic polymers include: Polyflow series from Kyoeisha Chemical Co., Ltd., and "Disparlon (registered trademark)" series from Kusumoto Chemical Co., Ltd., which can be obtained from each company. But it is not limited to these.

The content of the surfactant is preferably 0.001 part by mass or more and 1 part by mass or less with respect to 100 parts by mass of (a) alkali-soluble resin. By setting it as the above range, defects such as bubbles and pinholes are not generated, and the wettability with the substrate and the film thickness uniformity of the coating film can be improved.

<Compounds with phenolic hydroxyl group>

啉、蒽-1,2,10-三醇、蒽-1,8,9-三醇、8-喹啉酚等。藉由含有該等具有酚性羥基的化合物，所獲得之感光性樹脂組成物，由於曝光前幾乎不溶解於鹼性顯影液，若進行曝光則會容易地溶解於鹼性顯影液的緣故，因顯影所致的膜縮減少，且以短時間進行顯影變得容易。因此，靈敏度變得易提升。 The photosensitive resin composition that can be used in the present invention can contain a compound having a phenolic hydroxyl group for the purpose of supplementing the alkaline developability of the photosensitive resin composition as needed. For example, compounds having a phenolic hydroxyl group include: Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP -EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCRIPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (P-DO-BPA), TrisPHAP, TrisP-PA , TrisP-PHBA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T -OCHP, methylene ginseng-FR-CR, BisRS-26X, BisRS-OCHP, (the above are trade names, can be obtained from Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PCBIR-PC, BIR-PTBP , BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (the above are trade names, which can be obtained from Asahi Organic Materials Industry Co., Ltd.), 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2, 4-dihydroxyquinoline, 2,6-dihydroxyquinoline, 2,3-dihydroxyquinoline

Phyline, anthracene-1,2,10-triol, anthracene-1,8,9-triol, 8-quinolinol, etc. By containing these compounds having phenolic hydroxyl groups, the obtained photosensitive resin composition is almost insoluble in the alkaline developer before exposure, and will easily dissolve in the alkaline developer after exposure. Film shrinkage due to development is reduced, and development becomes easy in a short time. Therefore, the sensitivity becomes easy to improve.

The content of the compound having a phenolic hydroxyl group is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of (a) alkali-soluble resin. By setting it in the above range, in addition to maintaining high heat resistance, the alkaline developability of the photosensitive resin composition can be improved.

<Inorganic particles>

In addition, the photosensitive resin composition that can be used in the present invention can also contain inorganic particles for the purpose of increasing the relative permittivity of the cured film, increasing the hardness, and reducing the coefficient of thermal expansion. Preferred specific examples include silicon oxide, titanium oxide, barium titanate, barium sulfate, barium oxide, zirconium oxide, hafnium oxide, tantalum oxide, tungsten oxide, yttrium oxide, aluminum oxide, and talc. Especially for the purpose of increasing the relative permittivity of the cured film, particularly preferred examples include titanium oxide (εr=115) and zirconium oxide (εr= 30), barium titanate (εr=400) or hafnium oxide (εr=25), but not limited to these. The primary particle size of the inorganic particles is preferably 100 nm or less, more preferably 60 nm or less. The particle size of each inorganic particle is obtained by measuring the length with a scanning electron microscope (Scanning Electron Microscope manufactured by JEOL Ltd., JSM-6301NF). The primary particle size of the inorganic particles that can be used in the present invention can be calculated by measuring the length of 100 particles randomly selected from scanning electron micrographs, and obtaining the arithmetic average.

The content of the inorganic particles is preferably 5 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of (a) alkali-soluble resin. By setting it as the above-mentioned range, in addition to maintaining the alkaline development performance, the effects of the addition of the above-mentioned inorganic particles, such as an increase in the relative dielectric constant, can be exhibited.

<Thermal Acid Generator>

唑環結構時，會促進該等的環化，能夠使硬化膜的機械特性更提升。 The photosensitive resin composition that can be used in the present invention may contain a thermal acid generator. The thermal acid generator generates acid due to heating and promotes the crosslinking reaction of the thermal crosslinking agent. (a) The alkali-soluble resin has an unclosed amide ring structure,

In the case of an azole ring structure, these cyclizations are promoted, and the mechanical properties of the cured film can be further improved.

The thermal decomposition initiation temperature of the thermal acid generator that can be used in the present invention is preferably 50°C to 270°C, more preferably 250°C or less. In addition, if the following is selected: no acid is generated during drying (pre-baking: about 70 to 140°C) after the photosensitive resin composition of the present invention is applied to the substrate, and the subsequent exposure and development are patterned Those that generate acid during the subsequent final heating (curing: about 100 to 400°C) are preferable because they can suppress the decrease in sensitivity during development.

The acid produced from the thermal acid generator that can be used in the present invention is preferably a strong acid. Alkyl sulfonic acids such as acid, butane sulfonic acid, and haloalkyl sulfonic acids such as trifluoromethanesulfonic acid. These are used as salts like onium salts or covalent bond compounds like iminessulfonates. Two or more of these may be contained.

The content of the thermal acid generator that can be used in the present invention is preferably not less than 0.01 parts by mass and not more than 10 parts by mass relative to 100 parts by mass of (a) alkali-soluble resin. By setting it as the said range, in addition to maintaining high heat resistance, the effect by adding the said thermal acid generator can be exhibited.

<(i) Cyclic amide, cyclic urea and their derivatives>

The photosensitive resin composition that can be used in the cured film of the present invention preferably contains one or more compounds selected from the group consisting of (i) cyclic amide, cyclic urea, and derivatives thereof. That is, the cured film of the present invention preferably contains one or more compounds selected from the group consisting of (i) cyclic amide, cyclic urea, and derivatives thereof. Since the cured film contains one or more compounds selected from the group consisting of (i) cyclic amide, cyclic urea, and derivatives thereof, the compound (i) functions as an acid gas quencher It suppresses the decrease in luminescence brightness and pixel shrink, and it is speculated that it becomes possible to provide sufficient long-term reliability as an organic EL device.

One or more compounds selected from the group consisting of (i) cyclic amide, cyclic urea, and derivatives thereof, preferably having a structure represented by the following general formula (11), and may also contain the Wait for more than 2 kinds.

(In the general formula (11), u represents an integer of 1 to 4, and Y represents CH or a nitrogen atom. R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom or an organic group with 1 to 20 carbon atoms.)

One or more compounds selected from the group consisting of (i) cyclic amide, cyclic urea, and derivatives thereof, from the viewpoint of making it easy to remain in the film after heat treatment, the boiling point is preferably Above 210°C. In addition, from the viewpoint of suppressing unevenness during coating, the boiling point is preferably 400°C or lower. When the boiling point cannot be measured under normal pressure, it can be converted to the boiling point under normal pressure using a boiling point conversion table.

Specific examples of cyclic amides, cyclic ureas and their derivatives include: 2-pyrrolidone, N-methyl-2-pyrrolidone (NMP), and N-ethyl-2-pyrrole Pyridone, N-propyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-(tertiary butyl)-2-pyrrolidine Ketone, N-pentyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone Ketone, N-methoxybutyl-2-pyrrolidone, N-(2-hydroxyethyl)-2-pyrrolidone, N-phenyl-2-pyrrolidone, N-vinyl-2- pyrrolidone, N, N '- dimethyl propylene urea, 2-imidazolyl piperidone, 1,3-dimethyl-imidazol-piperidone, 2-piperidone, [epsilon] caprolactam and the like. Among them, N-cyclohexyl-2-pyrrolidone (boiling point: 154°C/7mmHg, when converted to boiling point at normal pressure: 305°C), N-(2-hydroxyethyl)-2-pyrrolidone ( Boiling point: 175°C/10mmHg, when converted to normal pressure boiling point: 313°C), it is preferred because it has a high boiling point and is easy to remain in the membrane after heat treatment.

In the 100% by mass cured film, the total content of one or more compounds selected from the group consisting of (i) cyclic amide, cyclic urea, and derivatives thereof is preferably 0.005% by mass or more and 5% by mass or less . Furthermore, in the photosensitive resin composition forming the cured film, the addition amount of the compound (i) is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of the (a) alkali-soluble resin. It is preferably 15 parts by mass or less, and more preferably 10 parts by mass or less. By setting the addition amount of the compound (i) to 0.1 part by mass or more, the long-term reliability of an excellent organic EL device can be improved, and by setting it to 15 parts by mass or less, pattern formation can be performed with excellent sensitivity.

<Manufacturing method of resin composition>

Next, the manufacturing method of the photosensitive resin composition of this invention is demonstrated. For example, by dissolving the aforementioned components (a) to (c) with thermal crosslinking agents, adhesion modifiers, surfactants, compounds with phenolic hydroxyl groups, inorganic particles, thermal acid generators, etc. as needed, The photosensitive resin composition was obtained. As for the dissolution method, stirring and heating can be mentioned. When heating, the heating temperature is preferably set in a range that does not impair the performance of the photosensitive resin composition, and is usually room temperature to 80°C. In addition, the order of dissolving each component is not particularly limited. For example, there is a method of sequentially dissolving compounds with low solubility. In addition, for surfactants and some adhesion modifiers, components that tend to generate bubbles during stirring and dissolution can be dissolved in other components and then added at the end to prevent poor dissolution of other components due to bubbles.

The obtained photosensitive resin composition is preferably filtered using a filter type filter to remove dust and particles. The pore diameter of the filter includes, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, 0.02 μm, etc., and is not limited to these. The filter material includes polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., preferably polyethylene and nylon.

<Cured film>

Next, the manufacturing method of the cured film using the photosensitive resin composition of this invention is demonstrated in detail. The obtained cured film can be suitably used as a gate insulating layer or an interlayer insulating layer of a thin film transistor.

The method for producing a cured film using the photosensitive resin composition of the present invention includes the steps of: applying the photosensitive resin composition to a substrate to form a photosensitive resin film; and drying the photosensitive resin film The step of exposing the photosensitive resin film; the step of developing the photosensitive resin film after exposure; and the step of heating and curing. The detailed content of each step is described below.

The photosensitive resin composition of the present invention is applied by a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method, etc., to obtain a coating film of the photosensitive resin composition. Among these, the slit coating method is preferably used. Since the slit coating method can be applied with a small amount of coating liquid, it is advantageous in reducing the cost. The amount of coating liquid required for the slit coating method is, for example, about 1/5 to 1/10 when compared with the spin coating method. There are no particular restrictions on the slit nozzle used for coating, and those listed by multiple manufacturers can be used. Specifically, examples include: "Linear Coater" manufactured by Dainippon Krane Manufacturing Co., Ltd., "Spinless" manufactured by Tokyo Ohka Kogyo Co., Ltd., and "Spinless" manufactured by Toray Engineering Co., Ltd. "TS coater", "Table coater" manufactured by Chugai Furnishing Co., Ltd., "CS series" and "CL series" manufactured by Tokyo Electronics Co., Ltd., and "online slit coater" manufactured by Cermatronics Trading Co., Ltd. ", "Head coater HC series" manufactured by Hirata Kiko (Stocks), etc. The coating speed is generally in the range of 10 mm/sec to 400 mm/sec. Although the film thickness of the coating film differs depending on the solid content concentration, viscosity, etc. of the photosensitive resin composition, in general, coating is applied so that the film thickness after drying becomes 0.1 to 10 μm, preferably 0.3 to 5 μm.

Before coating, the substrate on which the photosensitive resin composition is to be coated may be pre-treated with the aforementioned adhesion modifier. For example, it can be used to dissolve 0.5-20 mass in solvents such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate. % Of the adhesion modifier solution to treat the surface of the substrate. The surface treatment methods of the substrate may include spin coating, slot die coating, bar coating, dip coating, spray coating, steam treatment and other methods.

After coating, apply a reduced-pressure drying treatment as needed. Generally, each substrate on which the coating film is formed is dried under reduced pressure. For example, a substrate on which a coating film is formed is placed on a proximity pin arranged in a vacuum chamber, and the vacuum chamber is depressurized to perform decompression drying. At this time, if the substrate and the top plate of the vacuum chamber are separated far away, the air between the substrate and the top plate of the vacuum chamber will flow in a large amount with the reduced pressure drying and become prone to haze and unevenness. . Therefore, it is preferable to adjust the height of the proximity pin to narrow the interval. The distance between the substrate and the top plate of the vacuum chamber is preferably about 2-20 mm, more preferably 2-10 mm.

The vacuum drying speed also depends on the volume of the vacuum chamber, the capacity of the vacuum pump, the pipe diameter between the chamber and the pump, etc. However, for example, in the state of uncoated substrates, set the vacuum chamber to reduce pressure to 40 Pa after 60 seconds. Conditions and so on. The general reduced-pressure drying time is usually from 30 seconds to about 100 seconds, and the ultimate pressure in the vacuum chamber at the end of the reduced-pressure drying is usually 100 Pa or less with the coated substrate. By setting the ultimate pressure to 100 Pa or less, the surface of the coating film can be made into a non-adhesive dry state, thereby suppressing surface contamination and particle generation during subsequent substrate transportation.

After coating or drying under reduced pressure, the coating film is generally heated and dried. This step is also called pre-bake. Drying uses hot plates, ovens, infrared rays, etc. When a hot plate is used, the coating film is directly held on the plate, or the coating film is held on a jig such as a proximity pin already installed on the plate and heated. Proximity pins are made of metal materials such as aluminum and stainless steel, or synthetic resins such as polyimide resin and "Teflon (registered trademark)". As long as they have heat resistance, it does not matter if they are made of any material. Although the height of the proximity pin varies depending on the size of the substrate, the type of coating film, the purpose of heating, etc., it is preferably about 0.1 to 10 mm. The heating temperature varies depending on the type and purpose of the coating film, but it is preferably performed in the range from 50°C to 180°C for 1 minute to several hours.

Next, the method of forming a pattern from the obtained photosensitive resin film is demonstrated. The photosensitive resin film is irradiated with chemical rays through a mask having a desired pattern for exposure. As for the chemical rays that can be used for exposure, there are ultraviolet rays, visible rays, electron rays, X rays, etc. In the present invention, it is preferable to use the i-line (365nm), h-line (405nm), and g-line (436nm) of a mercury lamp. When it has positive photosensitivity, the exposed area will dissolve in the developer. When it has negative photosensitivity, the exposed area will harden and will not dissolve in the developer.

After exposure, a developer is used. When it is a positive type, the exposed portion is removed, and when it is a negative type, the non-exposed portion is removed, thereby forming a desired pattern. As for the developer, when it is either of the positive type or the negative type, it is preferably both: tetramethylammonium hydroxide, diethanolamine, diethylamine ethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate , Triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine , Hexamethylene diamine and other aqueous solutions showing basic compounds. Furthermore, depending on the situation, the following may be added to the alkaline aqueous solution alone or in a combination of multiple: N-methyl-2-pyrrolidone, N,N-dimethylformamide, N , N-dimethyl acetamide, dimethyl sulfide, γ-butyrolactone, dimethyl acrylamide and other polar solvents, methanol, ethanol, isopropanol and other alcohols, ethyl lactate, propylene glycol monomethyl ether Esters such as acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone, etc. As for the development method, it can be spray, puddle, dipping, ultrasonic and other methods.

Secondly, the pattern formed by development is preferably rinsed with distilled water. Here, alcohols such as ethanol and isopropanol, esters such as ethyl lactate, propylene glycol monomethyl ether acetate, etc. can also be added to distilled water for rinsing treatment.

唑前驅物之中的鹼可溶性樹脂、該等的共聚物或該等與聚醯亞胺的共聚物時，由於藉由加熱硬化能夠形成醯亞胺環、

唑環的緣故，能夠使耐熱性及耐藥品性提升，又，當包含至少具有2個烷氧基甲基、羥甲基、環氧基、或氧環丁基的化合物時，藉由加熱硬化能夠使熱交聯反應進行，且能夠使耐熱性及耐藥品性提升。該加熱硬化是選擇溫度且階段性升溫、或者選擇某溫度範圍邊連續地升溫邊實施5分鐘~5小時。作為一例，在150℃、250℃下各進行30分鐘熱處理。或者可舉耗時2小時由室溫直線地升溫至300℃等方法。就本發明中的加熱硬化條件，就使得從硬化膜產生的釋氣量降低之觀點，較佳為300℃以上，更佳為350℃以上。又，就賦予硬化膜充分的膜韌性之觀點，較佳為500℃以下，更佳為450℃以下。 Next, heat curing is performed. Since components with low heat resistance can be removed by heat hardening, heat resistance and chemical resistance can be improved. Especially when the photosensitive resin composition of the present invention contains a precursor selected from polyimide, polybenzo

In the case of alkali-soluble resins, copolymers of these, or copolymers of these with polyimine in the azole precursor, the amide ring can be formed by curing by heating,

Because of the azole ring, heat resistance and chemical resistance can be improved. In addition, when a compound having at least two alkoxymethyl, hydroxymethyl, epoxy, or oxocyclobutyl is included, it is cured by heating The thermal crosslinking reaction can be advanced, and the heat resistance and chemical resistance can be improved. The heat hardening is performed by selecting a temperature and raising the temperature step by step, or selecting a certain temperature range while continuously raising the temperature for 5 minutes to 5 hours. As an example, heat treatment is performed at 150°C and 250°C for 30 minutes each. Alternatively, a method such as linear heating from room temperature to 300°C over 2 hours can be mentioned. With regard to the heat curing conditions in the present invention, from the viewpoint of reducing the amount of outgass generated from the cured film, it is preferably 300°C or higher, and more preferably 350°C or higher. In addition, from the viewpoint of imparting sufficient film toughness to the cured film, it is preferably 500°C or lower, and more preferably 450°C or lower.

Next, the manufacturing method of the cured film using the photosensitive sheet formed from the photosensitive resin composition of this invention is demonstrated. In addition, here, the photosensitive sheet is defined as a sheet obtained by coating a photosensitive resin composition on a peelable substrate and drying it.

When a photosensitive sheet formed from the photosensitive resin composition of the present invention is used, when the photosensitive sheet has a protective film, it is peeled off, and the photosensitive sheet is opposed to the substrate, and is formed by thermocompression bonding. Bonding to obtain a photosensitive resin film. The photosensitive sheet can be obtained by applying the photosensitive resin composition of the present invention to a release substrate, that is, a support film composed of polyethylene terephthalate or the like, and drying it.

The thermocompression bonding can be performed by thermocompression processing, thermal lamination processing, thermal vacuum lamination processing, or the like. The bonding temperature is preferably 40° C. or more from the viewpoint of adhesion to the substrate and embedding properties. In addition, when the photosensitive sheet has photosensitivity, the photosensitive sheet will be hardened during bonding. In order to prevent a decrease in the resolution of pattern formation in the exposure/development step, the bonding temperature is preferably 140°C or less.

The photosensitive resin film obtained by bonding the photosensitive sheet to the substrate can be cured by imitating the step of exposing the above-mentioned photosensitive resin film, the step of developing the exposed photosensitive resin film, and the step of heating and curing membrane.

The cured film obtained by curing the photosensitive resin composition or photosensitive sheet of the present invention can be used for electronic parts such as organic EL display devices, semiconductor devices, and multilayer wiring boards. Specifically, it can be suitably used for insulating layers of organic EL elements, planarization layers of substrates with drive circuits in display devices using organic EL elements, and interlayer insulating films between rewiring of semiconductor devices or semiconductor components , Semiconductor passivation film (passivation film), semiconductor element protective film, interlayer insulating film for high-density mounting multilayer wiring, circuit board wiring protective insulating layer, solid-state imaging element on-chip microlens, and various displays/solid-state imaging Flattening layer for components. Examples of electronic devices having a surface protective film or an interlayer insulating film provided with the cured film of the present invention include MRAM with low heat resistance. That is, the cured film of the present invention is suitable as a surface protection film of MRAM. In addition to MRAM, there are polymer memory (Polymer Ferroelectric RAM: PFRAM) and phase change memory (Phase Change RAM: PCRAM, or Ovonics Unified Memory: OUM) that are expected to be the next-generation memory. Compared with the body, the possibility of using new materials with low heat resistance is also high. Therefore, the cured film of the present invention is also suitable for use as these surface protection films. In addition, it can be used in a display device including a first electrode formed on a substrate and a second electrode provided opposite to the first electrode, specifically, for example, LCD, ECD, ELD, and organic Insulation layer of electroluminescence element display device (organic electroluminescence device) etc. Hereinafter, an organic EL display device will be described as an example.

<Organic EL display device>

The organic EL display device of the present invention has a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, and the planarization layer and/or the insulating layer include the cured film of the present invention. Taking an active matrix display device as an example, a substrate such as a glass or resin film has a TFT, and wiring connected to the side of the TFT and connected to the TFT, and a flattening layer is provided on the substrate so as to cover the unevenness. A display element is arranged on the planarization layer. The display element and the wiring are connected through contact holes formed in the planarization layer. In particular, the flexibility of organic EL display devices has become the mainstream in recent years, and the aforementioned organic EL display device in which the substrate with the drive circuit includes a resin film is preferable. If the cured film formed by curing the photosensitive resin composition or photosensitive sheet of the present invention is used as an insulating layer or a planarizing layer of such a flexible display, it can be used particularly preferably because of its excellent flexibility. From the viewpoint of improving the adhesion with the cured film formed by curing the photosensitive resin composition or photosensitive sheet of the present invention, the resin film is particularly preferably polyimide.

FIG. 1 shows a cross-sectional view of an example of a TFT substrate. On the substrate 6, bottom-gate or top-gate TFTs (Thin Film Transistors) 1 are arranged in a matrix, and an insulating layer 3 is formed in a state of covering the TFTs 1. In addition, a wiring 2 connected to the TFT 1 is provided on the insulating layer 3. Furthermore, a planarization layer 4 is provided on the insulating layer 3 in a state where the wiring 2 is buried. The planarization layer 4 is provided with a contact hole 7 reaching the wiring 2. Then, through the contact hole 7, ITO (transparent electrode) 5 is formed on the planarization layer 4 in a state of being connected to the wiring 2. Here, ITO5 is an electrode of a display element (for example, an organic EL element). Then, the insulating layer 8 is formed so as to cover the periphery of the ITO5. The organic EL element may be a top emission type that emits light from the side opposite to the substrate 6 or a bottom emission type that emits light from the side of the substrate 6. In this way, an active matrix organic EL display device in which TFT1 for driving each organic EL element is connected to it can be obtained.

Such insulating layer 3, planarization layer 4, and/or insulating layer 8, as described above, can be formed by the following steps: a step of forming a photosensitive resin film containing the resin composition or resin sheet of the present invention; The step of exposing the aforementioned photosensitive resin film; the step of developing the exposed photosensitive resin film; and the step of heating the developed photosensitive resin film. The organic EL display device can be obtained by the manufacturing method having these steps.

In addition, the photosensitive resin composition of the present invention can also be suitably used in a fan-out wafer level package (fan-out WLP (fan-out WLP)). Fan-out WLP is a type of semiconductor package that uses sealing resin such as epoxy resin to provide an expansion part around the semiconductor chip, rewiring is applied from the electrode on the semiconductor chip to the expansion part, and solder balls are also mounted on the expansion part , To ensure the required number of terminals. In the fan-out WLP, wiring is provided so as to straddle the boundary line formed by the main surface of the semiconductor wafer and the main surface of the sealing resin. That is, an interlayer insulating film is formed on a substrate composed of two or more materials of a semiconductor wafer to which metal wiring is applied and a sealing resin, and wiring is formed on the interlayer insulating film. In addition, in the semiconductor package of the type in which the semiconductor wafer is embedded in the recess formed in the glass epoxy substrate, wiring is provided so as to straddle the boundary line between the main surface of the semiconductor wafer and the main surface of the printed circuit board. In this aspect, an interlayer insulating film is also formed on a substrate made of two or more materials, and wiring is formed on the interlayer insulating film. The cured film formed by curing the photosensitive resin composition of the present invention has high adhesion to semiconductor wafers to which metal wiring is applied, and also has high adhesion to sealing resins such as epoxy resins, so it can be suitably used as a device An interlayer insulating film on a substrate made of two or more materials.

[Example]

The present invention will be described in the following examples, but the present invention is not limited by these examples. In addition, the evaluation of the photosensitive resin composition in the Example was performed by the following method.

<Method of measuring film thickness>

Using Lambda Ace STM-602 manufactured by Dainippon Crein Co., Ltd., the film thickness after pre-baking, development, and curing was measured with polyimide as the target and refractive index 1.629.

<Measurement of the number average particle size of the pigment>

Using a Zeta potential-particle size-molecular weight measuring device (Zetasizer Nano ZSP; manufactured by Sysmex Co., Ltd.), and using PGMEA as a dilution solvent, dilute the pigment dispersion to a concentration of 1.0×10 ^-5 to 40% by volume, and dilute the solvent The refractive index of PGMEA was set to PGMEA, the refractive index of the measurement object was set to 1.8, and laser light with a wavelength of 633 nm was irradiated to measure the number average particle size of the pigment in the pigment dispersion.

(1-1) Sensitivity evaluation of positive photosensitive resin composition

The photosensitive resin composition (varnish) produced in the Examples and Comparative Examples was spin-coated on an 8-inch silicon wafer, and then developed using a hot plate at 120°C (using a coating and development made by Tokyo Electronics Co., Ltd.) Device Act-8) baked for 3 minutes to produce a pre-baked film with a thickness of 2.5 μm. Using an i-line stepper (stepper) (NIKON NSR i9) in an exposure amount 0 ~ 1000mJ / cm ² of the film was 10mJ / cm ² exposure step to come. After exposure, develop with a 2.38% by mass tetramethylammonium (TMAH) aqueous solution (manufactured by Mitsubishi Gas Chemical Co., Ltd., ELM-D) for 90 seconds, and then rinse with pure water to obtain a development with an isolated pattern of 10 μm Membrane A.

Use an FPD inspection microscope (MX-61L; Olympus (Olympus) Co., Ltd.) to observe the analysis pattern of the developed film. The 10μm line and space pattern is formed into a width of 1:1. The exposure level (called the optimal exposure level Eop) is set to the sensitivity.

(1-2) Sensitivity evaluation of negative photosensitive resin composition

After coating the photosensitive resin composition (varnish) produced in the Examples and Comparative Examples on the ITO substrate by spin coating using a spin coater (MS-A100; Mikasa (manufactured by Mikasa)) at an arbitrary rotation speed , Using a hot plate (SCW-636; manufactured by Dainippon Crein Co., Ltd.), pre-baked at 100°C for 120 seconds to produce a pre-baked film with a film thickness of about 2.0 μm. Use the double-sided alignment single-sided exposure device (mask aligner (mask aligner) PEM-6M; manufactured by UNION Optical Co., Ltd.) to pass the pre-baked film through the grayscale mask (MDRM) used for sensitivity measurement. MODEL 4000-5-FS; manufactured by Opto-Line International), the i-line (wavelength: 365nm), h-line (wavelength: 405nm), and g-line (wavelength: 436nm) of an ultra-high pressure mercury lamp were patterned and exposed. After exposure, using a small developing device for photolithography (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), developed with 2.38% by mass TMAH aqueous solution for 60 seconds and rinsed with water for 30 seconds to produce a development with an isolated pattern of 10 μm membrane.

Using an FPD inspection microscope (MX-61L; manufactured by Olympus Co., Ltd.), observe the analysis pattern of the developed film, and set the 10μm line and space pattern into a 1:1 width of exposure (called Set the sensitivity for the best exposure (Eop).

(2) Evaluation of residual film rate

Set the ratio of the developed film to the film thickness of the pre-baked film as the residual film rate (residual film rate=(film thickness of the developed film)/(film thickness of the pre-baked film)×100), and set 80% or more as qualified .

(3) Evaluation of bendability

After applying the varnish to the PI film substrate by spin coating using a spin coater (MS-A100; manufactured by Mikasa) at an arbitrary rotation speed, a hot plate (SCW-636; manufactured by Dainippon Crein Co., Ltd.) is used ) Pre-baked at 120°C for 120 seconds to produce a pre-baked film with a thickness of approximately 3.0 μm. Using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.), the pre-baked film was heated to 250°C at an oxygen concentration of 20 ppm or less at 5°C/min, and heated at 250°C for 1 hour. The cured film of the composition was produced.

After thermal curing, the PI film substrate with the cured film produced was cut out to a length of 50 mm × a width of 10 mm. The surface of the cured film was set to the outside, and the PI film substrate was held on a line 25 mm in length and bent at 180° for 30 seconds. After 30 seconds, the bent PI film substrate was opened, and the bent portion on the 25mm line of the cured film surface was observed using an FPD inspection microscope (MX-61L; manufactured by Olympus Co., Ltd.), and the cured film surface was evaluated. The appearance changes. The case where the cured film was not peeled from the PI film substrate and there was no appearance change such as cracks or deformation on the cured film surface was regarded as pass (A), and the other cases were regarded as unacceptable (B).

(4) Long-term reliability evaluation of organic EL display devices

A schematic diagram of the manufacturing process of the organic EL display device is shown in FIG. 2. First, a 10 nm transparent conductive film of ITO is formed on the entire surface of the substrate on a 38 mm×46 mm alkali-free glass substrate 9 by a sputtering method, and the first electrode 10 is etched. At the same time, an auxiliary electrode 11 for taking out the second electrode is also formed. The obtained substrate was ultrasonically cleaned with Semicoclean 56 (trade name, manufactured by FURUCHI Chemical Co., Ltd.) for 10 minutes, and then cleaned with ultrapure water. Next, the entire surface of the substrate was coated with the photosensitive resin composition shown in Table 2 by a spin coating method, and prebaked on a hot plate at 120°C for 2 minutes. After UV exposure of the film through a photomask, it was developed with a 2.38% by mass TMAH aqueous solution to dissolve unnecessary parts and rinsed with pure water. Using a high temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.), the obtained resin pattern was subjected to heat treatment at 250° C. for 1 hour in a nitrogen atmosphere. In this way, openings with a width of 70 μm and a length of 260 μm are arranged with a pitch of 155 μm in the width direction and a pitch of 465 μm in the length direction. The exposed shape of the first electrode. In this way, an insulating layer with an opening ratio of 25% of the insulating layer is formed in the effective area of the square substrate with a side of 16mm. The thickness of the insulating layer is about 1.0 μm.

Next, after performing a nitrogen plasma treatment as a pretreatment, an organic EL layer 13 including a light-emitting layer is formed by a vacuum evaporation method. In addition, the degree of vacuum during vapor deposition is 1×10 ^-3 Pa or less, and the substrate is rotated relative to the vapor deposition source during vapor deposition. First, a 10nm compound (HT-1) was vapor-deposited as a hole injection layer, and a 50nm compound (HT-2) was vapor-deposited as a hole transport layer. Next, on the light-emitting layer, the compound (GH-1) as the host material and the compound (GD-1) as the dopant material were vapor-deposited to a thickness of 40 nm so that the doping concentration became 10%. Next, the compound (ET-1) and the compound (LiQ), which are electron transport materials, are laminated with a volume ratio of 1:1 to a thickness of 40 nm. The structure of the compound used in the organic EL layer is shown below.

Next, after the 2nm compound (LiQ) was vapor-deposited, Mg and Ag were vapor-deposited 10nm at a volume ratio of 10:1 to form the second electrode (transparent electrode) 14. In the end, an epoxy resin adhesive is used in a low-humidity nitrogen environment, and a cap-shaped glass plate is bonded to seal, and four organic ELs of the top emission type with a square shape of 5 mm on one side are fabricated on a single substrate. Display device. Furthermore, the film thickness referred to here is the value displayed in a crystal oscillation film thickness monitor.

The produced organic EL display device was placed on a hot plate heated to 80° C. so that the light-emitting surface was irradiated with UV light having a ^{wavelength of 365 nm and an illuminance of 0.6 mW/cm 2.} Immediately after irradiation (0 hours), after 250 hours, 500 hours, and 1000 hours, the organic EL display device was driven to emit light by a DC drive of 0.625 mA, and the area ratio of the light-emitting part relative to the area of the light-emitting pixel was measured ( Pixel light-emitting area rate). Based on this evaluation method, if the pixel light-emitting area ratio after 1000 hours has passed is 80% or more, it can be said that the long-term reliability is excellent, and it is better if it is 90% or more.

The names of the abbreviations of acid dianhydrides, diamines, and other reagents shown in the following Examples and Comparative Examples are as follows.

6FDA: 4,4’-hexafluoroisopropylenediphthalic dianhydride

ABP: 2-amino-4-tertiary butyl phenol

BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

Bk-S0100CF: "IRGAPHOR" (registered trademark) BLACK S0100CF (made by BASF; benzofuranone-based black pigment with a primary particle size of 40 to 80 nm)

BIS-AT-AF: 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane

CBDA: Cyclobutane tetracarboxylic dianhydride

DAE: 4,4’-diaminodiphenyl ether

DFA: N,N-dimethylformamide dimethyl acetal

DPHA: "KAYARAD" (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd.; dineopentaerythritol hexaacrylate)

MA: Maleic anhydride

MAP: 3-aminophenol; m-aminophenol

MBA: 3-Methoxy-n-Butyl Acetate

NCI-831: "Adeka arc Luz" (registered trademark) NCI-831 (manufactured by ADEKA (stock); 1-(9-ethyl-6-nitro-9H-carbazol-3-yl)-1-[2 -Methyl-4-(1-methoxypropan-2-yloxy)phenyl)methanone-1-(O-acetyl)oxime)

NMP: N-methyl-2-pyrrolidone

S-20000: "SOLSPERSE" (registered trademark) 20000 (manufactured by Lubrizol; polyether-based dispersant)

SiDA: 1,1,3,3-tetramethyl-1,3-bis(3-aminopropyl)disiloxane

TFM-DHB: 2,2’-bis(trifluoromethyl)-5,5’-dihydroxybenzidine

TMEG: 1,2-ethylenebis(anhydro trimellitate).

It is shown below: the alkoxymethyl-containing thermally crosslinkable compound (e-1), NIKALAC MX-270(e-2), VG-3101L(e-3) used in each example and comparative example And the phenolic compound BisP-AF (h-1).

<Synthesis Example 1 Synthesis of hydroxyl-containing diamine compound (α)>

18.3 g (0.05 mol) of BAHF was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15°C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzyl chloride in 100 mL of acetone was dropped here. After completion of the dropping, the reaction was carried out at -15°C for 4 hours, and then returned to room temperature. The precipitated white solid was separated by filtration, and vacuum dried at 50°C.

30 g of the obtained white solid was put into a 300 mL stainless steel autoclave, and dispersed in 250 mL of methyl ceroxu, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here with a balloon, and the reduction reaction was carried out at room temperature. After about 2 hours, confirm that the balloon is no longer deflated, and then let the reaction end. After the reaction, the catalyst was filtered to remove the palladium compound, and it was concentrated by a rotary evaporator to obtain a hydroxyl-containing diamine compound (α) represented by the following formula. The obtained solid is directly used in the reaction.

<Synthesis Example 2 Synthesis of Quinonediazide Compound (b1-1)>

烷中，並使為室溫。把與50g之1,4-二

烷混合的15.18g三乙胺， 以使得系統內不會成為35℃以上的方式滴下於此。滴下後，在30℃下攪拌2小時。濾過三乙胺鹽，將濾液投入至水中。其後，利用過濾收集析出的沈澱。利用真空乾燥機使該沈澱乾燥，獲得以下述式表示的醌二疊氮化合物(b1-1)。 Under a stream of dry nitrogen, 21.22g (0.05mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 26.86g (0.10mol) of 5-naphthoquinone diazidesulfonyl chloride, 13.43g (0.05 Mol) 4-naphthoquinone diazide sulfonyl chloride dissolved in 50g 1,4-bis

In alkane, and allowed to room temperature. Put and 50g of 1,4-two

15.18 g of triethylamine mixed with alkane is dropped here so that the system does not become 35°C or higher. After dripping, it stirred at 30 degreeC for 2 hours. The triethylamine salt is filtered, and the filtrate is poured into water. After that, the deposited precipitate was collected by filtration. The precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (b1-1) represented by the following formula.

<Synthesis Example 3 Synthesis of Quinonediazide Compound (b1-2)>

烷中，並使為室溫。使用已與50g之1,4-二

烷混合的15.18g三乙胺，與合成例2同樣地進行而獲得了以下述式所表示的醌二疊氮化合物(b1-2)。 Under a stream of dry nitrogen, 15.31 g (0.05 mol) of TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 40.28 g (0.15 mol) of 5-naphthoquinone diazide sulfonate chloride were dissolved in 450 g of 1 ,4-two

In alkane, and allowed to room temperature. Used with 50g of 1,4-two

15.18 g of triethylamine mixed with alkane was carried out in the same manner as in Synthesis Example 2 to obtain a quinonediazide compound (b1-2) represented by the following formula.

<Synthesis Example 4 Synthesis of Quinonediazide Compound (b1-3)>

烷中，並使為室溫。使用已與50g之1,4-二

烷混合之20.24g三乙胺，與合成例2同樣地進行而獲得以下述式所表示之醌二疊氮化合物(b1-3)。 Under a stream of dry nitrogen, 28.83 g (0.05 mol) of TekP-4HBPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 13.43 g (0.125 mol) of 5-naphthoquinone diazide sulfonate chloride were dissolved in 450 g of 1 ,4-two

In alkane, and allowed to room temperature. Used with 50g of 1,4-two

20.24 g of triethylamine mixed with alkane was carried out in the same manner as in Synthesis Example 2 to obtain a quinonediazide compound (b1-3) represented by the following formula.

[Example 1]

Under a stream of dry nitrogen, 15.11 g (0.025 mol) of the hydroxyl-containing diamine compound (α) obtained in Synthesis Example 1, 3.66 g (0.01 mol) of BAHF, and 0.62 g (0.0025 mol) of SiDA were dissolved in 200g of NMP. 20.51 g (0.05 mol) of TMEG was added together with 50 g of NMP, and stirred at 40°C for 1 hour. Then, 2.73 g (0.025 mol) of MAP was added as a terminal sealing agent, and it stirred at 40 degreeC for 1 hour. Thereafter, the solution diluted with 11.9 g (0.1 mol) of DFA with 5 g of NMP was dropped over a period of 10 minutes, and after the dropping, stirring was continued for 1 hour at 40°C. After the stirring, the solution was poured into 2L of water, and the solid precipitate was collected by filtration. Furthermore, washing was performed 3 times with 2 L of water, and the collected polymer solid was dried in a vacuum dryer at 50°C for 72 hours to obtain a polyamide resin (A).

Add 10 g of the obtained resin (A), 3.0 g of the quinonediazide compound (b1-1) obtained in Synthesis Example 2, and 1.0 g of the alkoxymethyl-containing thermal crosslinking agent (e-1) to 50 g of GBL was obtained and varnish A1 of the positive photosensitive resin composition was obtained. Using the obtained varnish A1, sensitivity evaluation, residual film rate evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device were performed as described above. The evaluation results are shown in Table 2.

[Example 2]

In addition to changing 3.66g (0.01 mol) of BAHF to 3.62g (0.01 mol) of BIS-AT-AF, and changing the MAP of 2.73g (0.025 mol) as an end sealant to 4.13g (0.025 mol) Except for the ABP of ear), the same procedure as in Example 1 was carried out to obtain a polyamide resin (B).

Add 10 g of the resin (B) obtained, 3.0 g of the quinonediazide compound (b1-2) obtained in Synthesis Example 3, and 0.5 g of the cross-linking agent NIKALAC MX-270 (e-2) to 50 g of GBL And the varnish B1 of the positive photosensitive resin composition was obtained. Using the obtained varnish B1, evaluations of sensitivity evaluation, residual film rate evaluation, bendability, and long-term reliability evaluation of the organic EL display device were performed as described above. The evaluation results are shown in Table 2.

[Example 3]

Under a stream of dry nitrogen, 15.56 g (0.0425 mol) of BAHF and 0.62 g (0.0025 mol) of SiDA were dissolved in 100 g of NMP. 20.51 g (0.05 mol) of TMEG and 10 g of NMP were added here, and reacted at 60°C for 1 hour. After that, 1.09 g (0.01 mol) of MAP was added as a terminal sealant, and further stirring was continued for 1 hour at 60°C. Then, it was stirred at 180°C for 4 hours, and after the completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and dried with a vacuum dryer at 50° C. for 72 hours to obtain a powder of the ring-closed polyimide resin (C).

10g of the resin (C) obtained, 3.0g of the quinonediazide compound (b1-1), 1.0g of the alkoxymethyl-containing thermal crosslinking agent (e-1), 1.0g of the phenol compound BisP-AF ( h-1) It is added to 50 g of GBL to obtain varnish C1 of the positive photosensitive resin composition. Using the obtained varnish C1, evaluations of sensitivity evaluation, residual film rate evaluation, bendability, and long-term reliability evaluation of the organic EL display device were performed as described above. The evaluation results are shown in Table 2.

[Example 4]

Except that 15.56g (0.0425 mol) of BAHF was changed to 10.98g (0.03 mol), 1.09g (0.01 mol) of MAP was changed to 1.65g (0.01 mol) of ABP, and 6.05g (0.01 mol) was added ) Except for the hydroxyl-containing diamine compound (α), the same procedure as in Example 3 was carried out to obtain a closed ring polyimide resin (D).

10 g of the obtained resin (D), 3.0 g of quinonediazide compound (b1-1), and 1.0 g of cross-linking agent VG-3101L (e-3) were added to 50 g of GBL to obtain a positive photosensitive resin composition Varnish D1. Using the obtained varnish D1, sensitivity evaluation, residual film rate evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device were performed as described above. The evaluation results are shown in Table 2.

[Example 5]

Under a stream of dry nitrogen, 11.9 g (0.0325 mol) of BAHF, 5.43 g (0.015 mol) of BIS-AT-AF, and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP. 15.39 g (0.0375 mol) of TMEG and 10 g of NMP were added here, and reacted at 60°C for 1 hour. Thereafter, 2.45 g (0.025 mol) of MA was added as a terminal sealing agent, and further stirring was continued at 60°C for 1 hour. Then, it was stirred at 180°C for 4 hours, and after the completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried with a vacuum dryer at 50°C for 72 hours to obtain a closed ring polyimide resin (E).

10g of the obtained resin (E), 3.0g of quinonediazide compound (b1-2), and 1.0g of alkoxymethyl-containing thermal crosslinking agent (e-1) were added to 50g of GBL to obtain a positive type Varnish E1 of photosensitive resin composition. Using the obtained varnish E1, sensitivity evaluation, residual film rate evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device were performed as described above. The evaluation results are shown in Table 2.

[Example 6]

In addition to changing 11.9g (0.0325 mol) of BAHF to 8.24g (0.0225 mol), 2.45g (0.025 mol) of MA was changed to 4.9g (0.05 mol), and 15.39g (0.0375 mol) TMEG was changed to 10.26g (0.025 mol), and 15.11g (0.025 mol) of hydroxyl-containing diamine compound (α) was added instead of 5.43g (0.015 mol) of BIS-AT-AF, and it was the same as in Example 5. In the same manner, a closed ring polyimide resin (F) was obtained.

Add 10 g of the resin (F) obtained, 3.0 g of the quinonediazide compound (b1-3) obtained in Synthesis Example 4, and 0.5 g of the cross-linking agent NIKALAC MX-270 (e-2) to 50 g of GBL And the varnish F1 of the positive photosensitive resin composition was obtained. Using the obtained varnish F1, sensitivity evaluation, residual film rate evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device were performed as described above. The evaluation results are shown in Table 2.

[Example 7]

Except that 7.25g (0.02 mol) of BIS-AT-AF and 4.0g (0.02 mol) of DAE were used instead of 15.56g (0.0425 mol) of BAHF, and the MAP of 1.09g (0.01 mol) was changed to 1.64 Except g (0.015 mol), it carried out similarly to Example 3, and obtained the ring-closed polyimide resin (G).

10g of the obtained resin (G), 3.0g of quinonediazide compound (b1-1), 1.0g of alkoxymethyl-containing thermal crosslinking agent (e-1) were added to 50g of GBL to obtain a positive type Varnish G1 of photosensitive resin composition. Using the obtained varnish G1, sensitivity evaluation, residual film rate evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device were performed as described above. The evaluation results are shown in Table 2.

[Example 8]

Under dry nitrogen flow, make 13.21g (0.0375 mol) of 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine (TFM-DHB), 0.62g (0.0025 mol) of SiDA Dissolved in 200g of NMP. 20.51 g (0.05 mol) of TMEG and 50 g of NMP were added here, and the mixture was stirred at 60°C for 1 hour. After that, 2.73 g (0.025 mol) of MAP was added as a terminal sealant, and further stirring was continued at 60°C for 1 hour. Then, it was stirred at 180°C for 4 hours, and after the completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration and washed with water three times, and then dried with a vacuum dryer at 50° C. for 72 hours to obtain a powder of the ring-closed polyimide resin (H).

Add 10 g of the obtained resin (H), 3.0 g of quinonediazide compound (b1-3), and 1.0 g of crosslinking agent VG-3101L (e-3) to 50 g of GBL to obtain a positive photosensitive resin composition Material varnish H1. Using the obtained varnish H1, sensitivity evaluation, residual film rate evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device were performed as described above. The evaluation results are shown in Table 2.

[Example 9]

Except that 15.56 g (0.0425 mol) of BAHF was changed to 10.07 g (0.0275 mol), and 3.0 g (0.015 mol) of DAE was added, the same procedure as in Example 3 was carried out to obtain a closed-loop polyimide Resin (I).

10g of the obtained resin (I), 3.0g of quinonediazide compound (b1-3), 1.0g of alkoxymethyl-containing thermal crosslinking agent (e-1), 1.0g of phenol compound BisP-AF ( h-1) The varnish I1 of the positive photosensitive resin composition was obtained by adding to 50 g of GBL. Using the obtained varnish I1, sensitivity evaluation, residual film rate evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device were performed as described above. The evaluation results are shown in Table 2.

[Example 10]

10g of resin (C), 3.0g of quinonediazide compound (b1-3), 1.0g of crosslinking agent VG-3101L (e-3) were added to 50g of GBL to obtain varnish C2 of the positive photosensitive resin composition . Using the obtained varnish C2, sensitivity evaluation, residual film rate evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device were performed as described above. The evaluation results are shown in Table 2.

[Example 11]

10g of resin (D), 3.0g of quinonediazide compound (b1-3), 1.0g of alkoxymethyl-containing thermal crosslinking agent (e-1), 1.0g of phenol compound BisP-AF (h-1 ) The varnish D2 of the positive photosensitive resin composition was obtained by adding to 50 g of GBL. Using the obtained varnish D2, evaluations of sensitivity evaluation, residual film rate evaluation, bendability, and long-term reliability evaluation of the organic EL display device were performed as described above. The evaluation results are shown in Table 2.

[Example 12]

10g of resin (G), 3.0g of quinonediazide compound (b1-1), 1.0g of crosslinking agent VG-3101L (e-3) were added to 50g of GBL to obtain varnish G2 of a positive photosensitive resin composition . Using the obtained varnish G2, sensitivity evaluation, residual film rate evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device were performed as described above. The evaluation results are shown in Table 2.

[Example 13]

Combine 10g of resin (A), 3.0g of quinonediazide compound (b1-1), 1.0g of alkoxymethyl-containing thermal crosslinking agent (e-1), and 0.5g of cyclic amide compound N-form Nyl-2-pyrrolidone (NMP) was added to 50 g of GBL to obtain varnish A2 of the positive photosensitive resin composition. Using the obtained varnish A2, sensitivity evaluation, residual film rate evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device were performed as described above. The evaluation results are shown in Table 2.

Using the coating and developing device Mark-7 (manufactured by Tokyo Electron Co., Ltd.), the varnish was applied on an 8-inch silicon wafer by spin coating, and baked on a hot plate at 120 ℃ for 3 minutes to produce a film thickness of 3.2 μm pre-baked film. After that, the Mark-7 developing device was used, and the film was reduced to 0.5μm during development. After developing with 2.38% TMAH, it was rinsed with distilled water and then shaken to dry. After development, the solid film (solid film ) Fired in an oven at a predetermined temperature under a nitrogen atmosphere at 250°C for 60 minutes to obtain a cured film.

The film thickness of the obtained cured film was measured, 1x5cm was cut out from it, and the air blow trap method was used to adsorb and capture. Specifically, the collected cured film is heated at 400° C. for 60 minutes using helium as the flushing gas, and the desorbed components are collected in the adsorption tube. Use a thermal desorption device to desorb the trapped components under the first desorption conditions at 260°C for 15 minutes, and the second adsorption desorption conditions at -27°C and 320°C for 5 minutes to conduct thermal desorption, and then use the GC-MS device 7890/5975C (Agilent Manufactured by the company), GC-MS analysis was performed under the conditions of column temperature: 40~300℃, carrier gas: helium (1.5mL/min), and scanning range: m/Z29~600. The NMP was analyzed by GC-MS under the same conditions as the above, and a calibration curve was created to calculate the amount of gas generated. Divide the obtained value (μg) by the area of 5cm ² to obtain μg/cm ² . Divide this value by the value obtained by multiplying the specific gravity of (a) alkali-soluble resin by the film thickness, and then multiply it by 100 times to calculate the total content of NMP in the cured film to be 0.5% by mass.

[Comparative Example 1]

Under a stream of dry nitrogen, 15.11 g (0.025 mol) of the hydroxyl-containing diamine compound (α) obtained in Synthesis Example 1, 3.66 g (0.01 mol) of BAHF, and 0.62 g (0.0025 mol) of SiDA were dissolved in 200g of NMP. 10.26 g (0.025 mol) of TMEG, 11.11 g (0.025 mol) of 6FDA, and 50 g of NMP were added here, and stirred at 40°C for 1 hour. After that, 2.73 g (0.025 mol) of MAP was added as a terminal sealant, and the mixture was stirred at 40°C for 1 hour. After that, the solution prepared by diluting 11.9 g (0.1 mol) of DFA with 5 g of NMP was dropped over a period of 10 minutes, and after the dropping, stirring was continued for 1 hour at 40°C. After the stirring, the solution was poured into 2L of water and the solid precipitate was collected by filtration. Furthermore, washing was performed three times with 2 L of water, and the collected polymer solid was dried with a vacuum dryer at 50° C. for 72 hours to obtain a polyamide resin (J).

10g of the obtained resin (J), 3.0g of quinonediazide compound (b1-1), 1.0g of alkoxymethyl-containing thermal crosslinking agent (e-1) were added to 50g of GBL to obtain a positive type Varnish J1 of photosensitive resin composition. Using the obtained varnish J1, sensitivity evaluation, residual film rate evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device were performed as described above. The evaluation results are shown in Table 2.

[Comparative Example 2]

Under a stream of dry nitrogen, 10.07 g (0.0275 mol) of BAHF, 7.25 g (0.02 mol) of BIS-AT-AF, and 0.62 g (0.0025 mol) of SiDA were dissolved in 200 g of NMP. 14.36 g (0.035 mol) of TMEG, 2.94 g (0.015 mol) of CBDA, and 50 g of NMP were added here, and the mixture was stirred at 40°C for 1 hour. After that, the solution prepared by diluting 11.9 g (0.1 mol) of DFA with 5 g of NMP was dropped over a period of 10 minutes, and after the dropping, stirring was continued for 1 hour at 40°C. No end sealant is used. After the stirring, the solution was poured into 2L of water, and the solid precipitate was collected by filtration. Furthermore, washing was performed 3 times with 2 L of water, and the collected polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a polyamide resin (K).

Add 10g of the obtained resin (K), 3.0g of quinonediazide compound (b1-2), and 1.0g of alkoxymethyl-containing thermal crosslinking agent (e-1) to 50g of GBL to obtain a positive type Varnish K1 of photosensitive resin composition. Using the obtained varnish K1, sensitivity evaluation, residual film rate evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device were performed as described above. The evaluation results are shown in Table 2.

[Comparative Example 3]

Under a stream of dry nitrogen, 13.73 g (0.0375 mol) of BAHF, 3.62 g (0.01 mol) of BIS-AT-AF, and 0.62 g (0.0025 mol) of SiDA were dissolved in 100 g of NMP. 22.21 g (0.05 mol) of 6FDA and 10 g of NMP were added here, and reacted at 60°C for 1 hour. It was then stirred at 180°C for 4 hours. No end sealant is used. After the stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and dried with a vacuum dryer at 50° C. for 72 hours to obtain a powder of the ring-closed polyimide resin (L).

Add 10g of the obtained resin (L), 3.0g of quinonediazide compound (b1-1), and 0.5g of crosslinking agent NIKALAC MX-270(e-2) to 50g of GBL to obtain a positive photosensitive resin composition Material varnish L1. Using the obtained varnish L1, sensitivity evaluation, residual film rate evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device were performed as described above. The evaluation results are shown in Table 2.

[Comparative Example 4]

Under a stream of dry nitrogen, 14.64 g (0.04 mol) of BAHF and 0.62 g (0.0025 mol) of SiDA were dissolved in 100 g of NMP. 8.21 g (0.02 mol) of TMEG, 13.33 g (0.03 mol) of 6FDA, and 10 g of NMP were added here, and reacted at 60°C for 1 hour. After that, 1.64 g (0.015 mol) of MAP was added as a terminal sealing agent, and further stirring was continued for 1 hour at 60°C. Then, it was stirred at 180°C for 4 hours. After the stirring was completed, the solution was poured into 2 L of water to obtain a white precipitate. After the precipitate was collected by filtration and washed with water three times, it was dried in a vacuum dryer at 50° C. for 72 hours to obtain a powder of the ring-closed polyimide resin (M).

10g of the obtained resin (M), 3.0g of quinonediazide compound (b1-3), 1.0g of alkoxymethyl-containing thermal crosslinking agent (e-1), 1.0g of phenol compound BisP-AF ( h-1) The varnish M1 of the positive photosensitive resin composition was obtained by adding to 50 g of GBL. Using the obtained varnish M1, sensitivity evaluation, residual film rate evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device were performed as described above. The evaluation results are shown in Table 2.

[Comparative Example 5]

Under a stream of dry nitrogen, 6.05 g (0.01 mol) of the hydroxyl-containing diamine compound (α) obtained in Synthesis Example 1, 10.07 g (0.0275 mol) of BAHF, and 0.62 g (0.0025 mol) of SiDA were dissolved in 100g of NMP. 9.81 g (0.05 mol) of CBDA and 10 g of NMP were added here, and reacted at 60°C for 1 hour. After that, 2.18 g (0.02 mol) of MAP was added as a terminal sealant, and further stirring was continued at 60°C for 1 hour. Then, it was stirred at 180°C for 4 hours. After the stirring was completed, the solution was poured into 2 L of water to obtain a white precipitate. After collecting the precipitate by filtration and washing it with water three times, it was dried in a vacuum dryer at 50° C. for 72 hours to obtain a powder of the ring-closed polyimide resin (N).

Add 10g of the obtained resin (N), 3.0g of quinonediazide compound (b1-1), and 1.0g of alkoxymethyl-containing thermal crosslinking agent (e-1) to 50g of GBL to obtain a positive type Varnish N1 of photosensitive resin composition. Using the obtained varnish N1, sensitivity evaluation, residual film rate evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device were performed as described above. The evaluation results are shown in Table 2.

[Comparative Example 6]

Under a stream of dry nitrogen, 17.39 g (0.0475 mol) of BAHF and 0.62 g (0.0025 mol) of SiDA were dissolved in 200 g of NMP. 20.51 g (0.05 mol) of TMEG and 50 g of NMP were added here, and the mixture was stirred at 40°C for 1 hour. Thereafter, the solution prepared by diluting 11.9 g (0.1 mol) of DFA with 5 g of NMP was dropped over a period of 10 minutes, and after the dropping, stirring was continued for 1 hour at 40°C. No end sealant is used. After the stirring, the solution was poured into 2L of water, and the solid precipitate was collected by filtration. Furthermore, washing was performed three times with 2 L of water, and the collected polymer solid was dried for 72 hours with a vacuum dryer at 50° C. to obtain a polyamide resin (O).

10g of the obtained resin (O), 3.0g of quinonediazide compound (b1-1), 1.0g of alkoxymethyl-containing thermal crosslinking agent (e-1), 1.0g of phenol compound BisP-AF ( h-1) The varnish O1 of the positive photosensitive resin composition was obtained by adding to 50 g of GBL. Using the obtained varnish O1, sensitivity evaluation, residual film rate evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device were performed as described above. The evaluation results are shown in Table 2.

Regarding Examples 1 to 13 and Comparative Examples 1 to 6, each composition is shown in Table 1, and each evaluation result is shown in Table 2.

<Modulation example 1>

Weigh 138.0 g of the 30% by mass MBA solution of the resin (C) obtained in Example 3 as the resin, weigh 13.8 g of S-20000 as the dispersant, weigh 685.4 g of MBA as the solvent, and weigh 82.8 g of Bk-S0100CF It was mixed as a coloring agent, and stirred for 20 minutes using a high-speed disperser (homogeneous disperser 2.5 type; manufactured by PRIMIX (stock)) to obtain a preliminary dispersion liquid. The obtained preliminary dispersion is supplied to an Ultra Apex mill (UAM-015; manufactured by Kotobukiya Co., Ltd.) equipped with a centrifugal separator, which has been filled with 75% of 0.30mmΦ oxidation of ceramic beads for pigment dispersion Zirconium pulverized ball (YTZ; manufactured by Tosoh Co., Ltd.) was processed for 3 hours at a rotor peripheral speed of 7.0m/s to obtain a solid content concentration of 15% by mass, colorant/resin/dispersant=60/30/10 (mass Than) the pigment dispersion (Bk-1). The number average particle diameter of the pigment in the obtained pigment dispersion was 100 nm.

<Modulation example 2>

Except having used resin (M) instead of resin (C), it carried out similarly to Preparation Example 1, and obtained the pigment dispersion liquid (Bk-2).

[Example 14]

Under the yellow light, weigh 0.25 g of NCI-831, add 10.0 g of MBA, and stir to dissolve. Next, 3.5 g of the 30% by mass MBA solution of the resin (A) obtained in Example 1 was added, and 1.5 g of the 80% by mass MBA solution of DPHA was added and stirred to make a uniform solution to obtain a mixed solution. Next, 16.67 g of the pigment dispersion liquid (Bk-1) obtained in Preparation Example 1 was weighed, and the prepared liquid obtained above was added thereto and stirred to form a uniform solution. Thereafter, the obtained solution was filtered with a filter of 0.45 µmΦ to obtain a varnish BA of a negative photosensitive resin composition. Using the obtained varnish BA, sensitivity evaluation, residual film rate evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device were performed as described above. The composition is shown in Table 3, and the evaluation result is shown in Table 4.

[Examples 15 to 17 and Comparative Examples 7 to 11]

In the same manner as in Example 14, varnishes BB to BN of the photosensitive resin composition were prepared with the composition described in Table 3. Using each of the obtained compositions, in the same manner as in Example 14, sensitivity evaluation, residual film rate evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device were performed. The evaluation results are shown in Table 4.

Regarding Examples 14 to 17 and Comparative Examples 7 to 11, each composition and each evaluation result are shown in Table 3 and Table 4, respectively.

1‧‧‧TFT (Thin Film Transistor)

2‧‧‧Wiring

3‧‧‧TFT Insulation Layer

4‧‧‧Planarization layer

5‧‧‧ITO (transparent electrode)

6‧‧‧Substrate

7‧‧‧Contact hole

8‧‧‧Insulation layer

Claims (19)

A photosensitive resin composition containing (a) an alkali-soluble resin and (b) a photosensitive compound; the aforementioned (a) alkali-soluble resin has a structure represented by the general formula (1) of 95-100 mol% as a repeating unit , In the aforementioned (a) alkali-soluble resin, at least one end of the polymer molecular chain has an organic group derived from a monoamine or an acid anhydride as a terminal sealant, and is relative to 100 mol% of the general formula (1) As shown in the structural unit, the aforementioned (a) alkali-soluble resin has 20-100 mol% of organic groups derived from monoamines or acid anhydrides as terminal sealants:

(In the general formula (1), R ¹ represents a divalent organic group; R ² and R ³ each independently represent hydrogen or an organic group with 1 to 20 carbon atoms; X ¹ and X ² each independently represent an ethylidene group and an ethylidene group. R ¹ , X ¹ and X ² may be different from each other in multiple repeating units; m and n are integers from 0 to 100,000, m+n≧3). The photosensitive resin composition of claim 1, wherein the aforementioned monoamine is a compound having a structure represented by the general formula (2):

(In the general formula (2), R ⁴ represents a saturated hydrocarbon group with 1 to 6 carbon atoms, and r represents 0 or 1; A and B may be the same or different, and represent a hydroxyl group, a carboxyl group or a sulfonic acid group; s and t respectively Represents 0 or 1, s+t≧1). The photosensitive resin composition of claim 1 or 2, wherein the aforementioned (b) photosensitive compound is (b1) a photoacid generator. The photosensitive resin composition of claim 1 or 2, wherein the aforementioned (b) photosensitive compound is (b2) a photopolymerization initiator, and further contains (d) a radical polymerizable compound. The photosensitive resin composition of claim 1 or 2, which further contains (e) a thermal crosslinking agent. The photosensitive resin composition of claim 1 or 2, which further contains (f) a colorant. The photosensitive resin composition of claim 6, wherein the aforementioned (f) colorant is (f3) a black agent and/or (f4) a colorant other than black. The photosensitive resin composition of claim 6, wherein the aforementioned (f) colorant is (f1) pigment or (f2) dye. A photosensitive sheet comprising the photosensitive resin composition according to any one of claims 1 to 8. A cured film comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 8. A cured film comprising the cured product of the photosensitive sheet according to claim 9. The cured film of claim 10 or 11, which contains one or more compounds selected from the group consisting of (i) cyclic amide, cyclic urea, and derivatives thereof. The cured film of claim 12, wherein the total content of the above-mentioned one or more compounds selected from the group comprising (i) cyclic amide, cyclic urea, and derivatives thereof in the cured film is 0.005 mass % Above 5% by mass. A component having a cured film as in any one of Claims 10 to 13. An organic EL display device is provided with a planarization layer including the cured film of any one of claims 10 to 13 and/or an insulating layer on a first electrode on a substrate with a drive circuit. The organic EL display device of claim 15, wherein the aforementioned substrate with the driving circuit includes a resin film. A semiconductor electronic component is provided with an interlayer insulating film between redistribution lines, wherein the interlayer insulating film between the redistribution lines includes the cured film according to any one of claims 10 to 13. A semiconductor device provided with an interlayer insulating film between rewiring rooms, wherein the interlayer insulating film between rewiring rooms includes the cured film according to any one of claims 10 to 13. A method of manufacturing an organic EL display device, comprising the following steps: coating the photosensitive resin composition according to any one of claims 1 to 8 to a substrate, or laminating the photosensitive sheet according to claim 9 to the substrate, And forming a photosensitive resin film; drying the aforementioned photosensitive resin film; exposing the dried photosensitive resin film; developing the exposed photosensitive resin film; and developing the photosensitive resin film The step of heat-treating the flexible resin film.

Images