JP7106863B2 - Photosensitive resin composition for organic EL display device - Google Patents

Description

The present invention relates to a photosensitive resin composition. Specifically, it is used as a surface protective film and an interlayer insulating film of a semiconductor element, an insulating film of an organic electroluminescence (EL) element, and a thin film transistor (hereinafter referred to as a TFT) for driving a display device using an organic EL element. ) The present invention relates to a photosensitive resin composition suitable for applications such as flattening films for substrates, wiring protective insulating films for circuit boards, on-chip microlenses for solid-state imaging devices, and flattening films for various displays and solid-state imaging devices.

Since heat-resistant resins such as polyimide and polybenzoxazole have excellent heat resistance and electrical insulation properties, photosensitive resin compositions containing these heat-resistant resins can be used as surface protective films of semiconductor elements such as LSIs, It is used for interlayer insulating films, insulating layers for organic electric field devices and organic EL display devices, flattening films for TFT substrates for display devices, and the like.

In recent years, for reasons such as the increase in size of substrates and the improvement in productivity, high sensitivity is required for photosensitive resin compositions in order to shorten the exposure time. In addition, recently, since the flexible display has been actively studied by forming the substrate with an organic film, flexibility such as bending resistance is required for the insulating film and the flattening film.

For example, for a positive photosensitive heat-resistant composition that can be developed with an alkaline aqueous solution, there is a photosensitive resin composition that achieves high sensitivity using a highly transparent polyimide using a tetracarboxylic anhydride having an alicyclic structure. proposed (see, for example, Patent Documents 1 and 2).

Moreover, in order to achieve high sensitivity, a highly transparent polyimide resin using a tetracarboxylic acid anhydride having a fluorine atom such as a hexafluoropropyl group has also been proposed (see, for example, Patent Documents 3 and 4). .

Moreover, in order to achieve bending resistance, a photosensitive resin composition using a polyimide using a tetracarboxylic anhydride having an ester group has been proposed (see, for example, Patent Document 5).

WO2000/73853 JP 2010-196041 A JP 2007-183388 A JP 2011-202059 A WO2011/59089

However, the polyimide resin using a tetracarboxylic anhydride having an alicyclic structure, as described in Patent Documents 1 and 2, has too high solubility in an alkaline developer, resulting in a low residual film rate. there was a case.

In addition, as described in Patent Documents 3 and 4, polyimide resins using tetracarboxylic acid anhydrides having fluorine atoms such as hexafluoropropyl groups have brittle cured films and excellent bending resistance. was sometimes difficult to do.

In addition, polyimide resins using tetracarboxylic anhydrides having an ester group structure, such as those described in Patent Document 5, are excellent in bending resistance, but sometimes have insufficient sensitivity.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a highly sensitive photosensitive resin composition which has a high residual film ratio after development and a cured film having high bending resistance.

The present invention contains (a) an alkali-soluble resin and (b) a photosensitive compound, wherein the (a) alkali-soluble resin has 95 to 100 mol% of structural units represented by the general formula (1), The photosensitive resin composition (a) has an organic group derived from a monomamine or an acid anhydride at at least one end of the polymer molecular chain in the alkali-soluble resin.

(In 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 carbon atoms. X ¹ and X ² each represent independently represents a linear or branched alkylene group, 1,3-phenylene group or 1,4-phenylene group having 2 to 20 carbon atoms, wherein R ¹ , X ¹ and X ² each represent a plurality of repeating units; may be different, m and n are each an integer from 0 to 100,000, and m+n≧3.)

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which contains alkali-soluble resin with high solubility with respect to the organic solvent, and has high sensitivity, a film retention rate, and flexibility can be obtained.

Cross-sectional view of an example of a TFT substrate Schematic diagram of organic EL display device

<(a) alkali-soluble resin>
The resin of the present invention is an alkali-soluble resin selected from alkali-soluble polyimides, polyimide precursors, and copolymers thereof having a structural unit represented by the general formula (1).

(a) A photosensitive resin composition containing an alkali-soluble resin is preferably used for manufacturing an organic EL display device.

As a polyimide precursor, for example, a tetracarboxylic acid, a corresponding tetracarboxylic dianhydride or tetracarboxylic acid diester dichloride, etc., and a diamine, a corresponding diisocyanate compound or trimethylsilylated diamine, etc. are obtained by reacting. and have a tetracarboxylic acid and/or derivative residue thereof and a diamine and/or derivative residue thereof. Polyimide precursors include, for example, polyamic acid, polyamic acid ester, polyamic acid amide, or polyisoimide.

Examples of polyimides include those obtained by dehydrating and ring-closing the above-mentioned polyamic acid, polyamic acid ester, polyamic acid amide or polyisoimide by heating or by reaction using an acid or a base, tetracarboxylic acid and It has/or a derivative residue thereof and a diamine and/or a derivative residue thereof.

An ester group-containing tetracarboxylic acid dianhydride is used to obtain a resin having a structural unit represented by general formula (1) as a repeating unit. By containing an ester structure, free rotation of the polymer main chain is facilitated compared to a rigid polyimide having only an imide structure, so that a cured film having high solvent solubility and flexibility can be obtained.

The ester group-containing tetracarboxylic dianhydride is not particularly limited, and commercially available products and those obtained by conventionally known production methods can also be used.

X ¹ and X ² in the general formula (1) are a linear or branched alkylene group, 1,3-phenylene group or 1,4-phenylene group having 2 to 20 carbon atoms, preferably a carbon number 2 to 20 linear or branched alkylene groups. Since the alkylene group can take various conformations, the flexibility of the cured film can be further enhanced by having the alkylene group in the molecular chain of the resin. From the viewpoint of improving the heat resistance of the resin, it is preferably a linear or branched alkylene group having 2 to 6 carbon atoms, more preferably a linear or branched alkylene group having 2 to 4 carbon atoms. , especially the ethylene group. 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 general formula (1) are preferably an ethylene group, a propylene group, or a butylene group. , as described above, is more preferably an ethylene group. When X ¹ and X ² are ethylene groups, a cured film having a particularly excellent balance between heat resistance and flexibility can be provided.

Specific examples of ester group-containing tetracarboxylic dianhydrides include 1,2-ethylenebis(anhydrotrimellitate), 1,3-propylenebis(anhydrotrimellitate), and 1,4-tetramethylene. Bis(anhydrotrimellitate), 1,5-pentamethylenebis(anhydrotrimellitate), 1,6-hexamethylenebis(anhydrotrimellitate), 1,7-heptamethylenebis(anhydrotrimellitate) mellitate), 1,8-octamethylene bis (anhydro trimellitate), 1,9-nonamethylene bis (anhydro trimellitate), 1,10-decamethylene bis (anhydro trimellitate), 1 , 12-dodecamethylenebis(anhydrotrimellitate), 1,3-phenylenebis(anhydrotrimellitate), 1,4-phenylenebis(anhydrotrimellitate) and the like. Among these, 1,2-ethylenebis(anhydrotrimellitate) is preferably used because it has a particularly excellent balance between heat resistance and flexibility.

The (a) alkali-soluble resin used in the present invention has 95 to 100 mol % of the structural unit represented by the general formula (1), thereby improving the solubility in organic solvents and increasing the flexibility of the resin composition. can improve sexuality. A structural unit is a repeating unit, and indicates a structure represented by repeating numbers m and n, and the structure represented by repeating numbers m and n may be random or block.

The alkali-soluble resin having 95 to 100 mol% of the structural unit represented by the general formula (1) is prepared according to a known method for producing a polyimide precursor described later, with respect to 100 mol% of the diamine component. It is obtained by using 95 to 100 mol % of anhydride. (a) When the alkali-soluble resin has 95 mol % or more of the structural unit represented by the general formula (1), it is possible to provide a resin having excellent flexibility and high bending resistance. Further, X ¹ and X ² in the general formula (1) are a linear or branched alkylene group having 2 to 20 carbon atoms, a 1,3-phenylene group or a 1,4-phenylene group. Since it exhibits hydrophobicity, it is possible to provide a resin with a high residual film rate after development. In particular, when (a) the alkali-soluble resin has 95 mol % or more of the structural unit represented by the general formula (1), it is possible to provide a resin having a high residual film rate after development.

In addition, the (a) alkali-soluble resin used in the present invention contains a structure derived from other acid dianhydrides in addition to the ester group-containing tetracarboxylic acid dianhydride within a range that does not deteriorate the above-mentioned properties. good too.

Other acid dianhydrides specifically include pyromellitic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyl Tetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3, 3′-benzophenonetetracarboxylic 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 product, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9, 9-bis(3,4-dicarboxyphenyl)fluoric acid dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluoric acid dianhydride, 2,3,6,7 -naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4 -dicarboxyphenyl)hexafluoropropane dianhydride, aromatic tetracarboxylic dianhydrides such as acid dianhydrides having the structures shown in the following general formulas (3) and (4), and butanetetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-cyclopentanetetracarboxylic dianhydride. You may use 2 or more types of these.

(In 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 general formula (1), R ¹ is a structure derived from diamine. In general formula (1), R ¹ is preferably an organic group having a fluorine atom. The presence of fluorine atoms imparts water repellency to the surface of the film during alkali development, and can suppress permeation from the surface, resulting in a highly residual film with no tack in unexposed areas or residue from development on processed patterns. A photosensitive resin film of a rate is obtained.

In general formula (1), in order to obtain the effect of preventing permeation at the interface and an appropriate dissolution rate, the organic group having a fluorine atom is preferably 30 mol % or more when the total amount of R ¹ is 100 mol %. Such a structure is introduced by using 30 mol % or more of a monomer containing a fluorine atom among the monomer components for introducing R ¹ . Further, in order to obtain adhesion to the substrate, the content of the monomer containing fluorine atoms is preferably 90 mol % or less.

Specific examples of diamines having a fluorine atom include bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2, Aromatic diamines such as 2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine, and some of the hydrogen atoms of these aromatic rings are substituted with an alkyl group having 1 to 10 carbon atoms or a fluoroalkyl group, and compounds substituted with halogen atoms and the like. The resin having the structure represented by formula (1) is preferably a resin containing a structure derived from these compounds.

Moreover, (a) the alkali-soluble resin of the present invention preferably has a phenolic hydroxyl group. In general formula (1), R ¹ is preferably an organic group having a phenolic hydroxyl group. A phenolic hydroxyl group provides moderate solubility in an alkaline developer, and interacts with a photosensitive agent to suppress the solubility of unexposed areas, thereby improving the residual film ratio and increasing the sensitivity. In addition, since the phenolic hydroxyl group also contributes to the reaction with the cross-linking agent, it is also preferable in that high mechanical properties and chemical resistance can be obtained.

In general formula (1), the organic group having a phenolic hydroxyl group is preferably 30 mol % or more when the total amount of R ¹ is 100 mol % in order to obtain appropriate solubility in an alkaline developer. Such a structure is introduced by using 30 mol % or more of a monomer containing a phenolic hydroxyl group among the monomer components for introducing R ¹ . More preferably, it is 50 mol % or more. Moreover, in order to improve the residual film ratio after development, it is preferable that the monomer containing a phenolic hydroxyl group is 90 mol % or less.

Specific examples of diamines having a phenolic hydroxyl group include bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxy phenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4- hydroxyphenyl)fluorene, 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine and other hydroxyl group-containing diamines, and some of the hydrogen atoms of these aromatic rings are substituted with 1 to 10 carbon atoms. and compounds substituted with an alkyl group, a fluoroalkyl group, a halogen atom, or the like. The resin having the structure represented by formula (1) is preferably a resin containing a structure derived from these compounds.

By using the above-mentioned ester group-containing tetracarboxylic dianhydride, the diamine having a phenolic hydroxyl group, and the diamine having a fluorine atom within the above range, during development, a high residual film rate without tack or development residue can be obtained. A highly sensitive photosensitive resin composition is obtained.

Moreover, R ¹ in the general formula (1) of the present invention may have a structure derived from other diamine in addition to the diamine described above.

Other diamines include aliphatic diamines containing polyethylene oxide groups such as "Jeffamine" (registered trademark) KH-511, "Jeffamine" ED-600, "Jeffamine" ED-900, "Jeffamine" ED. -2003, "Jeffamine" EDR-148, "Jeffamine" EDR-176, polyoxypropylenediamine D-200, D-400, D-2000, D-4000 (these are trade names, manufactured by HUNTSMAN Co., Ltd.) etc. can be mentioned. Among them, the use of an aliphatic alkyldiamine is preferred because it imparts flexibility to improve the elongation at break, and lowers the elastic modulus to suppress warping of the wafer. These characteristics are effective in multilayers and thick films. When introduced, the content of residues derived from aliphatic alkyldiamine in all diamine residues is preferably 10 mol% or more, and preferably 50 mol% or less from the viewpoint of improving heat resistance.

In addition, other diamines may have an aliphatic group having a siloxane structure within a range that does not reduce the heat resistance, thereby improving the adhesiveness to the substrate. Specific examples thereof include those obtained by copolymerizing bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like in an amount of 1 to 15 mol %.

Still other diamines include bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, 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)fluorene, 2, hydroxyl group-containing diamines such as 2′-bis(trifluoromethyl)-5,5′-dihydroxybenzidine, sulfonic acid-containing diamines such as 3-sulfonic acid-4,4′-diaminodiphenyl ether, thiols such as dimercaptophenylenediamine group-containing diamines, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'- Diaminodiphenyl sulfone, 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)sulfone, bis(3-aminophenoxyphenyl)sulfone, 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'-diaminobiphenyl, 3,3 '-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3, Aromatic diamines such as 3′,4,4′-tetramethyl-4,4′-diaminobiphenyl and 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, and aromatic rings thereof A portion of the hydrogen atoms of is substituted with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, or the like, and alicyclic diamines such as cyclohexyldiamine and methylenebiscyclohexylamine. These diamines can be used as they are or as corresponding diisocyanate compounds, trimethylsilylated diamines. Moreover, you may use combining these 2 or more types of diamine components. From the viewpoint of improving heat resistance, it is preferable to use the aromatic diamine in an amount of 50 mol % or more of the total diamine.

Among these, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfide, 4, 4′-diaminodiphenyl sulfide, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, 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)phenyl]hexafluoropropane, 2,2 -bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2'-bis(trifluoromethyl)-5,5' -Dihydroxybenzidine, compounds in which these aromatic rings are substituted with alkyl groups or halogen atoms, and diamines having an amide group represented by the following general formulas (5) to (10) are preferred. These are used alone or in combination of two or more.

(In general formulas (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 represents a hydrogen atom or a hydroxyl group; show.)
Moreover, 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 an appropriate amount of sulfonic acid groups and thiol groups, a photosensitive resin composition having appropriate alkali solubility can be obtained.

The (a) alkali-soluble resin used in the photosensitive resin composition of the present invention has an organic group derived from a monoamine or an acid anhydride at at least one end of the polymer molecular chain. Here, monoamines or acid anhydrides are end capping agents. By using a terminal blocking agent, it becomes easy to adjust the photosensitive resin composition to an appropriate viscosity. In addition, the effect of suppressing the hydrolysis of the resin by the acid terminal, and the effect of suppressing the deterioration of the quinonediazide compound, which is a photosensitive agent, by the amine terminal when a positive photosensitive resin composition is formed, and the photosensitive of the present invention. When the flexible resin composition is used as a planarization layer and/or an insulating layer of an organic EL display device, it has the effect of improving the long-term reliability of the organic EL display device. The terminal blocking agent preferably has a hydroxyl group, a carboxyl group or a sulfonic acid group as a substituent, and more preferably a hydroxyl group from the viewpoint of improving heat resistance. By having a hydroxyl group, a carboxyl group, or a sulfonic acid group as a substituent, the terminal blocker can improve the solubility of the resulting resin in an alkaline aqueous solution and provide a highly sensitive resin. In addition, since the resin has a hydroxyl group, a carboxyl group or a sulfonic acid group at its terminal, when it is made into a positive photosensitive resin composition, it interacts with the quinonediazide compound through hydrogen bonding, making the unexposed area insoluble. , it is possible to provide a resin with a high residual film rate after development.

Although the monoamine used for the terminal blocking agent is not particularly limited, a compound represented by the following general formula (2) is preferable for the following reasons. By containing a saturated hydrocarbon group or an aromatic hydrocarbon group in the terminal group, the hydrophobicity of the resin is increased, and when it is made into a photosensitive resin composition described later, it is possible to reduce the amount of film loss during alkaline development. can. Furthermore, by containing at least one group selected from a hydroxyl group, a carboxyl group, or a sulfonic acid group, moderate solubility in an alkaline developer can be obtained, and when a positive photosensitive resin composition is formed, the quinonediazide compound By interacting with through hydrogen bonding, the unexposed area becomes insoluble, and it is possible to 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 cross-linking agent, it is also preferable in that high mechanical properties and chemical resistance can be obtained.

(In 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 may be a hydroxyl group, a carboxyl group, or represents a sulfonic acid group, s and t each represent 0 or 1, and from the viewpoint of improving the solubility of the resulting resin in an alkaline aqueous solution, s+t≧1.)
Preferred examples of monoamines represented by the 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-xylenol, 4-amino-3 ,5-xylenol, 6-amino-2,4-xylenol, 2-amino-4-ethylphenol, 3-amino-4-ethylphenol, 2-amino-4-tert-butylphenol, 2-amino-4-phenyl Phenol, 4-amino-2,6-diphenylphenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic 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-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 4-aminotoluene-3-sulfonic acid and the like can be mentioned. Two or more of these may be used, or other terminal blocking agents may be used in combination.

The introduction ratio of the monoamine used as the terminal blocking agent is preferably 10 to 100 mol%, more preferably 40 to 80 mol%, relative to 100 mol% of the structural units represented by general formula (1). By making it 10 mol% or more, preferably 40 mol% or more, the solubility of the obtained resin in an organic solvent is improved, and the viscosity when a photosensitive resin composition is formed using the obtained resin is adjusted appropriately. can do. From the viewpoint of the solubility of the resulting 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 used for the terminal blocking agent is not particularly limited, but from the viewpoint of heat resistance of the cured film of the photosensitive resin composition using the obtained resin, it has an acid anhydride having a cyclic structure or a crosslinkable group. Acid anhydrides are preferred. Examples include phthalic anhydride, maleic anhydride (MA), nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, and the like.

The introduction ratio of the acid anhydride used as the terminal blocking agent is preferably 10 to 100 mol%, more preferably 50 to 100 mol%, relative to 100 mol% of the structural units represented by general formula (1). By making it 10 mol% or more, preferably 50 mol% or more, the solubility of the obtained resin in an organic solvent is improved, and the viscosity when a photosensitive resin composition is formed using the obtained resin is adjusted appropriately. can do. From the viewpoint of the solubility of the resulting resin in an alkaline aqueous solution and the mechanical strength of the cured film, the content is preferably 100 mol % or less, more preferably 90 mol % or less.

The terminal blocking agent introduced into the resin can be easily detected by the following method. For example, a resin into which a terminal blocking agent has been introduced is dissolved in an acidic solution, decomposed into an amine component and an acid component, which are structural units of the resin, and subjected to gas chromatography (GC) or NMR measurement. End capping agents can be easily detected. Apart from this, it is possible to directly detect the resin into which the terminal blocking agent has been introduced by pyrolysis gas chromatography (PGC), infrared spectrum and 13C NMR spectrum measurement.

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

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

The (a) alkali-soluble resin of the present invention can be produced according to a known method for producing a polyimide precursor. For example, (I) a method of reacting an ester group-containing tetracarboxylic acid dianhydride, a diamine compound having an R ¹ group, and a monoamine as a terminal blocking agent under low temperature conditions, (II) an ester group-containing tetracarboxylic acid diamine A method of obtaining a diester from an anhydride and an alcohol, then reacting a diamine compound having an R ¹ group, a monoamine as a terminal blocker and a condensing agent in the presence of (III) an ester group-containing tetracarboxylic acid dianhydride and an alcohol to obtain a diester, then acid chloride the remaining two carboxyl groups, react with a diamine compound having an R ¹ group, and a monoamine terminal blocker. The resin polymerized by the above method is desirably put into a large amount of water or a mixture of methanol/water, etc., precipitated, separated by filtration and dried, and isolated. This precipitation operation removes unreacted monomers and oligomer components such as dimers and trimers, thereby improving film properties after thermal curing. Further, imidization of the polyimide precursor is recommended, and the ring-closed polyimide can be synthesized by using a known imidization reaction method after obtaining the above polyimide precursor.

Hereinafter, as a preferable example of (I), an example of a method for producing a polyimide precursor will be described. First, a diamine compound having an R ¹ group is dissolved in a polymerization solvent. An ester group-containing tetracarboxylic dianhydride is gradually added to this solution in an amount substantially equimolar with the diamine compound. Using a mechanical stirrer, stir at −20 to 100° C., preferably 10 to 50° C., for 0.5 to 100 hours, more preferably 2 to 24 hours. After adding the tetracarboxylic dianhydride, the terminal blocking agent may be added gradually after stirring at a predetermined temperature for a predetermined time, or may be added at once and allowed to react. .

The polymerization solvent is not particularly limited as long as it can dissolve the tetracarboxylic dianhydrides and diamines, which are raw material monomers. For example, N,N-dimethylformamide, N,N-dimethylacetamide, amides of N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α -Cyclic esters such as 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, sulfolane, dimethylsulfoxide and the like can be mentioned. The polymerization solvent is preferably used in an amount of 100 to 1,900 parts by mass, more preferably 150 to 950 parts by mass, per 100 parts by mass of the resulting resin.

The photosensitive resin composition of the present invention may contain an alkali-soluble resin other than (a) the alkali-soluble resin. Specifically, alkali-soluble polybenzoxazole, polybenzoxazole precursor, polyamide, acrylic polymer obtained by copolymerizing acrylic acid, novolac resin, resole resin, siloxane resin, polyhydroxystyrene resin, methylol group, alkoxymethyl Examples thereof include resins into which cross-linking groups such as groups and epoxy groups have been introduced, and copolymers thereof. Such resins are soluble in alkaline aqueous solutions such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, 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 adhesion of the heat-resistant resin film and excellent sensitivity. It is preferable that (a) the alkali-soluble resin of the present invention accounts for 30% by mass or more of the resins contained in the photosensitive resin composition of the present invention.

<(b) Photosensitive compound>
The photosensitive resin composition of the present invention contains (b) a photosensitive compound. Examples of the photosensitive compound include (b1) a photoacid generator and (b2) a photopolymerization initiator. (b1) The photoacid generator is a compound that generates an acid when exposed to light and imparts the property of increasing the solubility of the light-irradiated portion in an alkaline aqueous solution. A compound that generates a radical by bond cleavage and/or reaction by

(b1) By containing a photoacid generator, an acid is generated in the light-irradiated area and the solubility of the light-irradiated area in an alkaline aqueous solution increases, so that a positive relief pattern in which the light-irradiated area dissolves can be obtained. can. In addition, (b1) by containing a photoacid generator and an epoxy compound or a thermal cross-linking agent described later, the acid generated in the light-irradiated portion accelerates the cross-linking reaction of the epoxy compound and the thermal cross-linking agent, and the light-irradiated portion becomes insoluble. A negative relief pattern can be obtained. Further, by containing (b2) a photopolymerization initiator and a radically polymerizable compound described later, radical polymerization proceeds, and the exposed portion of the film of the resin composition becomes insoluble in an alkaline developer, resulting in a negative type. pattern can be formed.

(b1) Photoacid generators include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts.

Examples of the quinonediazide compound include those in which the sulfonic acid of quinonediazide is bonded to a polyhydroxy compound via an ester bond, the sulfonic acid of quinonediazide to a polyamino compound in a sulfonamide bond, and the sulfonic acid of quinonediazide to a polyhydroxypolyamino compound in an ester bond and/or a sulfone bond. Examples thereof include those with an amide bond. It is preferable that 50 mol % or more of all the functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide. Moreover, it is preferable to contain two or more kinds of (b1) photoacid generators, and a highly sensitive photosensitive resin composition can be obtained.

In the present invention, both 5-naphthoquinonediazide sulfonyl group and 4-naphthoquinonediazide sulfonyl group are preferably used as quinonediazide. A 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. A 5-naphthoquinonediazide sulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinonediazide sulfonyl ester compound or a 5-naphthoquinone diazidesulfonyl ester compound depending on the exposure wavelength. Further, it may contain a naphthoquinonediazide sulfonyl ester compound having a 4-naphthoquinone diazidesulfonyl group and a 5-naphthoquinone diazidesulfonyl group in the same molecule, or a 4-naphthoquinone diazidesulfonyl ester compound and a 5-naphthoquinone diazidesulfonyl ester compound. may contain.

The naphthoquinonediazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinonediazide sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinonediazide compounds, the resolution, sensitivity and film retention rate are further improved.

Among the photoacid generators (b1), sulfonium salts, phosphonium salts and diazonium salts are preferred because they moderately stabilize the acid component generated by exposure. Among them, sulfonium salts are preferred. Furthermore, a sensitizer and the like can be contained as necessary.

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

(b2) Photopolymerization initiators include, for example, benzyl ketal photopolymerization initiators, α-hydroxyketone photopolymerization initiators, α-aminoketone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, and oxime esters. photoinitiator, acridine photoinitiator, titanocene photoinitiator, benzophenone photoinitiator, acetophenone photoinitiator, aromatic ketoester photoinitiator or benzoic acid ester photoinitiator From the viewpoint of improving sensitivity during exposure, α-hydroxyketone photopolymerization initiators, α-aminoketone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, oxime ester photopolymerization initiators, acridine A benzophenone-based photopolymerization initiator or a benzophenone-based photopolymerization initiator is more preferred, and an α-aminoketone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and an oxime ester-based photopolymerization initiator are more preferred.

Benzyl ketal photopolymerization initiators include, for example, 2,2-dimethoxy-1,2-diphenylethan-1-one.

Examples of α-hydroxyketone-based photopolymerization initiators include 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1 -one, 1-hydroxycyclohexylphenyl ketone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one or 2-hydroxy-1-[4-[4-( 2-Hydroxy-2-methylpropionyl)benzyl]phenyl]-2-methylpropan-1-one.

Examples of α-aminoketone-based photopolymerization initiators include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4 -morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one or 3,6-bis(2-methyl- 2-morpholinopropionyl)-9-octyl-9H-carbazole.

Examples of acylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and bis(2,6-dimethoxybenzoyl). )-(2,4,4-trimethylpentyl)phosphine oxide.

Examples of oxime ester photopolymerization initiators include 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2-dione-2-(O-methoxy carbonyl)oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-( O-benzoyl)oxime, 1-[4-[4-(carboxyphenyl)thio]phenyl]propane-1,2-dione-2-(O-acetyl)oxime, 1-[9-ethyl-6-(2 -methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, 1-[9-ethyl-6-[2-methyl-4-[1-(2,2-dimethyl- 1,3-dioxolan-4-yl)methyloxy]benzoyl]-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime or 1-(9-ethyl-6-nitro-9H-carbazole- 3-yl)-1-[2-methyl-4-(1-methoxypropan-2-yloxy)phenyl]methanone-1-(O-acetyl)oxime.

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

Titanocene-based photopolymerization initiators include, for example, bis(η5-2,4-cyclopentadien-1-yl)-bis[2,6-difluoro)-3-(1H-pyrrol-1-yl)phenyl]titanium (IV) or bis(η5-3-methyl-2,4-cyclopentadien-1-yl)-bis(2,6-difluorophenyl)titanium (IV).

Examples of benzophenone-based photopolymerization initiators include benzophenone, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, 4- Hydroxybenzophenone, alkylated benzophenone, 3,3′,4,4′-tetrakis(t-butylperoxycarbonyl)benzophenone, 4-methylbenzophenone, dibenzylketone or fluorenone.

Acetophenone-based photopolymerization initiators include, for example, 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-t-butyldichloroacetophenone, benzalacetophenone, and 4-azidobenzalacetophenone.

Examples of aromatic ketoester-based photopolymerization initiators include methyl 2-phenyl-2-oxyacetate.

Examples of benzoic acid ester photopolymerization initiators include ethyl 4-dimethylaminobenzoate, (2-ethyl)hexyl 4-dimethylaminobenzoate, ethyl 4-diethylaminobenzoate and methyl 2-benzoylbenzoate. .

In the present invention, the content of (b2) the photopolymerization initiator is 0.1 parts by mass or more when the total of (a) the alkali-soluble resin and (d) the radically polymerizable compound described below is 100 parts by mass. is preferred, 0.5 parts by mass or more is more preferred, 0.7 parts by mass or more is even more preferred, and 1 part by mass or more is particularly preferred. When 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, even more preferably 17 parts by mass or less, and particularly preferably 15 parts by mass or less. When the content is within the above range, the resolution after development can be improved, and a low taper pattern shape can be obtained.

<(c) Solvent>
The photosensitive resin composition of the present invention contains (c) a solvent. 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, diethylene glycol ethyl methyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, Esters such as ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, alcohols such as ethanol, isopropanol, butanol, pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, methyl ethyl ketone , methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, cyclopentanone, ketones such as diacetone alcohol, N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, Examples include polar aprotic solvents such as dimethylsulfoxide and 1,3-dimethyl-2-imidazolidinone, and aromatic hydrocarbons such as toluene and xylene. You may contain 2 or more types of these. (c) The content of the solvent is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, and preferably 2000 parts by mass or less, more preferably 100 parts by mass of the alkali-soluble resin (a). is 1500 parts by mass or less.

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

(d) Radically polymerizable compound refers to a compound having a plurality of ethylenically unsaturated double bond groups in its molecule. During exposure, the radicals generated from the (b2) photopolymerization initiator described above promote radical polymerization of the (d) radically polymerizable compound, and the exposed portion of the film of the resin composition becomes insoluble in an alkaline developer. , a negative pattern can be formed.

(d) Inclusion of a radically polymerizable compound promotes UV curing during exposure, and can improve sensitivity during exposure. In addition, the crosslink density after thermosetting is improved, and the hardness of the cured film can be improved.

(d) As the radically polymerizable compound, a compound having a (meth)acrylic group, which facilitates radical polymerization, is preferable. Compounds having two or more (meth)acrylic groups in the molecule are more preferable from the viewpoint of improving the sensitivity during exposure and the hardness of the cured film. (d) The double bond equivalent of the radically polymerizable compound is preferably 80 to 400 g/mol from the viewpoint of improving the sensitivity during exposure and improving the hardness of the cured film.

(d) Radically polymerizable compounds include, for example, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane ( meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane di(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate ) acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1, 9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, Pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta (Meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, pentapentaerythritol undeca(meth)acrylate, pentapentaerythritol dodeca(meth)acrylate , ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-(3-(meth)acryloxy-2-hydroxypropoxy)phenyl]propane, 1,3,5-tris((meth)acryloxyethyl ) isocyanuric acid, 1,3-bis((meth)acryloxyethyl)isocyanuric acid, 9,9-bis[4-(2-(meth)acryloxyethoxy)phenyl]fluorene, 9,9-bis[4- (3-(meth)acryloxypropoxy)phenyl]fluorene or 9,9-bis(4-(meth)acrylo xyphenyl)fluorene or acid modified products thereof, ethylene oxide modified products or propylene oxide modified products thereof. From the viewpoint of improving the sensitivity during exposure and improving the hardness of the cured film, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, 2,2-bis [ 4-(3-(meth)acryloxy-2-hydroxypropoxy)phenyl]propane, 1,3,5-tris((meth)acryloxyethyl)isocyanuric acid, 1,3-bis((meth)acryloxyethyl) isocyanuric acid, 9,9-bis[4-(2-(meth)acryloxyethoxy)phenyl]fluorene, 9,9-bis[4-(3-(meth)acryloxypropoxy)phenyl]fluorene or 9,9 -Bis(4-(meth)acryloxyphenyl)fluorene or an acid modified product thereof, an ethylene oxide modified product or a propylene oxide modified product thereof is preferred, and from the viewpoint of improving resolution after development, an acid modified product thereof or an ethylene oxide modified product thereof is preferred. more preferred. Further, from the viewpoint of improving resolution after development, a compound obtained by a ring-opening addition reaction between a compound having two or more glycidoxy groups in the molecule and an unsaturated carboxylic acid having an ethylenically unsaturated double bond group. A compound obtained by reacting a polybasic carboxylic acid or a polybasic carboxylic acid anhydride is also preferred.

In the present invention, the content of (d) the radically polymerizable compound is preferably 15 parts by mass or more, and 20 parts by mass when the total of (a) the alkali-soluble resin and (d) the radically polymerizable compound is 100 parts by mass. Parts or more are more preferable, 25 parts by mass or more are still more preferable, and 30 parts by mass or more are particularly preferable. When the content is within the above range, the sensitivity during exposure can be improved, and a pattern shape with a low taper 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, even 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 low taper pattern shape can be obtained. Driving stability of the completed organic EL panel can be enhanced by making the pattern shape low taper.

<(e) Thermal cross-linking agent>
The photosensitive resin composition of the present invention may further contain (e) a thermal cross-linking agent. A thermal cross-linking agent refers to a compound having at least two thermally reactive functional groups such as an alkoxymethyl group, a methylol group, an epoxy group, and an oxetanyl group in the molecule. The thermal cross-linking agent (a) can cross-link the alkali-soluble resin or other additive components to enhance the heat resistance, chemical resistance and hardness of the film after thermal curing.

Preferred examples of compounds having at least two alkoxymethyl groups or methylol groups include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML- OCHP, 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 (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC ( Registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (trade names, manufactured by Sanwa Chemical Co., Ltd.), respectively. It is available from each company mentioned above.

As compounds having an epoxy group or an oxetanyl group, those having two epoxy groups in one molecule include "Epikote" (registered trademark) 807, "Epicote" 828, "Epikote" 1002, "Epicote" 1750, and "Epicote". 1007, YX8100-BH30, E1256, E4250, E4275 (trade names, manufactured by Japan Epoxy Co., Ltd.), "Epiclon" (registered trademark) EXA-4880, "Epiclon" EXA-4822, "Epiclon" EXA-9583, HP4032 (Trade names above, manufactured by Dainippon Ink and Chemicals 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 (trade names, manufactured by Kyoeisha Chemical Co., Ltd.), “Denacol” (registered trademark) EX-212L, “Denacol” "EX-214L", "Denacol" EX-216L, "Denacol" EX-252, "Denacol" EX-850L (trade names, manufactured by Nagase ChemteX Co., Ltd.), GAN, GOT (trade names, Nippon Kayaku Co., Ltd.), “Celoxide” (registered trademark) 2021P (trade name, manufactured by Daicel Corporation), “Rikaresin” (registered trademark) DME-100, “Rikaresin” BEO-60E (trade names, Shin Nippon Rika (manufactured by Co., Ltd.) and the like, which are available from each company.

In addition, as those having three or more epoxy groups, VG3101L (trade name, manufactured by Printec Co., Ltd.), “Tepic” (registered trademark) S, “Tepic” G, “Tepic” P (trade names, Nissan Chemical Kogyo Co., Ltd.), "Epiclone" N660, "Epiclone" N695, HP7200 (trade names, manufactured by Dainippon Ink and Chemicals Co., Ltd.), "Denacol" EX-321L (trade name, Nagase ChemteX Corporation) ), NC6000, EPPN502H, NC3000 (trade names, manufactured by Nippon Kayaku Co., Ltd.), “Epotato” (registered trademark) YH-434L (trade name, manufactured by Tohto Kasei Co., Ltd.), EHPE-3150 (trade name , manufactured by Daicel Co., Ltd.), and compounds having two or more oxetanyl groups include OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (these are trade names, Toagosei ( Co., Ltd.), “Ethanacol” (registered trademark) OXBP, “Ethanacol” OXTP (both trade names, manufactured by Ube Industries, Ltd.), and the like, which are available from each company.

(e) The content of the thermal cross-linking agent is preferably 5 parts by mass or more with respect to 100 parts by mass of the alkali-soluble resin (a) because the cross-linking density increases and the chemical resistance improves. Furthermore, when it is 10 parts by mass or more, higher mechanical properties can be obtained. On the other hand, from the viewpoint of the 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 even more preferably 30 parts by mass or less.

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

(f) The colorant is a compound that absorbs light of a specific wavelength, and in particular, a compound that colors by absorbing light of a visible light wavelength (380 to 780 nm).

(f) By containing a coloring agent, the film obtained from the resin composition can be colored, and the light transmitted through the film of the resin composition or the light reflected from the film of the resin composition can be controlled as desired. It is possible to impart colorability to color the material. In addition, it is possible to impart a light-shielding property of shielding light having a wavelength that is absorbed by the (f) colorant from the light transmitted through the resin composition film or the light reflected from the resin composition film.

(f) Coloring agents include compounds that absorb visible light wavelengths and are colored white, red, orange, yellow, green, blue, or purple. By combining two or more colors, the light transmitted through the desired resin composition film of the resin composition or the light reflected from the resin composition film is toned to desired color coordinates. can be improved.

The (f) colorant is preferably (f1) a pigment and/or (f2) a dye, which will be described later.
The (f) coloring agent is preferably (f3) a black agent and/or (f4) a coloring agent other than black.

(f3) A black agent refers to a compound that absorbs light in the visible wavelength range to give a black color, and may be a pigment or a dye.

(f3) Inclusion of a black agent causes the film of the resin composition to be blackened, so that light passing through the film of the resin composition or light reflected from the film of the resin composition is blocked. can be improved. Therefore, it is suitable for light-shielding films such as black matrixes of color filters or black column spacers of liquid crystal displays, and applications requiring high contrast by suppressing external light reflection.

(f3) As the black agent, from the viewpoint of light shielding properties, a compound that absorbs light of all wavelengths of visible light and is colored black is preferable. Mixtures of two or more color compounds selected from white, red, orange, yellow, green, blue or purple are also preferred. By combining two or more of these colors, a pseudo-black color can be obtained, and light-shielding properties can be improved.

In the photosensitive resin composition of the present invention, the (f3) black agent preferably contains one or more selected from black pigments, black dyes and mixtures of dyes of two or more colors. It is more preferable to contain a black pigment.

(f4) Coloring agent other than black refers to a compound that is colored by absorbing light with a wavelength of visible light. That is, it is a coloring agent that colors white, red, orange, yellow, green, blue, or purple, excluding black, as described above.

By containing (f3) a black agent and (f4) a coloring agent other than black, light-shielding properties as well as coloring properties and toning properties can be imparted to the film of the resin composition.

In the photosensitive resin composition of the present invention, the (f4) coloring agent other than black preferably contains a pigment other than black and/or a dye other than black, and has light-shielding properties and heat resistance or weather resistance. From the viewpoint of, it is more preferable to contain a pigment other than black.

The content of the (f) colorant in the solid content of the photosensitive resin composition of the present invention, excluding the solvent, is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. When the content ratio is within the above range, it is possible to improve light shielding properties, colorability and toning properties. On the other hand, the content ratio is preferably 70% by mass or less, more preferably 65% by mass or less, and even more preferably 60% by mass or less. When the content ratio is within the above range, the sensitivity during exposure can be improved.

<(f1) pigment>
In the photosensitive resin composition of the present invention, the (f) colorant preferably contains (f1) a pigment. As a mode in which the (f) colorant contains (f1) pigment, it is preferable that the (f3) black agent and/or (f4) non-black colorant contain (f1) pigment.

(f1) pigment refers to a compound that colors an object by physical adsorption of (f1) pigment on the surface of the object, or interaction between the surface of the object and (f1) pigment. , generally insoluble in solvents and the like. In addition, coloring with the (f1) pigment has a high concealing property and is resistant to fading due to ultraviolet rays or the like.

By including the pigment (f1), the resin composition can be colored in a color having excellent hiding properties, and the light-shielding properties and weather resistance of the film of the resin composition can be improved.

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

Here, the number average particle diameter of the (f1) pigment is measured by a submicron particle size distribution measuring device (N4-PLUS; manufactured by Beckman Coulter, Inc.) or a zeta potential/particle size/molecular weight measuring device (Zetasizer Nano ZSP; (manufactured by Sysmex Corporation) to measure laser scattering due to Brownian motion of the (f1) pigment in solution (dynamic light scattering method). Further, the number average particle size of the (f1) pigment in the cured film obtained from the resin composition can be obtained by measuring using SEM and TEM. (f1) The number average particle size of the pigment is directly measured at a magnification of 50,000 to 200,000 times. (f1) When the pigment is a true sphere, the diameter of the true sphere is measured and taken as the number average particle diameter. (f1) When the pigment is not spherical, the longest diameter (hereinafter referred to as "major axis diameter") and the longest diameter in the direction orthogonal to the major axis diameter (hereinafter referred to as "minor axis diameter") are measured, and the major axis diameter The biaxial average diameter obtained by averaging the minor axis diameters is taken as the number average particle diameter.

(f1) Pigments include, for example, organic pigments and inorganic pigments.

By containing an organic pigment, it is possible to impart colorability or toning properties to the film of the resin composition. In addition, since it is an organic substance, it can transmit or block light of a desired specific wavelength by chemical structure change or functional conversion, thereby adjusting the transmission spectrum or absorption spectrum of the film of the resin composition and improving the toning properties. be able to.

Examples of organic pigments include phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, pyranthrone pigments, dioxazine pigments, thioindigo pigments, diketopyrrolopyrrole pigments, quinophthalone pigments, threne pigments, indoline pigments, Isoindoline pigments, isoindolinone pigments, benzofuranone pigments, perylene pigments, aniline pigments, azo pigments, azomethine pigments, condensed azo pigments, carbon black, metal complex pigments, lake pigments, toner pigments, or Fluorescent pigments may be mentioned. From the viewpoint of heat resistance, anthraquinone-based pigments, quinacridone-based pigments, pyranthrone-based pigments, diketopyrrolopyrrole-based pigments, benzofuranone-based pigments, perylene-based pigments, condensed azo-based pigments, and carbon black are preferred.

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

Examples of anthraquinone-based pigments include aminoanthraquinone-based compounds, diaminoanthraquinone-based compounds, anthrapyrimidine-based compounds, flavanthrone-based compounds, anthantrone-based compounds, indanthrone-based compounds, pyranthrone-based compounds, and violanthrone-based compounds.

Examples of azo pigments include disazo compounds and polyazo compounds.

By containing the inorganic pigment, it is possible to impart colorability or toning properties to the film of the resin composition. In addition, since it is an inorganic substance and has excellent heat resistance and weather resistance, it is possible to improve the heat resistance and weather resistance of the film of the resin composition.

Examples of inorganic pigments include titanium oxide, barium carbonate, zirconium oxide, zinc white, zinc sulfide, lead white, calcium carbonate, barium sulfate, white carbon, alumina white, silicon dioxide, kaolin clay, talc, bentonite, red iron oxide, and molybdenum. Red, molybdenum orange, chrome vermillion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, Viridian, titanium cobalt green, cobalt green, cobalt chrome green, victoria green, ultramarine blue, dark blue, cobalt blue, cerulean blue , cobalt silica blue, cobalt zinc silica blue, manganese violet, cobalt violet, graphite or silver-tin alloys, or fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium or silver, oxidized compounds, composite oxides, sulfides, sulfates, nitrates, carbonates, nitrides, carbides or oxynitrides.

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

The content ratio of the (f1) pigment in the solid content of the photosensitive resin composition of the present invention excluding the solvent is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. When the content ratio is within the above range, it is possible to improve the light-shielding properties, the coloring properties, or the toning properties. On the other hand, the content ratio is preferably 70% by mass or less, more preferably 65% by mass or less, and even more preferably 60% by mass or less. When 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 (f) colorant preferably contains (f2) a dye. As a mode in which the (f) colorant contains (f2) dye, it is preferable that (f2) dye is contained as (f3) black agent and/or (f4) colorant other than black.

The (f2) dye is a compound that colors the object by chemically adsorbing or strongly interacting with a substituent such as an ionic group or a hydroxyl group in the (f2) dye on the surface structure of the object. It is generally soluble in solvents and the like. Further, coloring with (f2) dye has high coloring power and high coloring efficiency because each molecule adsorbs to the object.

By including the dye (f2), the resin composition can be colored in a color having excellent coloring power, and the coloring property and toning property of the film of the resin composition can be improved.

Examples of (f2) dyes include direct dyes, reactive dyes, sulfur dyes, vat dyes, sulfur dyes, acid dyes, metallized dyes, metallized acid dyes, basic dyes, mordant dyes, acid mordant dyes, and disperse dyes. , cationic dyes or fluorescent brightening dyes.

(f2) Dyes include anthraquinone dyes, azo dyes, azine dyes, phthalocyanine dyes, methine dyes, oxazine dyes, quinoline dyes, indigo dyes, indigoid dyes, carbonium dyes, and threne dyes. , perinone dyes, perylene dyes, triarylmethane dyes and xanthene dyes. Anthraquinone-based dyes, azo-based dyes, azine-based dyes, methine-based dyes, triarylmethane-based dyes, and xanthene-based dyes are preferred from the viewpoint of solubility in solvents and heat resistance described later.

(f2) Inclusion of a dye can impart colorability or toning properties to the film of the resin composition.

The content ratio of the dye (f2) in the solid content of the photosensitive resin composition of the present invention excluding the solvent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0.1% by mass. The above is more preferable. When the content ratio is within the above range, it is possible to improve the coloring property or the toning property. On the other hand, the content ratio is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less. When 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.

(g) The dispersant includes (f1) a surface affinity group that interacts with the surface of the pigment or disperse dye, and (f1) a dispersion stabilizing structure that improves the dispersion stability of the pigment or disperse dye. A compound having (g) The dispersion stabilizing structure of the dispersant includes polymer chains and/or substituents having an electrostatic charge.

By containing (g) a dispersant, when the resin composition contains (f1) a pigment or disperse dye, the dispersion stability thereof can be improved, and the resolution after development can be improved. . In particular, for example, when the (f1) pigment is a particle crushed to a number average particle diameter of 1 μm or less, the surface area of the (f1) pigment particles increases, so aggregation of the (f1) pigment particles tends to occur. Become. On the other hand, when the (f1) pigment is contained, the surface of the crushed (f1) pigment interacts with the (g) surface affinity group of the dispersant, and (g) the dispersion stabilizing structure of the dispersant The steric hindrance and/or electrostatic repulsion by (f1) can inhibit aggregation of pigment particles and improve dispersion stability.

Examples of (g) dispersants having a surface affinity group include (g) dispersants having only an amine value, (g) dispersants having an amine value and an acid value, and (g) dispersants having only an acid value. or (g) dispersants that have neither an amine value nor an acid value. (f1) From the viewpoint of improving the dispersion stability of pigment particles, (g) a dispersant having only an amine value and (g) a dispersing agent having an amine value and an acid value are preferred.

The (g) dispersing agent having a surface affinity group preferably has a structure in which an amino group and/or an acid group, which are surface affinity groups, form a salt with an acid and/or a base.

Dispersants (g) having only an amine value include, for example, "DISPERBYK" (registered trademark) -108, -109, -160, -161, -162, -163, -164, -166, -167, -168, -182, -184, -185, -2000, -2008, -2009, -2022, -2050, -2055, -2150 , -2155, -2163, -2164, or -2061, "BYK" (registered trademark) -9075, -9077, -LP-N6919, -LP-N21116 or -LP-N21324 ( All of the above are manufactured by BYK-Chemie Japan Co., Ltd.), "EFKA" (registered trademark) 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4330, 4340, 4400, 4401, 4402, 4403 or 4800 (all manufactured by BASF), "Ajisper" (registered trademark) PB711 (manufactured by Ajinomoto Fine-Techno Co., Inc.) or "SOLSPERSE" (registered trademark) 13240, 13940, 20000, 71000 or 76500 (all manufactured by Lubrizol).

Dispersants (g) having an amine value and an acid value include, for example, "ANTI-TERRA" (registered trademark)-U100 or -204, "DISPERBYK" (registered trademark)-106, -140 and -142. , -145, -180, -2001, -2013, -2020, -2025, -187 or -191, "BYK" (registered trademark) -9076 (manufactured by BYK Chemie Japan Co., Ltd. , "Ajisper" (registered trademark) PB821, PB880 or PB881 (all manufactured by Ajinomoto Fine-Techno Co., Ltd.) or "SOLSPERSE" (registered trademark) 9000, 11200, 13650, 24000, 32000, 32500, 32500, 32600, 33000, 34750, 35100, 35200, 37500, 39000, 56000, or 76500 (all manufactured by Lubrizol).

Dispersants (g) having only an acid value include, for example, "DISPERBYK" (registered trademark) -102, -110, -111, -118, -170, -171, -174, -2060 or -2096, "BYK" (registered trademark) -P104, -P105 or -220S (all manufactured by BYK Chemie Japan Co., Ltd.) or "SOLSPERSE" (registered trademark) 3000, 16000, 17000, 18000, 21000, 26000, 28000, 36000, 36600, 38500, 41000, 41090, 53095 or 55000 (all manufactured by Lubrizol).

As the (g) dispersant having neither an amine value nor an acid value, for example, "DISPERBYK" (registered trademark) -103, -2152, -2200 or -192 (both of which are BYK Chemie Japan ( Co., Ltd.) or "SOLSPERSE" (registered trademark) 27000, 54000 or X300 (all of which are manufactured by Lubrizol).

(g) The amine value of the dispersant is preferably 5 mgKOH/g or more, more preferably 8 mgKOH/g or more, and even 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 even more preferably 100 mgKOH/g or less. When the amine value is within the above range, the storage stability of the resin composition can be improved.

The amine value referred to herein is (g) the mass of potassium hydroxide equivalent to the acid that reacts with 1 g of the dispersant, and the unit is mgKOH/g. (g) It can be determined by titration with an aqueous potassium hydroxide solution after neutralizing 1 g of the dispersant with an acid. From the value of the amine value, the amine equivalent weight (unit: g/mol), which is the resin mass per 1 mol of amino groups, can be calculated, and (g) the number of amino groups in the dispersant can be determined.

(g) The acid value of the dispersant is preferably 5 mgKOH/g or more, more preferably 8 mgKOH/g or more, and even more preferably 10 mgKOH or more. When 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 even more preferably 150 mgKOH/g or less. When the acid value is within the above range, the storage stability of the resin composition can be improved.

The acid value as used herein refers to the mass of potassium hydroxide that reacts with (g) per 1 g of the dispersant, and the unit is mgKOH/g. (g) It can be determined by titrating 1 g of the dispersant with an aqueous potassium hydroxide solution. From the acid value, the acid equivalent (unit: g/mol), which is the mass of resin per 1 mol of acidic groups, can be calculated, and (g) the number of acidic groups in the dispersant can be determined.

The (g) dispersant having a polymer chain includes an acrylic resin-based dispersant, a polyoxyalkylene ether-based dispersant, a polyester-based dispersant, a polyurethane-based dispersant, a polyol-based dispersant, a polyethyleneimine-based dispersant, or a polyallylamine-based dispersant. Dispersants are included. From the viewpoint of pattern processability with an alkaline developer, an acrylic resin-based dispersant, a polyoxyalkylene ether-based dispersant, a polyester-based dispersant, a polyurethane-based dispersant, or a polyol-based dispersant is preferred.

When the photosensitive resin composition of the present invention contains a disperse dye as (f1) pigment and/or (f2) dye, the content ratio of (g) dispersant in the photosensitive resin composition of the present invention is (f1 ) pigment and/or (f2) dye, and (g) when the total amount of dispersant is 100% by mass, preferably 1% by mass or more, more preferably 5% by mass or more, and even 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 even more preferably 50% by mass or less. When 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 sensitizer is a compound capable of absorbing energy due to exposure, generating excited triplet electrons by internal conversion and intersystem crossing, and transferring energy to the above-mentioned (b2) photopolymerization initiator or the like. Say.

By containing a sensitizer, the sensitivity at the time of exposure can be improved. This is because (b2) the sensitizer absorbs long-wavelength light that the photopolymerization initiator or the like does not absorb, and the energy is transferred from the sensitizer to the (b2) photopolymerization initiator or the like. This is presumed to be because the photoreaction efficiency can be improved.

As the sensitizer, a thioxanthone-based sensitizer is preferred. Thioxanthone-based sensitizers include, for example, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone. .

The content of the sensitizer in the photosensitive resin composition of the present invention is 0.01 parts by mass or more when the total of (a) the alkali-soluble resin and (d) the radically polymerizable compound is 100 parts by mass. It is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and particularly preferably 1 part by mass or more. When 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, even 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 low taper pattern shape can be obtained.

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

A chain transfer agent refers to a compound capable of accepting radicals from the growing end of a polymer chain obtained by radical polymerization during exposure and transferring the radicals to another polymer chain.

By containing a chain transfer agent, the sensitivity at the time of exposure can be improved. It is presumed that this is because the radicals generated by the exposure are radically transferred to other polymer chains by the chain transfer agent, thereby causing radical cross-linking to the deep part of the film. In particular, for example, when the resin composition contains (f3) a black agent as the (f) colorant described above, the light from exposure is absorbed by the (f3) black agent, so the light does not reach deep into the film. Sometimes. On the other hand, when a chain transfer agent is contained, the radical transfer by the chain transfer agent causes radical cross-linking to the deep part of the film, so that the sensitivity during exposure can be improved.

Moreover, a pattern shape with a low taper can be obtained by containing a chain transfer agent. It is presumed that this is because the radical transfer by the chain transfer agent can control the molecular weight of the polymer chain obtained by radical polymerization during exposure. That is, the inclusion of a chain transfer agent inhibits the formation of a significant high-molecular-weight polymer chain due to excessive radical polymerization during exposure, and suppresses an increase in the softening point of the resulting film. Therefore, it is considered that the reflow property of the pattern at the time of heat curing is improved, and a pattern shape with a low taper can be obtained.

As the chain transfer agent, a thiol-based chain transfer agent is preferred. Thiol-based chain transfer agents include, for example, β-mercaptopropionic acid, methyl β-mercaptopropionate, ethyl β-mercaptopropionate, 2-ethylhexyl β-mercaptopropionate, n-octyl β-mercaptopropionate, β- methoxybutyl mercaptopropionate, β-stearyl mercaptopropionate, β-isononyl mercaptopropionate, β-mercaptobutanoic acid, methyl β-mercaptobutanoate, ethyl β-mercaptobutanoate, 2-ethylhexyl β-mercaptobutanoate, β - n-octyl mercaptobutanoate, β-methoxybutyl β-mercaptobutanoate, stearyl β-mercaptobutanoate, isononyl β-mercaptobutanoate, methyl thioglycolate, n-octyl thioglycolate, methoxybutyl thioglycolate, 1, 4-bis(3-mercaptobutanoyloxy)butane, 1,4-bis(3-mercaptopropionyloxy)butane, 1,4-bis(thioglycoloyloxy)butane, ethylene glycol bis(thioglycolate), tri Methylolethane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), methylolpropane tris (thioglycolate), 1,3,5-tris[(3-mercaptopropionyloxy)ethyl]isocyanuric acid, 1,3,5-tris[(3-mercaptobutanoyloxy)ethyl]isocyanuric acid, Pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (thioglycolate), dipentaerythritol hexakis (3-mercaptopropionate) or dipentaerythritol hexa kiss (3-mercaptobutyrate). From the viewpoint of improving sensitivity during exposure and a low taper pattern shape, 1,4-bis(3-mercaptobutanoyloxy)butane, 1,4-bis(3-mercaptopropionyloxy)butane, 1,4-bis( thioglycoloyloxy)butane, ethylene glycol bis(thioglycolate), trimethylolethane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate) pionate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(thioglycolate), 1,3,5-tris[(3-mercaptopropionyloxy)ethyl]isocyanuric acid, 1,3, 5-tris[(3-mercaptobutanoyloxy)ethyl]isocyanuric acid, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (thioglycolate), di Pentaerythritol hexakis (3-mercaptopropionate) or dipentaerythritol hexakis (3-mercaptobutyrate) are preferred.

The content of the chain transfer agent in the photosensitive resin composition of the present invention is 0.01 parts by mass or more when the total of (a) the alkali-soluble resin and (d) the radically polymerizable compound is 100 parts by mass. It is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and particularly preferably 1 part by mass or more. When the content is within the above range, the sensitivity during exposure can be improved, and a pattern shape with a low taper 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, even 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 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 polymerization inhibitor captures the radicals generated during exposure or the radicals at the growing terminal of the polymer chain obtained by radical polymerization during exposure and holds them as stable radicals, thereby terminating radical polymerization. Refers to possible compounds.

By containing an appropriate amount of the polymerization inhibitor, the generation of residue after development can be suppressed, and the resolution after development can be improved. It is presumed that this is because the polymerization inhibitor captures excess radicals generated during exposure or radicals at growing ends of high-molecular-weight polymer chains, thereby suppressing the progress of excessive radical polymerization.

As the polymerization inhibitor, a phenol-based polymerization inhibitor is preferred. Phenolic polymerization inhibitors include, for example, 4-methoxyphenol, 1,4-hydroquinone, 1,4-benzoquinone, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 4 -t-butylcatechol, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-1,4-hydroquinone or 2,5-di-t-amyl-1,4 - hydroquinone or "IRGANOX" (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, 3114, 565 or 295 (both of which are manufactured by BASF).

The content of the polymerization inhibitor in the photosensitive resin composition of the present invention is 0.01 parts by mass or more when the total of (a) the alkali-soluble resin and (d) the radically polymerizable compound is 100 parts by mass. It is preferably 0.03 parts by mass or more, more preferably 0.05 parts by mass or more, and particularly preferably 0.1 parts by mass or more. When 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, even more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less. When 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 improver. Adhesion improvers include vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, Silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents, aromatic amine compounds and alkoxy group-containing Examples thereof include compounds obtained by reacting silicon compounds. You may contain 2 or more types of these. By containing these adhesion improvers, it is possible to improve the adhesion to a base material such as a silicon wafer, ITO, SiO ₂ , silicon nitride, etc. when developing a photosensitive resin film. In addition, resistance to oxygen plasma and UV ozone treatment used for cleaning can be enhanced. The content of the adhesion improver is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the (a) alkali-soluble resin.

<Surfactant>
The photosensitive resin composition used in the present invention may optionally 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. Commercially available compounds can be used as surfactants. Specifically, silicone-based surfactants include SH series, SD series, and ST series from Toray Dow Corning Silicone Co., Ltd., "BYK" series from BYK Chemie Japan, Examples include the KP series of Shin-Etsu Silicone Co., Ltd., the Disfoam series of NOF Corporation, the TSF series of Toshiba Silicone Co., Ltd., and the like. Sumitomo 3M's Florado series, Asahi Glass's "Surflon (registered trademark)" series, "Asahi Guard (registered trademark)" series, Shin-Akita Kasei's EF series, Omnova Solution's Polyfox series, and the like. Examples of surfactants composed of acrylic and/or methacrylic polymers include the Polyflow series of Kyoeisha Chemical Co., Ltd., and the "Disparon (registered trademark)" series of Kusumoto Kasei Co., Ltd., which are available from each company. , but not limited to.

The content of the surfactant is preferably 0.001 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the (a) alkali-soluble resin. Within the above range, the wettability with the substrate and the uniformity of the film thickness of the coating film can be improved without causing defects such as air bubbles and pinholes.

<Compound having a phenolic hydroxyl group>
The photosensitive resin composition used in the present invention may optionally contain a compound having a phenolic hydroxyl group for the purpose of compensating for the alkali developability of the photosensitive resin composition. Examples of 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, and BisP-EZ. , Bis26X-CP, BisP-PZ, BisP-IPZ, BisCRIPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (tetrakis 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 , Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP, (the above are trade names, available 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 (these are trade names, available from Asahi Organic Chemicals Industry Co., Ltd.), 1,4-dihydroxynaphthalene, 1,5-dihydroxy Naphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,4-dihydroxyquinoline, 2,6-dihydroxyquinoline , 2,3-dihydroxyquinoxaline, anthracene-1,2,10-triol, anthracene-1,8,9-triol, 8-quinolinol and the like. By containing a compound having these phenolic hydroxyl groups, the resulting photosensitive resin composition is almost insoluble in an alkaline developer before exposure, and readily dissolves in an alkaline developer after exposure. Less film loss and easy development in a short time. Therefore, it becomes easier to improve the sensitivity.

The content of such a 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 the (a) alkali-soluble resin. By setting it as the above-mentioned range, after maintaining high heat resistance, the alkali developability of a photosensitive resin composition can be improved.

<Inorganic particles>
In addition, the photosensitive resin composition used in the present invention may contain inorganic particles for the purpose of improving the dielectric constant of the cured film, improving the hardness, reducing the coefficient of thermal expansion, and the like. Preferred specific examples include silicon oxide, titanium oxide, barium titanate, barium sulfate, barium oxide, zirconium oxide, hafnium oxide, tantalum oxide, tungsten oxide, yttrium oxide, alumina and talc. In particular, for the purpose of improving the relative dielectric constant of the cured film, titanium oxide (εr = 115), zirconium oxide (εr = 30), barium titanate (εr = 400), or Hafnium oxide (εr=25) is a particularly preferred example, but is not limited thereto. The primary particle diameter of these inorganic particles is preferably 100 nm or less, more preferably 60 nm or less. The particle size of each inorganic particle was measured with a scanning electron microscope (scanning electron microscope manufactured by JEOL Ltd., JSM-6301NF). The primary particle size of the inorganic particles used in the present invention can be calculated by measuring the diameter of 100 particles randomly selected from a scanning electron micrograph and calculating the arithmetic mean.

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 the (a) alkali-soluble resin. When the amount is within the above range, the effect of adding the inorganic particles, such as the improvement of the dielectric constant, can be exhibited while maintaining the alkali developing performance.

<Thermal acid generator>
The photosensitive resin composition used in the present invention may contain a thermal acid generator. The thermal acid generator generates an acid when heated to accelerate the cross-linking reaction of the thermal cross-linking agent. Cyclization can be promoted and the mechanical properties of the cured film can be further improved.

The thermal decomposition initiation temperature of the thermal acid generator used in the present invention is preferably 50° C. to 270° C., more preferably 250° C. or less. In addition, no acid is generated when the photosensitive resin composition of the present invention is applied to a substrate and then dried (prebaking: about 70 to 140° C.), and the final heating (curing: about It is preferable to select one that generates an acid at 100 to 400° C.), because it can suppress a decrease in sensitivity during development.

The acid generated from the thermal acid generator used in the present invention is preferably a strong acid, and examples thereof include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid and butanesulfonic acid. and haloalkylsulfonic acids such as trifluoromethylsulfonic acid and the like are preferred. They are used as salts, such as onium salts, or as covalent compounds, such as imidosulfonates. You may contain 2 or more types of these.

The content of the thermal acid generator used in the present invention is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the (a) alkali-soluble resin. By setting the amount within the above range, the effect of adding the above-described thermal acid generator can be exhibited while maintaining high heat resistance.

<(i) Cyclic amide, cyclic urea and derivatives thereof>
The photosensitive resin composition used for the cured film of the present invention preferably contains (i) one or more compounds selected from the group consisting of cyclic amides, cyclic ureas and derivatives thereof. That is, the cured film of the present invention preferably contains (i) one or more compounds selected from the group consisting of cyclic amides, cyclic ureas and derivatives thereof. By containing (i) one or more compounds selected from the group consisting of cyclic amides, cyclic ureas, and derivatives thereof in the cured film, the compound (i) acts as a quencher for acidic gases, thereby increasing the brightness of the emitted light. It is presumed that it is possible to suppress deterioration and pixel shrinkage and to provide sufficient long-term reliability as an organic EL device.

(i) one or more compounds selected from the group consisting of cyclic amides, cyclic ureas and derivatives thereof preferably have a structure represented by the following general formula (11) and contain two or more of these You may

(In general formula (11), u represents an integer of 1 to 4, Y represents CH or a nitrogen atom, and R ¹⁸ and R ¹⁹ each independently represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. )
(i) One or more compounds selected from the group consisting of cyclic amides, cyclic ureas, and derivatives thereof preferably have a boiling point of 210°C or higher from the viewpoint of making it easier to remain in the film after heat treatment. Moreover, the boiling point is preferably 400° C. or lower from the viewpoint of suppressing unevenness during coating. If the boiling point cannot be measured at normal pressure, it can be converted to the boiling point at normal pressure using a boiling point conversion table.

Specific examples of cyclic amides, cyclic ureas and derivatives thereof include 2-pyrrolidone, N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-isopropyl- 2-pyrrolidone, N-butyl-2-pyrrolidone, N-(t-butyl)-2-pyrrolidone, N-pentyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N -ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, N-(2-hydroxyethyl)-2-pyrrolidone, N-phenyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N,N' -dimethylpropylene urea, 2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, 2-piperidone, ε-caprolactam and the like. Among these, N-cyclohexyl-2-pyrrolidone (boiling point: 154° C./7 mmHg, boiling point at normal pressure: 305° C.), N-(2-hydroxyethyl)-2-pyrrolidone (boiling point: 175° C./10 mmHg, normal 313° C. in pressure boiling point conversion) is preferable because it has a high boiling point and tends to remain in the film even after heat treatment.

(i) The total content of one or more compounds selected from the group consisting of cyclic amides, cyclic ureas and derivatives thereof is 0.005% by mass or more and 5% by mass or less in 100% by mass of the cured film. is preferred. In the photosensitive resin composition that forms a cured film, the amount of the compound (i) added is preferably 0.1 parts by mass or more, more preferably 1 part by mass, relative to 100 parts by mass of the (a) alkali-soluble resin. or more, preferably 15 parts by mass or less, more preferably 10 parts by mass or less. When the amount of the compound (i) added is 0.1 parts by mass or more, the excellent long-term reliability of the organic EL device can be enhanced, and when it is 15 parts by mass or less, the pattern can be formed with excellent sensitivity. can be done.

<Method for producing resin composition>
Next, a method for producing the photosensitive resin composition of the present invention will be described. For example, by dissolving the above components (a) to (c) and, if necessary, a thermal cross-linking agent, an adhesion improver, a surfactant, a compound having a phenolic hydroxyl group, inorganic particles, a thermal acid generator, etc., A flexible resin composition can be obtained. Dissolution methods include stirring and heating. When heating, the heating temperature is preferably set within 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, and for example, there is a method of dissolving compounds in order of low solubility. In addition, for ingredients that tend to generate air bubbles during stirring and dissolution, such as surfactants and some adhesion improvers, dissolving the other ingredients before adding them at the end will prevent poor dissolution of other ingredients due to air bubbles. can be prevented.

The obtained photosensitive resin composition is preferably filtered using a filtration filter to remove dust and particles. Examples of filter pore sizes include, but are not limited to, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, 0.02 μm. Materials for the filter include polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., and polyethylene and nylon are preferred.

<Cured film>
Next, a method for producing a cured film using the photosensitive resin composition of the present invention will be described 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 comprises the steps of applying the photosensitive resin composition on a substrate to form a photosensitive resin film, drying the photosensitive resin film, It includes a step of exposing the photosensitive resin film, a step of developing the exposed photosensitive resin film, and a step of heat curing. Details of each step are 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, or the like to obtain a coating film of the photosensitive resin composition. Among these, the slit coating method is preferably used. The slit coating method is advantageous in terms of cost reduction because it can be applied with a small amount of application liquid. The amount of the coating liquid required for the slit coating method is, for example, about 1/5 to 1/10 of that for the spin coating method. The slit nozzle used for coating is not particularly limited, and those marketed by multiple manufacturers can be used. Specifically, "Linear Coater" manufactured by Dainippon Screen Mfg. Co., Ltd., "Spinless" manufactured by Tokyo Ohka Kogyo Co., Ltd., "TS Coater" manufactured by Toray Engineering Co., Ltd., "Table Coater" manufactured by Chugai Ro Co., Ltd. , "CS Series" and "CL Series" manufactured by Tokyo Electron Ltd., "Inline Slit Coater" manufactured by Thermatronics Trading Co., Ltd., and "Head Coater HC Series" manufactured by Hirata Corporation. The coating speed is generally in the range of 10 mm/sec to 400 mm/sec. The film thickness of the coating film varies depending on the solid content concentration and viscosity of the photosensitive resin composition, but it is usually applied so that the film thickness after drying is 0.1 to 10 μm, preferably 0.3 to 5 μm. be.

Prior to coating, the substrate to be coated with the photosensitive resin composition may be pretreated with the above-described adhesion improver. For example, a solution obtained by dissolving 0.5 to 20% by mass of an adhesion improver in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate is used. and a method of treating the substrate surface. Methods for treating the substrate surface include spin coating, slit die coating, bar coating, dip coating, spray coating, vapor treatment, and the like.

After coating, drying treatment under reduced pressure is performed as necessary. It is common to dry under reduced pressure together with the substrate on which the coating film is formed. For example, a substrate having a coating film formed thereon is placed on proxy pins placed in a vacuum chamber, and dried under reduced pressure by reducing the pressure in the vacuum chamber. At this time, if the substrate and the top plate of the vacuum chamber are separated from each other, a large amount of air between the substrate and the top plate of the vacuum chamber flows during drying under reduced pressure, which tends to cause unevenness. Therefore, it is preferable to adjust the proxy pin height so as to narrow the gap. 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 speed of drying under reduced pressure depends on the vacuum chamber volume, the vacuum pump capacity, the diameter of the pipe between the chamber and the pump, etc. For example, in the state where there is no coated substrate, the pressure in the vacuum chamber is reduced to 40 Pa after 60 seconds. set and used. A general vacuum drying time is often about 30 seconds to 100 seconds, and the ultimate pressure in the vacuum chamber at the end of the vacuum drying is usually 100 Pa or less with the coated substrate in place. By setting the ultimate pressure to 100 Pa or less, the surface of the coating film can be kept in a non-sticky and dry state, thereby suppressing surface contamination and generation of particles during subsequent substrate transport.

After coating or drying under reduced pressure, the coating film is generally dried by heating. This step is also called pre-baking. Dry using a hot plate, oven, infrared rays, etc. When a hot plate is used, the coating film is held and heated directly on the plate or on a jig such as a proxy pin placed on the plate. Materials for proxy pins include metal materials such as aluminum and stainless steel, and synthetic resins such as polyimide resin and "Teflon (registered trademark)." . The height of the proxy pin varies depending on the size of the substrate, the type of coating film, the purpose of heating, etc., but is preferably about 0.1 to 10 mm. The heating temperature varies depending on the type and purpose of the coating film, and is preferably in the range of 50° C. to 180° C. for 1 minute to several hours.

Next, a method for forming a pattern from the obtained photosensitive resin film will be described. The photosensitive resin film is exposed to actinic rays through a mask having a desired pattern. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc. In the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm) and g-rays (436 nm) of a mercury lamp. . In the case of positive photosensitivity, the exposed portion dissolves in the developer. In the case of negative photosensitivity, the exposed areas are cured and rendered insoluble in the developer.

After the exposure, a developer is used to form a desired pattern by removing the exposed portion in the case of a positive type and the non-exposed portion in the case of a negative type. As a developer for both positive and negative types, tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, Aqueous solutions of alkaline compounds such as dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine and hexamethylenediamine are preferred. In some cases, these alkaline aqueous solutions are added with a polar solvent such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be added alone or in combination. good. As a developing method, methods such as spray, puddle, immersion, and ultrasonic waves are possible.

Next, the pattern formed by development is preferably rinsed with distilled water. Also here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the distilled water for rinsing.

Next, heat curing is performed. Heat curing can remove components with low heat resistance, so heat resistance and chemical resistance can be improved. In particular, when the photosensitive resin composition of the present invention contains an alkali-soluble resin selected from a polyimide precursor, a polybenzoxazole precursor, a copolymer thereof, or a copolymer of them and a polyimide, heating Since imide rings and oxazole rings can be formed by curing, heat resistance and chemical resistance can be improved. , the thermal curing reaction can be advanced by heat curing, and the heat resistance and chemical resistance can be improved. For this heat curing, a temperature is selected and the temperature is raised stepwise, or a certain temperature range is selected and the temperature is raised continuously for 5 minutes to 5 hours. For example, heat treatment is performed at 150° C. and 250° C. for 30 minutes each. Alternatively, a method of linearly raising the temperature from room temperature to 300° C. over 2 hours can be used. The heat curing conditions in the present invention are preferably 300° C. or higher, more preferably 350° C. or higher, in order to reduce the amount of outgas generated from the cured film. In addition, the temperature is preferably 500° C. or lower, more preferably 450° C. or lower, from the viewpoint of imparting sufficient film toughness to the cured film.

Next, a method for producing a cured film using a photosensitive sheet formed from the photosensitive resin composition of the present invention will be described. Here, the photosensitive sheet is defined as a sheet obtained by coating a peelable substrate with a photosensitive resin composition and drying the composition.

When a photosensitive sheet formed from the photosensitive resin composition of the present invention is used, if the photosensitive sheet has a protective film, it is peeled off, the photosensitive sheet and the substrate are opposed to each other, and they are bonded together by thermocompression bonding. , to obtain a photosensitive resin film. The photosensitive sheet can be obtained by applying the photosensitive resin composition of the present invention onto a support film made of polyethylene terephthalate or the like, which is a peelable substrate, and drying it.

Thermocompression bonding can be performed by heat press treatment, heat lamination treatment, heat vacuum lamination treatment, or the like. The bonding temperature is preferably 40° C. or higher from the viewpoint of adhesion to the substrate and embedding. When the photosensitive sheet has photosensitivity, the bonding temperature is preferably 140° C. or less in order to prevent the photosensitive sheet from curing during bonding and lowering the resolution of pattern formation in the exposure/development process.

The photosensitive resin film obtained by laminating the photosensitive sheet to the substrate follows the steps of exposing the photosensitive resin film, developing the exposed photosensitive resin film, and heat curing. can be used to form a cured film.

A cured film obtained by curing the photosensitive resin composition or the photosensitive sheet of the present invention can be used for electronic parts such as an organic EL display device, a semiconductor device, and a multilayer wiring board. Specifically, insulating layers of organic EL elements, flattening layers of substrates with drive circuits of display devices using organic EL elements, interlayer insulating films between rewirings of semiconductor devices or semiconductor parts, passivation films of semiconductors, semiconductors Appropriate for applications such as protective films for devices, interlayer insulating films for multilayer wiring for high-density mounting, wiring protective insulating layers for circuit boards, on-chip microlenses for solid-state imaging devices, and flattening layers for various displays and solid-state imaging devices. be done. Examples of electronic devices having a surface protective film, an interlayer insulating film, or the like on which the cured film of the present invention is disposed include MRAMs with low heat resistance. That is, the cured film of the present invention is suitable for use as a surface protective film for MRAM. In addition to MRAM, polymer ferroelectric RAM (PFRAM) and phase change memory (PCRAM, or Ovonics Unified Memory (OUM)), which are promising next-generation memories, also have heat resistance compared to conventional memories. There is a high possibility of using new materials with low cost. Therefore, the cured film of the present invention is also suitable for these surface protective films. Further, 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, organic electroluminescence device It can be used for an insulating layer of a display device (organic electroluminescence device) or the like. An organic EL display device will be described below as an example.

<Organic EL display device>
The organic EL display device of the present invention has a drive circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer and a second electrode on a substrate, and the planarizing layer and/or the insulating layer is the hardening layer of the present invention. consists of a membrane. Taking an example of an active matrix type display device, a substrate such as a glass or resin film is provided with TFTs and wirings located on the sides of the TFTs and connected to the TFTs, and unevenness is covered thereon. A planarization layer is thus provided, and a display element is provided on the planarization layer. The display element and the wiring are connected through a contact hole formed in the planarization layer. In particular, flexible organic EL display devices have become mainstream in recent years, and it is preferable that the organic EL display device has a substrate having the aforementioned drive circuit made of a resin film. When a cured film obtained by curing the photosensitive resin composition or the photosensitive sheet of the present invention is used as an insulating layer or a flattening layer of such a flexible display, it is particularly preferably used because of its excellent flexibility. Polyimide is particularly preferable as the resin film from the viewpoint of improving adhesion to a cured film obtained by curing the photosensitive resin composition or photosensitive sheet of the present invention.

FIG. 1 shows a cross-sectional view of an example of a TFT substrate. Bottom gate type or top gate type TFTs (thin film transistors) 1 are provided in a matrix on a substrate 6 , and an insulating layer 3 is formed to cover the TFTs 1 . A wiring 2 connected to the TFT 1 is provided on the insulating layer 3 . Further, a planarizing layer 4 is provided on the insulating layer 3 so as to bury the wiring 2 therein. A contact hole 7 reaching the wiring 2 is provided in the planarization layer 4 . An ITO (transparent electrode) 5 is formed on the planarization layer 4 while being connected to the wiring 2 through the contact hole 7 . Here, the ITO 5 becomes an electrode of a display element (for example, an organic EL element). An insulating layer 8 is formed so as to cover the periphery of the ITO 5 . The organic EL element may be of a top emission type in which light is emitted from the side opposite to the substrate 6, or may be of a bottom emission type in which light is extracted from the substrate 6 side. In this manner, an active matrix type organic EL display device is obtained in which the TFTs 1 for driving the organic EL elements are connected to the respective organic EL elements.

The insulating layer 3, the planarizing layer 4 and/or the insulating layer 8 are formed by the steps of forming a photosensitive resin film made of the resin composition or resin sheet of the present invention, exposing the photosensitive resin film, and It can be formed by a step of developing the exposed photosensitive resin film and a step of heat-treating the developed photosensitive resin film. An organic EL display device can be obtained by a manufacturing method including these steps.

The photosensitive resin composition of the present invention is also suitably used for fan-out wafer level packages (fan-out WLP). The fan-out WLP uses sealing resin such as epoxy resin to provide an extended portion around the semiconductor chip, rewires from the electrodes on the semiconductor chip to the extended portion, and mounts solder balls on the extended portion. It is a semiconductor package that secures the required number of terminals. In the fan-out WLP, wiring is installed so as to straddle the boundary formed by the main surface of the semiconductor chip and the main surface of the sealing resin. That is, an interlayer insulating film is formed on a base material composed of two or more kinds of materials such as a semiconductor chip with metal wiring and a sealing resin, and wiring is formed on the interlayer insulating film. In addition to this, in a type of semiconductor package in which a semiconductor chip is embedded in a recess formed in a glass epoxy resin substrate, wiring is installed so as to straddle the boundary line between the main surface of the semiconductor chip and the main surface of the printed circuit board. . Also in this aspect, an interlayer insulating film is formed on a substrate made of two or more materials, and wiring is formed on the interlayer insulating film. The cured film obtained by curing the photosensitive resin composition of the present invention has high adhesion to a semiconductor chip provided with metal wiring, and also has high adhesion to epoxy resin or the like to a sealing resin. It is suitably used as an interlayer insulating film provided on a base material composed of at least one kind of material.

EXAMPLES The present invention will be described below with reference to examples, etc., but the present invention is not limited to these examples. In addition, evaluation of the photosensitive resin composition in the examples was performed by the following methods. Incidentally, Examples 1 to 12 shall be read as Reference Examples 1 to 12.

<Method for measuring film thickness>
Using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., the film thickness after pre-baking, development and curing was measured for polyimide with a refractive index of 1.629.

<Measurement of number average particle size of pigment>
Using a zeta potential/particle size/molecular weight measuring device (Zetasizer Nano ZSP; manufactured by Sysmex Corporation), using PGMEA as a dilution solvent, the pigment dispersion is adjusted to a concentration of 1.0 × 10 ^-5 to 40% by volume. After diluting, the refractive index of the dilution solvent was set to PGMEA and the refractive index of the object to be measured was set to 1.8, and a laser beam 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) prepared in Examples and Comparative Examples was spin-coated on an 8-inch silicon wafer, and then hot plated at 120 ° C. ( It was baked for 3 minutes using a coating and developing apparatus Act-8 manufactured by Tokyo Electron Ltd. to prepare a prebaked film having a thickness of 2.5 μm. This film was exposed using an i-line stepper (NIKON NSR i9) at an exposure dose of 0 to 1000 mJ/cm ² in steps of 10 mJ/cm ² . After exposure, the film was developed with a 2.38% by mass tetramethylammonium (TMAH) aqueous solution (ELM-D, manufactured by Mitsubishi Gas Chemical Co., Ltd.) for 90 seconds and then rinsed with pure water to develop an isolated pattern of 10 μm. Membrane A was obtained.

Using an FPD inspection microscope (MX-61L; manufactured by Olympus Co., Ltd.), the resolution pattern of the prepared film after development was observed, and the exposure dose to form a 10 μm line-and-space pattern with a width of 1:1. (referred to as optimum exposure Eop) was taken as the sensitivity.

(1-2) Sensitivity Evaluation of Negative Photosensitive Resin Composition The photosensitive resin compositions (varnishes) prepared in Examples and Comparative Examples were applied onto an ITO substrate by a spin coater (MS-A100; manufactured by Mikasa Co., Ltd.). After applying by spin coating at an arbitrary number of rotations, pre-bake at 100 ° C. for 120 seconds using a hot plate (SCW-636; manufactured by Dainippon Screen Mfg. Co., Ltd.) to pre-bake to a film thickness of about 2.0 μm. A membrane was prepared. The prepared pre-baked film is subjected to a grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International) using a double-sided alignment single-sided exposure device (mask aligner PEM-6M; manufactured by Union Optical Co., Ltd.). ), patterning exposure was performed with i-line (wavelength: 365 nm), h-line (wavelength: 405 nm) and g-line (wavelength: 436 nm) of an extra-high pressure mercury lamp. After exposure, using a small developing device for photolithography (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), the film was developed with a 2.38 wt% TMAH aqueous solution for 60 seconds and rinsed with water for 30 seconds to form an isolated pattern of 10 µm. A developed film having

Using an FPD inspection microscope (MX-61L; manufactured by Olympus Co., Ltd.), the resolution pattern of the prepared film after development was observed, and the exposure dose to form a 10 μm line-and-space pattern with a width of 1:1. (referred to as optimum exposure Eop) was taken as the sensitivity.

(2) Remaining film ratio evaluation The ratio of the film thickness of the developed film to the prebaked film is defined as the residual film ratio (remaining film ratio = (film thickness of developed film) / (film thickness of prebaked film) × 100), and 80% or more Passed.

(3) Evaluation of bendability On a PI film substrate, a spin coater (MS-A100; manufactured by Mikasa Co., Ltd.) was used to apply varnish by spin coating at an arbitrary number of rotations, followed by a hot plate (SCW-636; (manufactured by Dainippon Screen Mfg. Co., Ltd.) was prebaked at 120° C. for 120 seconds to prepare a prebaked film having a film thickness of about 3.0 μm. Using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.), the pre-baked film is heated to 250°C at an oxygen concentration of 20 ppm or less at a rate of 5°C/min, and heat-treated at 250°C for 1 hour. was performed to prepare a cured film of the composition.

After thermal curing, the prepared PI film substrate having the cured film was cut into a size of 50 mm long×10 mm wide. With the surface of the cured film facing outward, the PI film substrate was held for 30 seconds while being bent at 180° along a line of 25 mm in length. After 30 seconds, open the bent PI film substrate, using an FPD inspection microscope (MX-61L; manufactured by Olympus Co., Ltd.), to observe the bending portion on a vertical 25 mm line on the surface of the cured film, the appearance of the surface of the cured film. evaluated the changes. A case where there was no peeling of the cured film from the PI film substrate and no appearance change such as cracks or deformation on the surface of the cured film was evaluated as pass (A), and other cases were evaluated as failure (B).

(4) Long-Term Reliability Evaluation of Organic EL Display Device FIG. 1 shows a schematic diagram of the manufacturing procedure of an organic EL display device. First, an ITO transparent conductive film of 10 nm was formed on the entire surface of the alkali-free glass substrate 9 of 38 mm×46 mm by sputtering, and etched as the first electrode 10 . At the same time, an auxiliary electrode 11 for taking out the second electrode was also formed. The obtained substrate was ultrasonically cleaned for 10 minutes with Semico Clean 56 (trade name, manufactured by Furuuchi Chemical Co., Ltd.) and then cleaned with ultrapure water. Next, the photosensitive resin composition shown in Table 5 was applied to the entire surface of the substrate by spin coating, and prebaked on a hot plate at 120° C. for 2 minutes. This film was exposed to UV light through a photomask, developed with a 2.38% by mass TMAH aqueous solution to dissolve unnecessary portions, and rinsed with pure water. The resulting resin pattern was heat-treated at 250° C. for 1 hour in a nitrogen atmosphere using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.). In this way, the insulating layer 12 having a width of 70 μm and a length of 260 μm is arranged at a pitch of 155 μm in the width direction and a pitch of 465 μm in the length direction, and each opening exposes the first electrode. Formed only in the effective area. In this manner, an insulating layer having an insulating layer aperture ratio of 25% was formed in a square substrate effective area of 16 mm on a side. The thickness of the insulating layer was about 1.0 μm.

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

Next, after vapor-depositing a compound (LiQ) to a thickness of 2 nm, Mg and Ag were vapor-deposited to a thickness of 10 nm at a volume ratio of 10:1 to form a second electrode (transparent electrode) 14 . Finally, a cap-shaped glass plate was adhered with an epoxy resin-based adhesive under a low humidity nitrogen atmosphere for sealing. Four display devices were produced. Incidentally, the film thickness referred to here is a value displayed on a crystal oscillation type film thickness monitor.

The produced organic EL display device was placed on a hot plate heated to 80° C. with the light-emitting surface facing up, and irradiated with UV light having a wavelength of 365 nm and an illuminance of 0.6 mW/cm ² . Immediately after irradiation (0 hour), 250 hours, 500 hours, and 1000 hours later, the organic EL display device was driven to emit light by direct current driving at 0.625 mA, and the area ratio of the light emitting portion to the area of the light emitting pixel (pixel light emitting area ratio) was measured. did. According to this evaluation method, when the pixel emission area ratio after 1000 hours has passed is 80% or more, it can be said that the long-term reliability is excellent, and when it is 90% or more, it is more preferable.

Abbreviated names of acid dianhydrides, diamines and other reagents shown in the following examples and comparative examples are as follows.
6FDA: 4,4'-hexafluoroisopropylidene diphthalic dianhydride ABP: 2-amino-4-tert-butylphenol BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane Bk- S0100CF: “IRGAPHOR” (registered trademark) BLACK S0100CF (manufactured 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: cyclobutanetetracarboxylic dianhydride DAE: 4,4'-diaminodiphenyl ether DFA: N,N-dimethylformamide Dimethylacetal DPHA: "KAYARAD" (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd.; dipentaerythritol hexaacrylate)
MA: maleic anhydride MAP: 3-aminophenol; meta-aminophenol MBA: 3-methoxy-n-butyl acetate NCI-831: "Adeka Arkles" (registered trademark) NCI-831 (manufactured by ADEKA Corporation; 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 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(anhydrotrimellitate).

Alkoxymethyl group-containing thermal crosslinkable compound (e-1), Nicalac MX-270 (e-2), VG-3101L (e-3) and phenol compound BisP-AF (h- 1) is shown below.

<Synthesis Example 1 Synthesis of hydroxyl group-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-nitrobenzoyl chloride in 100 mL of acetone was added dropwise thereto. After completion of the dropwise addition, the mixture was allowed to react at -15°C for 4 hours, and then returned to room temperature. The precipitated white solid was collected by filtration and vacuum dried at 50°C.

30 g of the resulting white solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, 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, the reaction was terminated after confirming that the balloon did not deflate any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration and concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound (α) represented by the following formula. The obtained solid was used for the reaction as it was.

<Synthesis Example 2 Synthesis of quinonediazide compound (b1-1)>
Under a stream of dry nitrogen, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 26.86 g (0.10 mol) of 5-naphthoquinonediazidosulfonyl chloride, and 4-naphtho 13.43 g (0.05 mol) of quinonediazide sulfonyl chloride was dissolved in 50 g of 1,4-dioxane and brought to room temperature. To this, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the inside of the system did not reach 35° C. or higher. After dropping, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. After that, the deposited precipitate was collected by filtration. This precipitate was dried in a vacuum dryer to obtain a quinonediazide compound (b1-1) represented by the following formula.

<Synthesis Example 3 Synthesis of quinonediazide compound (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-naphthoquinonediazidosulfonyl chloride were mixed with 1,4 - dissolved in 450 g of dioxane and brought to room temperature. A quinonediazide compound (b1-2) represented by the following formula was obtained in the same manner as in Synthesis Example 2 using 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane.

<Synthesis Example 4 Synthesis of quinonediazide compound (b1-3)>
Under a dry nitrogen stream, 28.83 g (0.05 mol) of TekP-4HBPA (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.) and 13.43 g (0.125 mol) of 5-naphthoquinonediazide sulfonyl chloride were mixed with 1,4 - dissolved in 450 g of dioxane and brought to room temperature. A quinonediazide compound (b1-3) represented by the following formula was obtained in the same manner as in Synthesis Example 2 using 20.24 g of triethylamine mixed with 50 g of 1,4-dioxane.

[Example 1]
Under a dry nitrogen stream, 15.11 g (0.025 mol) of the hydroxyl group-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 200 g of NMP. 20.51 g (0.05 mol) of TMEG was added together with 50 g of NMP, and the mixture was stirred at 40° C. for 1 hour. After that, 2.73 g (0.025 mol) of MAP was added as a terminal blocking agent, and the mixture was stirred at 40°C for 1 hour. Thereafter, a solution of 11.9 g (0.1 mol) of DFA diluted with 5 g of NMP was added dropwise over 10 minutes, and after the dropwise addition, stirring was continued at 40° C. for 1 hour. After stirring, the solution was poured into 2 L of water, and solid precipitates were collected by filtration. Further, it was washed with 2 L of water three times, and the collected polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain polyamic acid ester resin (A).

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 group-containing thermal cross-linking agent (e-1) were added to 50 g of GBL to obtain a positive photosensitive composition. Varnish A1 of a flexible 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. Table 2 shows the evaluation results.

[Example 2]
3.66 g (0.01 mol) of BAHF was 3.62 g (0.01 mol) of BIS-AT-AF, and 2.73 g (0.025 mol) of MAP as a terminal blocking agent was 4.13 g (0.025 mol) of ABP. Surprisingly, polyamic acid ester resin (B) was obtained in the same manner as in Example 1.

10 g of the obtained resin (B), 3.0 g of the quinonediazide compound (b1-2) obtained in Synthesis Example 3, and 0.5 g of the cross-linking agent Nicalac MX-270 (e-2) were added to 50 g of GBL to obtain a positive photosensitive composition. A varnish B1 of a resin composition was obtained. Using the obtained varnish B1, the sensitivity evaluation, film remaining rate evaluation, bendability, and long-term reliability evaluation of the organic EL display device were evaluated as described above. Table 2 shows the evaluation results.

[Example 3]
Under a dry nitrogen stream, 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 was added together with 10 g of NMP, and reacted at 60° C. for 1 hour. After that, 1.09 g (0.01 mol) of MAP was added as a terminal blocker, and stirring was continued at 60° C. for 1 hour. Then, the mixture was stirred at 180° C. for 4 hours, and after stirring was completed, 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 dried in a vacuum dryer at 50° C. for 72 hours to obtain a powder of closed-ring polyimide resin (C).

10 g of the obtained resin (C), 3.0 g of the quinone diazide compound (b1-1), 1.0 g of the alkoxymethyl group-containing thermal cross-linking agent (e-1), and 1.0 g of the phenol compound BisP-AF (h-1) were In addition to 50 g of GBL, varnish C1 of a positive photosensitive resin composition was obtained. Using the obtained varnish C1, the sensitivity evaluation, film remaining rate evaluation, bendability, and long-term reliability evaluation of the organic EL display device were evaluated as described above. Table 2 shows the evaluation results.

[Example 4]
BAHF 15.56 g (0.0425 mol) was 10.98 g (0.03 mol), MAP 1.09 g (0.01 mol) was ABP 1.65 g (0.01 mol), and hydroxyl group-containing diamine compound (α) 6 A ring-closed polyimide resin (D) was obtained in the same manner as in Example 3, except that 0.05 g (0.01 mol) was added.

10 g of the obtained resin (D), 3.0 g of the quinonediazide compound (b1-1), and 1.0 g of the cross-linking agent VG-3101L (e-3) were added to 50 g of GBL to obtain a positive photosensitive resin composition varnish D1. rice field. 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. Table 2 shows the evaluation results.

[Example 5]
Under a dry nitrogen stream, 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 was added together with 10 g of NMP, and reacted at 60° C. for 1 hour. Then, 2.45 g (0.025 mol) of MA was added as a terminal blocking agent, and stirring was continued at 60° C. for 1 hour. Then, the mixture was stirred at 180° C. for 4 hours, and after stirring was completed, 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 dried in a vacuum dryer at 50° C. for 72 hours to obtain a ring-closed polyimide resin (E).

10 g of the obtained resin (E), 3.0 g of the quinonediazide compound (b1-2), and 1.0 g of the alkoxymethyl group-containing thermal cross-linking agent (e-1) were added to 50 g of GBL to obtain a positive photosensitive resin composition varnish E1. got 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. Table 2 shows the evaluation results.

[Example 6]
8.24 g (0.0225 mol) of 11.9 g (0.0325 mol) of BAHF, 4.9 g (0.05 mol) of 2.45 g (0.025 mol) of MA, and 15.39 g (0.0375 mol) of TMEG 10.26 g (0.025 mol), and 15.11 g (0.025 mol) of hydroxyl group-containing diamine compound (α) was added instead of 5.43 g (0.015 mol) of BIS-AT-AF. A ring-closed polyimide resin (F) was obtained in the same manner as in Example 5.

10 g of the obtained resin (F), 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) were added to 50 g of GBL to obtain a positive photosensitive composition. A varnish F1 of a resin composition was obtained. Using the obtained varnish F1, evaluation of sensitivity, evaluation of residual film ratio, evaluation of bendability, and evaluation of long-term reliability of the organic EL display device were performed as described above. Table 2 shows the evaluation results.

[Example 7]
Instead of 15.56 g (0.0425 mol) of BAHF, 7.25 g (0.02 mol) of BIS-AT-AF, 4.0 g (0.02 mol) of DAE, and 1.64 g (0.01 mol) of MAP 1.09 g (0.01 mol) A ring-closed polyimide resin (G) was obtained in the same manner as in Example 3, except that the content was 0.015 mol).

10 g of the obtained resin (G), 3.0 g of the quinonediazide compound (b1-1), and 1.0 g of the alkoxymethyl group-containing thermal cross-linking agent (e-1) were added to 50 g of GBL to obtain a positive photosensitive resin composition varnish G1. got 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. Table 2 shows the evaluation results.

[Example 8]
Under a dry nitrogen stream, 13.21 g (0.0375 mol) of 2,2′-bis(trifluoromethyl)-5,5′-dihydroxybenzidine (TFM-DHB) and 0.62 g (0.0025 mol) of SiDA were added to NMP. 200 g was dissolved. 20.51 g (0.05 mol) of TMEG was added together with 50 g of NMP, 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 blocking agent, and stirring was continued at 60° C. for 1 hour. Then, the mixture was stirred at 180° C. for 4 hours, and after stirring was completed, 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 dried in a vacuum dryer at 50° C. for 72 hours to obtain a powder of already-closed-ring polyimide resin (H).

10 g of the obtained resin (H), 3.0 g of the quinonediazide compound (b1-3), and 1.0 g of the cross-linking agent VG-3101L (e-3) were added to 50 g of GBL to obtain a varnish H1 of a positive photosensitive resin composition. rice field. 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. Table 2 shows the evaluation results.

[Example 9]
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 in the same manner as in Example 3 to obtain a closed-ring polyimide resin (I). Obtained.

10 g of the obtained resin (I), 3.0 g of the quinone diazide compound (b1-3), 1.0 g of the alkoxymethyl group-containing thermal cross-linking agent (e-1), and 1.0 g of the phenol compound BisP-AF (h-1) were In addition to 50 g of GBL, varnish I1 of a positive photosensitive resin composition was obtained. 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. Table 2 shows the evaluation results.

[Example 10]
10 g of resin (C), 3.0 g of quinonediazide compound (b1-3), and 1.0 g of cross-linking agent VG-3101L (e-3) were added to 50 g of GBL to obtain varnish C2 of a 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. Table 2 shows the evaluation results.

[Example 11]
10 g of resin (D), 3.0 g of quinonediazide compound (b1-3), 1.0 g of alkoxymethyl group-containing thermal cross-linking agent (e-1), and 1.0 g of phenol compound BisP-AF (h-1) were added to 50 g of GBL. Varnish D2 of a positive photosensitive resin composition was obtained. Using the obtained varnish D2, sensitivity evaluation, residual film rate evaluation, bending property, and long-term reliability evaluation of the organic EL display device were evaluated as described above. Table 2 shows the evaluation results.

[Example 12]
10 g of resin (G), 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 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. Table 2 shows the evaluation results.

[Example 13]
10 g of resin (A), 3.0 g of quinone diazide compound (b1-1), 1.0 g of alkoxymethyl group-containing thermal cross-linking agent (e-1), 0.0 g of N-methyl-2-pyrrolidone (NMP), which is a cyclic amide compound. 5 g was added to 50 g of GBL to obtain varnish A2 of a 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. Table 2 shows the evaluation results.

Using a coating and developing apparatus Mark-7 (manufactured by Tokyo Electron Co., Ltd.), a varnish is applied on an 8-inch silicon wafer by a spin coating method, and baked on a hot plate at 120 ° C. for 3 minutes to give a film thickness of 3. A pre-baked film of 2 μm was produced. After that, using the Mark-7 developing apparatus, after developing with 2.38% TMAH in a time such that the film reduction during development becomes 0.5 μm, rinsed with distilled water, dried by shaking off, and after development. The solid film was baked in an oven at a predetermined temperature at 250° C. for 60 minutes in a nitrogen atmosphere to obtain a cured film.

The film thickness of the obtained cured film was measured, and a 1×5 cm portion was cut out of the film and adsorbed and captured by the purge and trap method. Specifically, the sampled cured film was heated at 400° C. for 60 minutes using helium as a purge gas, and the desorbed components were collected in an adsorption tube. Using a thermal desorption apparatus, the captured components were thermally desorbed under the primary desorption conditions of 260°C for 15 minutes and the secondary adsorption/desorption conditions of -27°C and 320°C for 5 minutes. GC-MS analysis was performed using 5975C (manufactured by Agilent) under the conditions of column temperature: 40 to 300° C., carrier gas: helium (1.5 mL/min), scan range: m/Z 29 to 600. The amount of gas generated was calculated by preparing a calibration curve by GC-MS analysis of NMP under the same conditions as above. The obtained value (μg) was divided by the area of 5 cm ² to give μg/cm ² . The value was divided by the value obtained by multiplying the specific gravity of the alkali-soluble resin (a) by the film thickness and multiplied by 100 to calculate the total content of NMP in the cured film, which was 0.5% by mass.

[Comparative Example 1]
Under a dry nitrogen stream, 15.11 g (0.025 mol) of the hydroxyl group-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 200 g of NMP. 10.26 g (0.025 mol) of TMEG and 11.11 g (0.025 mol) of 6FDA were added together with 50 g of NMP, and the mixture was stirred at 40° C. for 1 hour. After that, 2.73 g (0.025 mol) of MAP was added as a terminal blocking agent, and the mixture was stirred at 40°C for 1 hour. Thereafter, a solution of 11.9 g (0.1 mol) of DFA diluted with 5 g of NMP was added dropwise over 10 minutes, and after the dropwise addition, stirring was continued at 40° C. for 1 hour. After stirring, the solution was poured into 2 L of water, and solid precipitates were collected by filtration. Further, it was washed with 2 L of water three times, and the collected polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain polyamic acid ester resin (J).

10 g of the obtained resin (J), 3.0 g of the quinonediazide compound (b1-1), and 1.0 g of the alkoxymethyl group-containing thermal cross-linking agent (e-1) were added to 50 g of GBL to obtain varnish J1 of a positive photosensitive resin composition. got 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. Table 2 shows the evaluation results.

[Comparative Example 2]
Under a dry nitrogen stream, 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 and 2.94 g (0.015 mol) of CBDA were added together with 50 g of NMP, and the mixture was stirred at 40° C. for 1 hour. Thereafter, a solution of 11.9 g (0.1 mol) of DFA diluted with 5 g of NMP was added dropwise over 10 minutes, and after the dropwise addition, stirring was continued at 40° C. for 1 hour. No end capping agent was used. After stirring, the solution was poured into 2 L of water, and solid precipitates were collected by filtration. Further, it was washed with 2 L of water three times, and the collected polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain polyamic acid ester resin (K).

10 g of the resulting resin (K), 3.0 g of the quinonediazide compound (b1-2), and 1.0 g of the alkoxymethyl group-containing thermal cross-linking agent (e-1) were added to 50 g of GBL to obtain varnish K1 of a positive photosensitive resin composition. got 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. Table 2 shows the evaluation results.

[Comparative Example 3]
Under a dry nitrogen stream, 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 was added together with 10 g of NMP, and reacted at 60° C. for 1 hour. Then, the mixture was stirred at 180°C for 4 hours. No end capping agent was used. After 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 dried in a vacuum dryer at 50° C. for 72 hours to obtain a powder of closed-ring polyimide resin (L).

10 g of the obtained resin (L), 3.0 g of the quinone diazide compound (b1-1), and 0.5 g of the cross-linking agent Nicalac MX-270 (e-2) were added to 50 g of GBL to obtain varnish L1 of the positive photosensitive resin composition. Obtained. 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. Table 2 shows the evaluation results.

[Comparative Example 4]
Under a dry nitrogen stream, 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 and 13.33 g (0.03 mol) of 6FDA were added together with 10 g of NMP, and reacted at 60° C. for 1 hour. After that, 1.64 g (0.015 mol) of MAP was added as a terminal blocking agent, and stirring was continued at 60° C. for 1 hour. Then, the mixture was stirred at 180° C. for 4 hours, and after stirring was completed, 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 dried in a vacuum dryer at 50° C. for 72 hours to obtain a powder of closed-ring polyimide resin (M).

10 g of the obtained resin (M), 3.0 g of the quinone diazide compound (b1-3), 1.0 g of the alkoxymethyl group-containing thermal cross-linking agent (e-1), and 1.0 g of the phenol compound BisP-AF (h-1) were In addition to 50 g of GBL, varnish M1 of a positive photosensitive resin composition was obtained. 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. Table 2 shows the evaluation results.

[Comparative Example 5]
Under a dry nitrogen stream, 6.05 g (0.01 mol) of the hydroxyl group-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 100 g of NMP. 9.81 g (0.05 mol) of CBDA was added together with 10 g of NMP, and reacted at 60° C. for 1 hour. After that, 2.18 g (0.02 mol) of MAP was added as a terminal blocker, and stirring was continued at 60° C. for 1 hour. Then, the mixture was stirred at 180° C. for 4 hours, and after stirring was completed, 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 dried in a vacuum dryer at 50° C. for 72 hours to obtain a powder of already-closed-ring polyimide resin (N).

10 g of the obtained resin (N), 3.0 g of the quinonediazide compound (b1-1), and 1.0 g of the alkoxymethyl group-containing thermal cross-linking agent (e-1) were added to 50 g of GBL to obtain varnish N1 of a positive photosensitive resin composition. got 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. Table 2 shows the evaluation results.

[Comparative Example 6]
Under a dry nitrogen stream, 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 was added together with 50 g of NMP, and the mixture was stirred at 40° C. for 1 hour. Thereafter, a solution of 11.9 g (0.1 mol) of DFA diluted with 5 g of NMP was added dropwise over 10 minutes, and after the dropwise addition, stirring was continued at 40° C. for 1 hour. No end capping agent was used. After stirring, the solution was poured into 2 L of water, and solid precipitates were collected by filtration. Further, it was washed with 2 L of water three times, and the collected polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain polyamic acid ester resin (O).

10 g of the obtained resin (O), 3.0 g of the quinone diazide compound (b1-1), 1.0 g of the alkoxymethyl group-containing thermal cross-linking agent (e-1), and 1.0 g of the phenol compound BisP-AF (h-1) were In addition to 50 g of GBL, varnish O1 of a positive photosensitive resin composition was obtained. 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. Table 2 shows the evaluation results.

Table 1 shows the compositions of Examples 1 to 13 and Comparative Examples 1 to 6, and Table 2 shows the evaluation results.

<Preparation Example 1>
As the resin, 138.0 g of the 30% by mass MBA solution of the resin (C) obtained in Example 3, as the dispersant, 13.8 g of S-20000, as the solvent, 685.4 g of MBA, and as the colorant. , and Bk-S0100CF 82.8 g were weighed and mixed, and stirred for 20 minutes using a high-speed disperser (Homodisper 2.5 type; manufactured by Primix Co., Ltd.) to obtain a preliminary dispersion. Ultra Apex Mill (UAM-015; Kotobuki Kogyo Co., Ltd.) equipped with a centrifugal separator filled with 75% of 0.30 mmφ zirconia grinding balls (YTZ; manufactured by Tosoh Corporation) as ceramic beads for pigment dispersion. (manufactured by mass ratio) to obtain a pigment dispersion (Bk-1). The number average particle size of the pigment in the resulting pigment dispersion was 100 nm.

<Preparation Example 2>
A pigment dispersion (Bk-2) was obtained in the same manner as in Preparation Example 1, except that the resin (M) was used instead of the resin (C).

[Example 14]
Under a yellow light, 0.25 g of NCI-831 was weighed, 10.0 g of MBA was added, and dissolved by stirring. Next, 3.5 g of the 30% by mass MBA solution of the resin (A) obtained in Example 1 and 1.5 g of the 80% by mass MBA solution of DPHA were added and stirred to obtain a uniform solution. Obtained. Next, 16.67 g of the pigment dispersion (Bk-1) obtained in Preparation Example 1 was weighed, and the prepared liquid obtained above was added thereto and stirred to obtain a uniform solution. Thereafter, the obtained solution was filtered through a 0.45 μmφ filter 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. Table 3 shows the composition, and Table 4 shows the evaluation results.

[Examples 15-17 and Comparative Examples 7-11]
In the same manner as in Example 14, varnishes BB to BN of photosensitive resin compositions were prepared according to the compositions shown in Table 3. As in Example 14, sensitivity evaluation, residual film ratio evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device were performed using each of the obtained compositions. Table 4 shows the evaluation results.

Tables 3 and 4 show the compositions and evaluation results of Examples 14 to 17 and Comparative Examples 7 to 11, respectively.

1: TFT (thin film transistor)
2: Wiring 3: TFT insulating layer 4: Flattening layer 5: ITO (transparent electrode)
6: Substrate 7: Contact hole 8: Insulating layer 9: Glass substrate 10: First electrode (non-transparent electrode)
11: auxiliary electrode 12: insulating layer 13: organic EL layer 14: second electrode (transparent electrode)

Claims (8)

(a) an alkali-soluble resin, (b) containing a photosensitive compound,
The (a) alkali-soluble resin has 95 to 100 mol% of the structure represented by the general formula (1) as a repeating unit, and at least one end of the polymer molecular chain in the (a) alkali-soluble resin is a monoamine or It has an organic group derived from an acid anhydride and contains (i) one or more compounds selected from the group consisting of cyclic amides and derivatives thereof, and the amount of compound (i) added is (a) alkali-soluble resin A photosensitive resin composition for an organic EL display device, which is 0.1 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass.

(In 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 carbon atoms. X ¹ and X ² each represent are independently an ethylene group, a propylene group, or a butylene group, R ¹ , X ¹ and X ² may be different in a plurality of repeating units, m and n are each an integer of 0 to 100,000, m+n≧3.) The alkali-soluble resin (a) according to claim 1, having 10 to 100 mol% of an organic group derived from a monoamine or an acid anhydride relative to 100 mol% of structural units represented by general formula (1). A photosensitive resin composition for an organic EL display device. 3. The photosensitive resin composition for an organic EL display device according to claim 1, wherein said monoamine is a compound having a structure represented by general formula (2).

(In 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 may be a hydroxyl group, a carboxyl group, or represents a sulfonic acid group, s and t each represent 0 or 1, and s+t≧1.) 4. The photosensitive resin composition for an organic EL display device according to claim 1, wherein the (b) photosensitive compound is (b1) a photoacid generator. The photosensitive resin for an organic EL display device according to any one of claims 1 to 3, wherein the (b) photosensitive compound is (b2) a photopolymerization initiator and further contains (d) a radically polymerizable compound. Composition. 6. The photosensitive resin composition for an organic EL display device according to claim 1, further comprising (f) a colorant. 7. The photosensitive resin composition for an organic EL display device according to claim 6, wherein the (f) colorant is (f3) a black agent and/or (f4) a colorant other than black. 8. The photosensitive resin composition for an organic EL display device according to claim 6, wherein the (f) colorant is (f1) a pigment or (f2) a dye .

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