JPWO2017217292A1 - Photosensitive resin composition, photosensitive sheet, cured film, element, organic EL display device, semiconductor electronic component, semiconductor device, and manufacturing method of organic EL display device - Google Patents

Abstract

The present invention provides a highly sensitive photosensitive resin composition having a high residual film ratio after development and high bending resistance in a cured film. The present invention includes (a) an alkali-soluble resin and (b) a photosensitive compound, and the (a) alkali-soluble resin has 95 to 100 mol% of the structure represented by the general formula (1) as a repeating unit. And (a) a photosensitive resin composition having an organic group derived from a monoamine or an acid anhydride at at least one end of a polymer molecular chain in the alkali-soluble resin. (In the general formula (1), R1 represents a divalent organic group. R2 and R3 each independently represent hydrogen or an organic group having 1 to 20 carbon atoms. X1 and X2 represent each independently. Represents a linear or branched alkylene group having 1 to 20 carbon atoms, 1,3-phenylene group or 1,4-phenylene group, wherein R1, X1 and X2 may be different in a plurality of repeating units. M and n are each an integer in the range of 0 to 100,000, where m + n ≧ 3.

Description

  The present invention relates to a photosensitive resin composition. Specifically, a surface protective film and an interlayer insulating film of a semiconductor element, an insulating film of an organic electroluminescence (hereinafter referred to as EL) element, a driving thin film transistor (Thin Film Transistor: hereinafter referred to as TFT) for a display device using the organic EL element. The present invention relates to a photosensitive resin composition suitable for applications such as a flattening film on a substrate, a wiring protective insulating film on a circuit board, an on-chip microlens for a solid-state imaging device, and a flattening film for various displays and solid-state imaging devices.

  Since heat-resistant resins such as polyimide and polybenzoxazole have excellent heat resistance and electrical insulation, photosensitive resin compositions containing these heat-resistant resins are used as surface protective films for semiconductor elements such as LSI, It is used for an interlayer insulating film, an insulating layer of an organic electric field element and an organic EL display element, a planarizing film of a TFT substrate for a display device, and the like.

  In recent years, high sensitivity is required for the photosensitive resin composition in order to shorten the exposure time for reasons such as an increase in substrate size and productivity. Recently, studies have been actively made to make a display flexible by forming a substrate from an organic film, and thus flexibility such as bending resistance is also required for an insulating film and a 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 with a highly transparent polyimide using a tetracarboxylic acid anhydride having an alicyclic structure. It has been proposed (see, for example, Patent Documents 1 and 2).

  In order to achieve high sensitivity, a highly transparent polyimide resin using a tetracarboxylic 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, the photosensitive resin composition using the polyimide which uses the tetracarboxylic anhydride which has an ester group is proposed (for example, refer patent document 5).

International Publication No. 2000/73853 JP 2010-196041 A JP 2007-183388 A JP 2011-202059 A International Publication No. 2011/59089

  However, the polyimide resin using tetracarboxylic acid anhydride having an alicyclic structure as described in Patent Documents 1 and 2 is too high in solubility in an alkali developer, resulting in a decrease in the remaining film ratio. There was a case.

  In addition, as described in Patent Documents 3 and 4, a polyimide resin using a tetracarboxylic acid anhydride having a fluorine atom such as a hexafluoropropyl group forms a cured film having a brittle cured film and excellent bending resistance. There were cases where it was difficult to do.

  Moreover, although the polyimide resin using the tetracarboxylic acid anhydride which has ester group structure as described in patent document 5 is excellent in bending tolerance, there existed a case where a sensitivity was inadequate.

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

  The present invention includes (a) an alkali-soluble resin, (b) a photosensitive compound, and the (a) alkali-soluble resin has 95 to 100 mol% of a structural unit represented by the general formula (1), (A) A photosensitive resin composition having an organic group derived from a monomeramine or an acid anhydride at at least one end of a 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 are each Independently represents a linear or branched alkylene group having 2 to 20 carbon atoms, a 1,3-phenylene group or a 1,4-phenylene group, wherein R ¹ , X ¹ and X ² each represent a plurality of repeating units; M and n are each an integer of 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 an organic solvent, and has a high sensitivity, a residual film rate, and a softness | flexibility can be obtained.

Cross-sectional view of an example 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 an alkali-soluble polyimide having a structural unit represented by the above general formula (1), a polyimide precursor, or a copolymer thereof.

  (A) The photosensitive resin composition which has alkali-soluble resin is preferably used for manufacture of an organic electroluminescence display.

  As the polyimide precursor, for example, it is obtained by reacting tetracarboxylic acid, corresponding tetracarboxylic dianhydride or tetracarboxylic diester dichloride and the like with diamine, corresponding diisocyanate compound or trimethylsilylated diamine, and the like. And having a tetracarboxylic acid and / or its derivative residue and a diamine and / or its derivative residue. Examples of the polyimide precursor include polyamic acid, polyamic acid ester, polyamic acid amide, and polyisoimide.

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

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

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

X ¹ and X ² in the general formula (1) are a C 2-20 linear or branched alkylene group, a 1,3-phenylene group or a 1,4-phenylene group, 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 increased 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. In particular, ethylene group. From the viewpoint of improving the heat resistance of the resin and improving the solvent solubility of the resin, it is preferable that X ¹ and X ² in the general formula (1) are an ethylene group, a propylene group, or a butylene group. As described above, 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 the ester group-containing tetracarboxylic dianhydride include 1,2-ethylenebis (anhydrotrimellitate), 1,3-propylenebis (anhydrotrimellitate), and 1,4-tetramethylene. Bis (anhydro trimellitate), 1,5-pentamethylene bis (anhydro trimellitate), 1,6-hexamethylene bis (anhydro trimellitate), 1,7-heptamethylene bis (anhydro trimellitate) 1,8-octamethylene bis (anhydro trimellitate), 1,9-nonamethylene bis (anhydro trimellitate), 1,10-decamethylene bis (anhydro trimellitate), 1 , 12-dodecamethylene bis (anhydro trimellitate), 1,3-phenylene bis (anhydro trimellitate), 1,4 Such phenylene bis (anhydrotrimellitate) and the like. Among these, 1,2-ethylenebis (anhydrotrimellitate) is preferably used because it is particularly excellent in the 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), so that the solubility in an organic solvent is improved and the flexibility of the resin composition is increased. Can be improved. The structural unit is a repeating unit and represents a structure represented by the repeating numbers m and n, respectively, and the structure represented by the repeating numbers m and n may be random or block.

The alkali-soluble resin having 95 to 100 mol% of the structural unit represented by the general formula (1) is obtained by adding an ester group-containing tetracarboxylic acid diester to 100 mol% of the diamine component in accordance with a known method for producing a polyimide precursor described later. It can be obtained by using 95 to 100 mol% of anhydride. (A) By having 95 mol% or more of the structural units represented by the general formula (1) in the alkali-soluble resin, 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) represents a linear or branched alkylene group having 2 to 20 carbon atoms, a 1,3-phenylene group or 1,4-phenylene group, both Since it exhibits hydrophobicity, a resin having a high residual film ratio after development can be provided. In particular, when (a) the alkali-soluble resin contains 95 mol% or more of the structural unit represented by the general formula (1), a resin having a high residual film ratio after development can be provided.

  Moreover, (a) alkali-soluble resin used for this invention contains the structure derived from other acid dianhydrides in addition to ester group containing tetracarboxylic dianhydride in the range which does not reduce the above-mentioned characteristic. Also good.

  Specific examples of other acid dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,3,3 ′, 4′-biphenyl. Tetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3 3′-benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1 , 1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride Bis (2,3-dicarbohydrate) Ciphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis (3,4-dicarboxy) Phenyl) fluorenic dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorenic 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 And aromatic tetracarboxylic dianhydrides such as acid dianhydrides having the structures shown in the following general formulas (3) and (4), butanetetracarboxylic dianhydride, 1,2,3,4- Siku And aliphatic tetracarboxylic dianhydrides such as pentane tetracarboxylic dianhydride and the like. Two or more of these may be used.

(In the general formulas (3) and (4), R ¹⁰ represents an oxygen atom, C (CF ₃ ) ₂ , or C (CH ₃ ) _2. R ¹¹ and R ¹² represent a hydrogen atom or a hydroxyl group.)
The (a) alkali-soluble resin of the present invention preferably has a fluorine atom. In general formula (1), R ¹ is a structure derived from diamine. In the general formula (1), R ¹ is preferably an organic group having a fluorine atom. By having fluorine atoms, water repellency is imparted to the surface of the film during alkali development, and soaking in from the surface can be suppressed. A photosensitive resin film having a high rate is obtained.

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

  Specific examples of the diamine 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 a part of hydrogen atoms of these aromatic rings are substituted with alkyl groups having 1 to 10 carbon atoms or fluoroalkyl groups, And compounds substituted with a halogen atom. The resin having the structure represented by the general formula (1) is preferably a resin including a structure derived from these compounds.

Moreover, it is preferable that (a) alkali-soluble resin of this invention has a phenolic hydroxyl group. In the general formula (1), R ¹ is preferably an organic group having a phenolic hydroxyl group. The phenolic hydroxyl group can be appropriately dissolved in an alkali developer, and can interact with the photosensitizer to suppress the solubility of the unexposed area, thereby improving the remaining film ratio and increasing the sensitivity. In addition, the phenolic hydroxyl group also contributes to the reaction with the cross-linking agent, and thus is preferable in that high mechanical properties and chemical resistance can be obtained.

In the general formula (1), in order to obtain solubility in an appropriate alkaline developer, the organic group having a phenolic hydroxyl group 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 phenolic hydroxyl group among the monomer components for introducing R ¹ . More preferably, it is 50 mol% or more. Further, in order to improve the remaining film ratio after development, the monomer containing a phenolic hydroxyl group is preferably 90 mol% or less.

  Specific examples of the diamine having a phenolic hydroxyl group include bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, and 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, hydroxyl group-containing diamines such as 2,2′-bis (trifluoromethyl) -5,5′-dihydroxybenzidine, and some of the hydrogen atoms of these aromatic rings are substituted with 1 to 10 carbon atoms. Compounds substituted with alkyl groups, fluoroalkyl groups, halogen atoms, etc. Can. The resin having the structure represented by the general formula (1) is preferably a resin including a structure derived from these compounds.

  By using the above-mentioned ester group-containing tetracarboxylic dianhydride, a diamine having a phenolic hydroxyl group and a diamine having a fluorine atom within the above-mentioned range, a high residual film ratio free from tack or development residue at the time of development. A highly sensitive photosensitive resin composition is obtained.

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

  Other diamines include "Jephamine" (registered trademark) KH-511, "Jephamine" ED-600, "Jeffamine" ED-900, "Jephamine" ED as aliphatic diamines containing polyethylene oxide groups. -2003, “Jeffamine” EDR-148, “Jeffamine” EDR-176, polyoxypropylenediamine D-200, D-400, D-2000, D-4000 (above trade names, manufactured by HUNTSMAN Co., Ltd.) And so on. Among these, the use of aliphatic alkyl diamines is preferable because flexibility is imparted and the elongation at break is improved, and the elastic modulus is lowered to suppress the warpage of the wafer. These characteristics are effective in multilayers and thick films. When introduced, the residue derived from the aliphatic alkyl diamine in all diamine residues is preferably 10 mol% or more, and from the viewpoint of improving heat resistance, it is preferably 50 mol% or less.

  In addition, the other diamine may have an aliphatic group having a siloxane structure as long as the heat resistance is not lowered, and the adhesion to the substrate can be improved. Specifically, what copolymerized 1-15 mol% of bis (3-aminopropyl) tetramethyl disiloxane, bis (p-aminophenyl) octamethylpentasiloxane, etc. are mentioned.

  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, and thiols such as dimercaptophenylenediamine Group-containing diamine, 3,4'-diaminodi Phenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′- Diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalene Diamine, 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, 3,3 ', 4,4'-tetramethyl-4,4' -Aromatic diamines such as diaminobiphenyl and 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, and a part of hydrogen atoms of these aromatic rings are substituted with alkyl having 1 to 10 carbon atoms. And alicyclic diamines such as cyclohexyldiamine and methylenebiscyclohexylamine. These diamines can be used as they are or as the corresponding diisocyanate compounds and 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 an 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'-diaminodiphenylsulfide, 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- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2′-bis (trifluoromethyl) -5,5′-dihydroxybenzidine or a compound in which these aromatic rings are substituted with an alkyl group or a halogen atom And diamines having an amide group represented by the following general formulas (5) to (10) are preferable. These are used alone or in combination of two or more.

(In the 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. Represents.)
In addition, the resin having a 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 moderately sulfonic acid groups and thiol groups, a photosensitive resin composition having moderate alkali solubility is 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 acid anhydride at at least one terminal of the polymer molecular chain. Here, monoamine or acid anhydride is a terminal blocking agent. By using a terminal sealing agent, it becomes easy to adjust the photosensitive resin composition to an appropriate viscosity. Further, it is possible to suppress hydrolysis of the resin by the acid terminal, and to suppress the deterioration of the quinonediazide compound, which is a photosensitizer by the amine terminal, when the positive photosensitive resin composition is obtained. When the conductive resin composition is used as a planarization layer and / or an insulating layer of an organic EL display device, the long-term reliability of the organic EL display device is improved. 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. When the terminal blocking agent has a hydroxyl group, a carboxyl group, or a sulfonic acid group as a substituent, the solubility of the resulting resin in an alkaline aqueous solution can be improved, and a highly sensitive resin can be provided. In addition, since the resin has a hydroxyl group, a carboxyl group or a sulfonic acid group at the terminal, when it is made a positive photosensitive resin composition, the unexposed portion is hardly soluble by interacting with the quinonediazide compound through a hydrogen bond. A resin having a high residual film ratio after development can be provided.

  Although the monoamine used for terminal blocker 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 the photosensitive resin composition described later is used, the amount of film loss during alkali development can be reduced. it 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 alkali developer can be obtained, and when a positive photosensitive resin composition is obtained, a quinonediazide compound By interacting with each other through a hydrogen bond, the unexposed portion becomes slightly soluble, and a resin having a high residual film ratio after development can be provided. In addition, the phenolic hydroxyl group also contributes to the reaction with the cross-linking agent, and thus is preferable in that high mechanical properties and chemical resistance can be obtained.

(In the general formula (2), R ⁴ represents a saturated hydrocarbon group having 1 to 6 carbon atoms, and r represents 0 or 1. A and B may be the same as or different from each other, and may be a hydroxyl group, a carboxyl group or Represents a sulfonic acid group, and s and t each represents 0 or 1, and s + t ≧ 1 from the viewpoint of improving the solubility of the resulting resin in an aqueous alkali solution.
Preferred examples of the monoamine represented by the general formula (2) include 2-aminophenol, 3-aminophenol (MAP), 2-amino-m-cresol, 2-amino-p-cresol, and 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-toluene Examples include 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. Two or more of these may be used, and other end-capping agents may be used in combination.

  The introduction ratio of the monoamine used as the end capping agent is preferably 10 to 100 mol%, more preferably 40 to 80 mol% with respect to 100 mol% of the structural unit represented by the general formula (1). By making it 10 mol% or more, preferably 40 mol% or more, the solubility of the resulting resin in an organic solvent is improved, and the viscosity when a photosensitive resin composition is made using the obtained resin is appropriately adjusted. can do. Further, 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 even more preferably 70 mol% or less.

  Although the acid anhydride used for terminal blocker is not particularly limited, it has an acid anhydride or a crosslinkable group having a cyclic structure from the viewpoint of heat resistance of the cured film of the photosensitive resin composition using the obtained resin. 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% with respect to 100 mol% of the structural unit represented by the general formula (1). By making it 10 mol% or more, preferably 50 mol% or more, the solubility of the resulting resin in an organic solvent is improved, and the viscosity when a photosensitive resin composition is made using the obtained resin is appropriately adjusted. can do. Moreover, 100 mol% or less is preferable and 90 mol% or less is more preferable from a viewpoint of the solubility with respect to the aqueous alkali solution of the resin obtained, and the mechanical strength of a cured film.

  The end-capping agent introduced into the resin can be easily detected by the following method. For example, a resin having a terminal blocking agent introduced therein is dissolved in an acidic solution and decomposed into an amine component and an acid component, which are constituent units of the resin, and this is measured by gas chromatography (GC) or NMR measurement. The end capping agent can be easily detected. Apart from this, it is possible to directly detect the resin into which the end-capping 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 represent a range of 0 to 100,000, where m + n ≧ 3. From the viewpoint of improving the elongation of the obtained resin, m + n is preferably 10 or more. On the other hand, m + n is 200,000 or less, preferably 1,000 or less, more preferably 100 or less, from the viewpoint of solubility of the resulting photosensitive resin composition containing a resin in an alkaline developer. Moreover, it is preferable that m / n> 1 from the viewpoint of reducing the shrinkage rate during curing. Preferably, m / n> 2, more preferably m / n> 4.

  The weight average molecular weight of the resin having the structural unit represented by the general formula (1) is preferably 3,000 to 80,000 in terms of polystyrene by gel permeation chromatography, and more preferably 8,000 to 50,000. It 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 dianhydride with a diamine compound having an R ¹ group and a monoamine which is a terminal blocking agent under low temperature conditions, (II) an ester group-containing tetracarboxylic acid bis A method of reacting in the presence of a diamine compound having an R ¹ group, a monoamine which is a terminal blocking agent, and a condensing agent after obtaining a diester by an anhydride and an alcohol, (III) an ester group-containing tetracarboxylic dianhydride Examples include a method in which a diester is obtained with alcohol and then the remaining two carboxyl groups are acid chlorideed and reacted with a diamine compound having an R ¹ group and a monoamine which is a terminal blocking agent. The resin polymerized by the above method is preferably put into a large amount of water or a methanol / water mixture, precipitated, filtered, dried and isolated. By this precipitation operation, unreacted monomers and oligomer components such as dimers and trimers are removed, and film properties after thermosetting are improved. Moreover, after imidating the polyimide precursor and ring-closing polyimide, after obtaining said polyimide precursor, it can synthesize | combine using the method of making a well-known imidation reaction.

Hereinafter, an example of a method for producing a polyimide precursor will be described as a preferred example of (I). First, a diamine compound having an R ¹ group is dissolved in a polymerization solvent. To this solution, an ester group-containing tetracarboxylic dianhydride, which is substantially equimolar with the diamine compound, is gradually added. Using a mechanical stirrer, the mixture is stirred at -20 to 100 ° C, preferably 10 to 50 ° C for 0.5 to 100 hours, more preferably 2 to 24 hours. The end-capping agent may be added after the addition of tetracarboxylic dianhydride and stirred at a predetermined temperature for a predetermined time, and then the end-capping agent may be gradually added, or may be reacted at once. .

  The polymerization solvent is not particularly limited as long as it can dissolve 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- Examples include 2-imidazolidinone, sulfolane, dimethyl sulfoxide, and the like. The polymerization solvent is preferably used in an amount of 100 to 1900 parts by weight, and more preferably 150 to 950 parts by weight, with respect to 100 parts by weight of the resulting resin.

  The photosensitive resin composition of the present invention may contain (a) an alkali-soluble resin other than the alkali-soluble resin. Specifically, alkali-soluble polybenzoxazole, polybenzoxazole precursor, polyamide, acrylic polymer copolymerized with acrylic acid, novolac resin, resol resin, siloxane resin, polyhydroxystyrene resin, and also methylol group, alkoxymethyl Examples thereof include resins introduced with a crosslinking group such as a group or an epoxy group, and copolymers thereof. Such a resin is soluble in an aqueous alkali solution such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate. By containing these alkali-soluble resins, the properties of each alkali-soluble resin can be imparted while maintaining the adhesion and excellent sensitivity of the heat-resistant resin film. Of the resins contained in the photosensitive resin composition of the present invention, the (a) alkali-soluble resin of the present invention is preferably 30% by mass or more.

<(B) Photosensitive compound>
The photosensitive resin composition of the present invention contains (b) a photosensitive compound. Examples of the photosensitive compound include (b1) a photoacid generator and (b2) a photopolymerization initiator. (B1) A photoacid generator is a compound that generates acid when irradiated with light and gives the property of increasing the solubility of the light-irradiated part in an alkaline aqueous solution, and (b2) a photopolymerization initiator is an exposure. Refers to a compound that generates a radical through bond cleavage and / or reaction.

  (B1) By containing a photoacid generator, acid is generated in the light irradiation part, the solubility of the light irradiation part in the alkaline aqueous solution is increased, and a positive relief pattern in which the light irradiation part dissolves can be obtained. it 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 irradiation part accelerates the cross-linking reaction of the epoxy compound and the heat cross-linking agent, and the light irradiation part becomes insoluble. A negative relief pattern can be obtained. In addition, (b2) by containing a photopolymerization initiator and a radical polymerizable compound described later, radical polymerization proceeds, and the exposed portion of the film of the resin composition is insolubilized in an alkali developer, so that the negative type is obtained. The pattern can be formed.

  (B1) Photoacid generators include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, and the like.

  The quinonediazide compound includes a polyhydroxy compound in which a sulfonic acid of quinonediazide is bonded with an ester, a polyamino compound in which a sulfonic acid of quinonediazide is bonded to a sulfonamide, and a sulfonic acid of quinonediazide in an ester bond and / or sulfone. Examples include amide-bonded ones. It is preferable that 50 mol% or more of the total functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide. Moreover, it is preferable to contain 2 or more types of (b1) photo-acid generators, and a highly sensitive photosensitive resin composition can be obtained.

  In the present invention, quinonediazide is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group. The 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazide sulfonyl ester compound has an 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-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed. Further, it may contain a naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound. You may contain.

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

  Among the photoacid generators (b1), sulfonium salts, phosphonium salts, and diazonium salts are preferable because they moderately stabilize the acid component generated by exposure. Of these, sulfonium salts are preferred. Furthermore, it can also contain a sensitizer etc. as needed.

  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 (a) alkali-soluble resin from the viewpoint of increasing sensitivity. Of these, the quinonediazide compound is preferably 3 to 40 parts by mass. The total amount of sulfonium salt, phosphonium salt and diazonium salt is preferably 0.5 to 20 parts by mass.

  (B2) Examples of the photopolymerization initiator include benzyl ketal photopolymerization initiator, α-hydroxyketone photopolymerization initiator, α-aminoketone photopolymerization initiator, acylphosphine oxide photopolymerization initiator, and oxime ester. Photopolymerization initiator, acridine photopolymerization initiator, titanocene photopolymerization initiator, benzophenone photopolymerization initiator, acetophenone photopolymerization initiator, aromatic ketoester photopolymerization initiator or benzoate photopolymerization initiator From the viewpoint of improving the sensitivity during exposure, an α-hydroxyketone photopolymerization initiator, an α-aminoketone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, an oxime ester photopolymerization initiator, an acridine -Based photopolymerization initiator or benzophenone-based photopolymerization initiator is more preferable, α-aminoketone-based photopolymerization initiator More preferred are acylphosphine oxide photopolymerization initiators and oxime ester photopolymerization initiators.

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

  Examples of the α-hydroxyketone photopolymerization initiator include 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and 2-hydroxy-2-methyl-1-phenylpropane-1. -One, 1-hydroxycyclohexyl phenyl 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 the α-aminoketone photopolymerization initiator 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 the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, or bis (2,6-dimethoxybenzoyl). )-(2,4,4-trimethylpentyl) phosphine oxide.

  Examples of the oxime ester photopolymerization initiator 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, -Dimethyl-1,3-dioxolan-4-yl) methyloxy] benzoyl] -9H-carbazol-3-yl] ethanone-1- (O-acetyl) oxime or 1- (9-ethyl-6-nitro-9H -Carbazol-3-yl) -1- [2-methyl-4- (1-methoxypropan-2-yloxy) phenyl] methanone-1- (O-acetyl) oxime.

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

  Examples of the titanocene photopolymerization initiator include 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 the benzophenone photopolymerization initiator include benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, 4- Examples include hydroxybenzophenone, alkylated benzophenone, 3,3 ′, 4,4′-tetrakis (t-butylperoxycarbonyl) benzophenone, 4-methylbenzophenone, dibenzyl ketone or fluorenone.

  Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-t-butyldichloroacetophenone, benzalacetophenone, and 4-azidobenzalacetophenone.

  Examples of the aromatic ketoester photopolymerization initiator include methyl 2-phenyl-2-oxyacetate.

  Examples of the benzoate photopolymerization initiator include ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (2-ethyl) hexyl, ethyl 4-diethylaminobenzoate or methyl 2-benzoylbenzoate. .

  In the present invention, the content of the (b2) photopolymerization initiator is 0.1 parts by mass or more when the total of (a) the alkali-soluble resin and the later-described (d) radical polymerizable compound is 100 parts by mass. Is preferably 0.5 parts by mass or more, more preferably 0.7 parts by mass or more, and particularly preferably 1 part by mass or more. The sensitivity at the time of exposure can be improved as content is in the said range. On the other hand, the content is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, further 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. As the solvent, 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, and other ethers, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, Esters such as ethyl acetate, butyl acetate, methyl lactate, ethyl lactate and butyl lactate, alcohols such as ethanol, isopropanol, butanol, pentanol, 3-methyl-2-butanol and 3-methyl-3-methoxybutanol, methyl ethyl ketone , Methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, Ketones such as pentanone and diacetone alcohol, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone Polar aprotic solvents such as, and aromatic hydrocarbons such as toluene and xylene. Two or more of these may be contained. The content of the solvent (c) 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 (a) alkali-soluble resin. Is 1500 parts by mass or less.

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

  (D) A radically polymerizable compound refers to a compound having a plurality of ethylenically unsaturated double bond groups in the molecule. At the time of exposure, (b) radical polymerization of the radical polymerizable compound proceeds by the radical generated from the photopolymerization initiator (b2), and the exposed portion of the film of the resin composition is insolubilized in the alkali developer. Thus, a negative pattern can be formed.

  (D) By containing a radically polymerizable compound, UV curing at the time of exposure is promoted, and the sensitivity at the time of exposure can be improved. 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 that facilitates radical polymerization is preferable. From the viewpoint of improving the sensitivity during exposure and improving the hardness of the cured film, a compound having two or more (meth) acryl groups in the molecule is more preferable. (D) As a double bond equivalent of a radically polymerizable compound, 80-400 g / mol is preferable from a viewpoint of the sensitivity improvement at the time of exposure, and the hardness improvement of a cured film.

  Examples of the radically polymerizable compound (d) include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meta) ) 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, tet Pentaerythritol 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) acryloxy Ethyl) 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 Xylenyl) fluorene or acid-modified products thereof, ethylene oxide-modified products or propylene oxide-modified products. From the viewpoint of improving the sensitivity during exposure and 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, 9,9-bis (4- (meth) acryloxyphenyl) fluorene, or an acid-modified product thereof, an ethylene oxide-modified product, or a propylene oxide-modified product is preferable. From the viewpoint of improving resolution after development, these acid-modified products. Or an ethylene oxide modified product is more preferable. Further, from the viewpoint of improving resolution after development, a compound obtained by subjecting a compound having two or more glycidoxy groups in the molecule and an unsaturated carboxylic acid having an ethylenically unsaturated double bond group to a ring-opening addition reaction Also preferred are compounds obtained by reacting polybasic acid carboxylic acids or polybasic carboxylic acid anhydrides.

  In the present invention, the content of the (d) radical 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 radical polymerizable compound is 100 parts by mass. Part or more is more preferable, 25 parts by weight or more is more preferable, and 30 parts by weight or more is particularly preferable. When the content is within the above range, the sensitivity at the time of exposure can be improved, and a low taper pattern shape 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, further 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. By setting the pattern shape to a low taper, driving stability of the completed organic EL panel can be enhanced.

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

  Preferred examples of the compound having at least two alkoxymethyl groups or methylol groups include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML- OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM- PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM- BP, TMOM-B E, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX -290, NIKACALAC MX-280, NIKACALAC MX-270, NIKACALAC MX-279, NIKACALAC MW-100LM, NIKACALAC MX-750LM (trade name, manufactured by Sanwa Chemical Co., Ltd.) it can.

  As compounds having an epoxy group or an oxetanyl group, “Epicoat” (registered trademark) 807, “Epicoat” 828, “Epicoat” 1002, “Epicoat” 1750, “Epicoat” have two epoxy groups in one molecule. 1007, YX8100-BH30, E1256, E4250, E4275 (above trade names, manufactured by Japan Epoxy Co., Ltd.), “Epicron” (registered trademark) EXA-4880, “Epicron” EXA-4822, “Epicron” EXA-9835, HP4032 (Trade name, manufactured by Dainippon Ink & Chemicals, Inc.), “Epolite” (registered trademark) 40E, “Epolite” 100E, “Epolite” 200E, “Epolite” 400E, “Epolite” 70P, “Epolite” 200P, "Epolite" 400P, “Epolite” 1500NP, “Epolite” 80MF, “Epolite” 4000, “Epolite” 3002 (above trade name, manufactured by Kyoeisha Chemical Co., Ltd.), “Denacol” (registered trademark) EX-212L, “Denacol” EX-214L, “ Denacol “EX-216L”, “Denacol” EX-252, “Denacol” EX-850L (above trade name, manufactured by Nagase ChemteX Corporation), GAN, GOT (above trade name, manufactured by Nippon Kayaku Co., Ltd.), “Celoxide” (registered trademark) 2021P (trade name, manufactured by Daicel Corporation), “Lika Resin” (registered trademark) DME-100, “Lika Resin” BEO-60E (trade name, manufactured by Shin Nippon Rika Co., Ltd.), etc. Are available from each company.

  In addition, VG3101L (trade name, manufactured by Printec Co., Ltd.), “Tepic” (registered trademark) S, “Tepic” G, “Tepic” P (above trade names, Nissan Chemical Co., Ltd.) have three or more epoxy groups. Kogyo Co., Ltd.), "Epicron" N660, "Epicron" N695, HP7200 (above trade name, Dainippon Ink and Chemicals Co., Ltd.), "Denacol" EX-321L (trade name, Nagase ChemteX Corporation) Manufactured), NC6000, EPPN502H, NC3000 (above trade name, manufactured by Nippon Kayaku Co., Ltd.), "Epototo" (registered trademark) YH-434L (trade name, manufactured by Toto Kasei Co., Ltd.), EHPE-3150 (trade name) As a compound having two or more oxetanyl groups, OXT-121, OXT-221, OX-SQ-H, OXT-191 PNOX-1009, RSOX (above, trade name, manufactured by Toa Gosei Co., Ltd.), “Etanacol” (registered trademark) OXBP, “Etanacol” OXTP (above, trade name, manufactured by Ube Industries, Ltd.), etc. Is available from

  (E) The content of the thermal crosslinking agent is preferably 5 parts by mass or more with respect to 100 parts by mass of the (a) alkali-soluble resin because the crosslinking density increases and chemical resistance is improved. Further, when it is 10 parts by mass or more, higher mechanical properties can be obtained. On the other hand, from the viewpoint of storage stability and mechanical strength of the composition, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 30 parts by mass or less.

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

  (F) A colorant is a compound that absorbs light having a specific wavelength, and particularly a compound that colors by absorbing light having a wavelength of visible light (380 to 780 nm).

  (F) By containing a colorant, a film obtained from the resin composition can be colored, and light transmitted through the resin composition film or light reflected from the resin composition film can be obtained in a desired manner. Coloring can be imparted to the color. In addition, light having a wavelength absorbed by the colorant (f) can be imparted from light transmitted through the resin composition film or reflected from the resin composition film.

  (F) Examples of the colorant include compounds that absorb light having a wavelength of visible light and are colored white, red, orange, yellow, green, blue, or purple. By combining two or more colors, the toning property of toning the light transmitted through the resin composition film of the resin composition or the light reflected from the resin composition film to the desired color coordinates Can be improved.

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

  (F3) The black agent refers to a compound that is colored black by absorbing light having a wavelength of visible light, and may be a pigment or a dye.

  (F3) Since the film of the resin composition is blackened by containing the black agent, the light transmitted through the resin composition film or the light reflected from the resin composition film is blocked. Can be improved. For this reason, it is suitable for a light shielding film such as a black matrix of a color filter or a black column spacer of a liquid crystal display, or an application that requires high contrast by suppressing reflection of external light.

  (F3) The black agent is preferably a compound that absorbs light of all wavelengths of visible light and is colored black from the viewpoint of light shielding properties. Also preferred is a mixture of two or more compounds selected from white, red, orange, yellow, green, blue or purple. By combining these two or more colors, it is possible to artificially color black and improve the light-shielding property.

  As the photosensitive resin composition of the present invention, the (f3) black agent preferably contains one or more selected from a black pigment, a black dye and a dye mixture of two or more colors, from the viewpoint of light shielding properties. It is more preferable to contain a black pigment.

  (F4) A colorant other than black refers to a compound that is colored by absorbing light having a wavelength of visible light. That is, the above-mentioned colorants that are colored white, red, orange, yellow, green, blue, or purple, excluding black.

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

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

  The content ratio of the colorant (f) 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 further preferably 15% by mass or more. When the content ratio is within the above range, light-shielding property, coloring property, and toning property can be improved. On the other hand, the content ratio is preferably 70% by mass or less, more preferably 65% by mass or less, and further preferably 60% by mass or less. When the content ratio is within the above range, the sensitivity at the time of exposure can be improved.

<(F1) Pigment>
In the photosensitive resin composition of the present invention, the colorant (f) preferably contains (f1) a pigment. As an aspect in which the (f) colorant contains the (f1) pigment, it is preferable to contain the (f1) pigment as the colorant other than the (f3) black agent and / or (f4) black.

  (F1) Pigment refers to a compound that colors an object by (f1) pigment being physically adsorbed on the surface of the object or (f1) pigment interacting with the surface of the object. Generally, it is insoluble in solvents. Further, (f1) coloring with a pigment is highly concealed, and fading due to ultraviolet rays or the like is difficult.

  (F1) By containing a pigment, it can be colored in an excellent concealing property, and the light shielding properties and weather resistance of the film of the resin composition can be improved.

  (F1) The number average particle diameter of the pigment is preferably 1 to 1,000 nm, more preferably 5 to 500 nm, and still more preferably 10 to 200 nm. When the number average particle diameter 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, (f1) The number average particle size of the pigment is 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; It can be determined by measuring laser scattering (dynamic light scattering method) due to the Brownian motion of the (f1) pigment in the solution using Sysmex Corporation. Moreover, the number average particle diameter of the (f1) pigment in the cured film obtained from a resin composition can be calculated | required by measuring using SEM and TEM. (F1) The number average particle diameter of the pigment is directly measured at an enlargement ratio of 50,000 to 200,000. (F1) When the pigment is a true sphere, the diameter of the true sphere is measured to obtain the number average particle diameter. (F1) When the pigment is not a true sphere, the longest diameter (hereinafter, “major axis diameter”) and the longest diameter (hereinafter, “minor axis diameter”) in the direction orthogonal to the major axis diameter are measured. The biaxial average diameter obtained by averaging the short axis diameters is defined as the number average particle diameter.

  (F1) As a pigment, an organic pigment or an inorganic pigment is mentioned, for example.

  By containing an organic pigment, coloring property or toning property can be imparted to the film of the resin composition. In addition, since it is an organic substance, it adjusts the transmission spectrum or absorption spectrum of the film of the resin composition, such as transmitting or blocking light of a desired specific wavelength by chemical structure change or functional conversion, thereby improving 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, selenium pigments, indoline pigments, Isoindoline pigment, isoindolinone pigment, benzofuranone pigment, perylene pigment, aniline pigment, azo pigment, azomethine pigment, condensed azo pigment, carbon black, metal complex pigment, lake pigment, toner pigment or A fluorescent pigment is mentioned. From the viewpoint of heat resistance, anthraquinone pigments, quinacridone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, benzofuranone pigments, perylene pigments, condensed azo pigments and carbon black are preferred.

  Examples of the phthalocyanine pigment include a copper phthalocyanine compound, a halogenated copper phthalocyanine compound, and a metal-free phthalocyanine compound.

  Examples of the anthraquinone pigments include aminoanthraquinone compounds, diaminoanthraquinone compounds, anthrapyrimidine compounds, flavantron compounds, anthanthrone compounds, indantron compounds, pyranthrone compounds, and violanthrone compounds.

  Examples of the azo pigments include disazo compounds and polyazo compounds.

  By containing an inorganic pigment, colorability or toning property can be imparted to the film of the resin composition. In addition, since it is an inorganic substance and is more excellent in heat resistance and weather resistance, the heat resistance and weather resistance of the film of the resin composition can be improved.

  Examples of inorganic pigments include titanium oxide, barium carbonate, zirconium oxide, zinc white, zinc sulfide, white lead, calcium carbonate, barium sulfate, white carbon, alumina white, silicon dioxide, kaolin clay, talc, bentonite, brown rice, molybdenum. Red, Molybdenum Orange, Chrome Vermillion, Yellow Lead, Cadmium Yellow, Yellow Iron Oxide, Titanium Yellow, Chrome Oxide, Viridian, Titanium Cobalt Green, Cobalt Green, Cobalt Chrome Green, Victoria Green, Ultramarine Blue, Bituminous Blue, Cobalt Blue, Cerulean Blue , Cobalt silica blue, cobalt zinc silica blue, manganese violet, cobalt violet, graphite or silver tin alloy, or titanium, copper, iron, manganese, cobalt, chromium, ni Kell, zinc, fine particles of a metal such as calcium or silver, oxides, composite oxides, sulfides, sulfates, nitrates, carbonates, nitrides, carbides or oxynitride.

  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 further preferably 15% by mass or more. When the content ratio is within the above range, light-shielding property, coloring property, or toning property can be improved. On the other hand, the content ratio is preferably 70% by mass or less, more preferably 65% by mass or less, and further preferably 60% by mass or less. When the content ratio is within the above range, the sensitivity at the time of exposure can be improved.

<(F2) Dye>
In the photosensitive resin composition of the present invention, the (f) colorant preferably contains (f2) a dye. As an aspect in which the (f) colorant contains the (f2) dye, it is preferable that the (f2) dye is contained as the colorant other than the (f3) black agent and / or (f4) black.

  (F2) Dye is a compound that colors an object by substitution of a substituent such as an ionic group or a hydroxy group in the dye on the surface structure of the object by chemical adsorption or strong interaction. In general, it is soluble in solvents and the like. In addition, (f2) coloring with a dye has high coloring power and high coloring efficiency because each molecule is adsorbed to an object.

  (F2) By containing a dye, it can be colored in a color excellent in coloring power, and the colorability and toning property of the film of the resin composition can be improved.

  (F2) Examples of the dye include a direct dye, a reactive dye, a sulfur dye, a vat dye, a sulfur dye, an acid dye, a metal-containing dye, a metal-containing acid dye, a basic dye, a mordant dye, an acid mordant dye, and a disperse dye. , Cationic dyes or fluorescent whitening dyes.

  (F2) As dyes, anthraquinone dyes, azo dyes, azine dyes, phthalocyanine dyes, methine dyes, oxazine dyes, quinoline dyes, indigo dyes, indigoid dyes, carbonium dyes, selenium dyes Perinone dyes, perylene dyes, triarylmethane dyes or xanthene dyes. Anthraquinone dyes, azo dyes, azine dyes, methine dyes, triarylmethane dyes, and xanthene dyes are preferable from the viewpoints of solubility in solvents and heat resistance described below.

  (F2) By containing a dye, coloring property or toning property can be imparted to the film of the resin composition.

  The content ratio of the (f2) dye 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, the colorability or toning property can be improved. On the other hand, the content ratio is preferably 50% by mass or less, more preferably 45% by mass or less, and further 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 is the aforementioned (f1) surface affinity group that interacts with the surface of the pigment or disperse dye, and (f1) the dispersion stabilization structure that improves the dispersion stability of the pigment or disperse dye. The compound which has. (G) Examples of the dispersion stabilizing structure of the dispersant include a polymer chain and / or a substituent having an electrostatic charge.

  (G) By containing a dispersing agent, when a resin composition contains (f1) a pigment or a disperse dye, those dispersion stability can be improved and the resolution after image development can be improved. . In particular, for example, when (f1) pigment is crushed to a number average particle size of 1 μm or less, the surface area of (f1) pigment particles increases, and (f1) aggregation of pigment particles tends to occur. Become. On the other hand, when (f1) a pigment is contained, the surface of the crushed (f1) pigment interacts with the surface affinity group of (g) the dispersant, and (g) a dispersion-stabilized structure of the dispersant. Due to the steric hindrance and / or electrostatic repulsion caused by (f1), the aggregation of pigment particles can be inhibited and the dispersion stability can be improved.

  Examples of the (g) dispersant having a surface affinity group include (g) a dispersant having only an amine value, (g) a dispersant having an amine value and an acid value, and (g) a dispersant having only an acid value. Or (g) a dispersant having neither an amine value nor an acid value. (F1) From the viewpoint of improving the dispersion stability of the pigment particles, (g) a dispersant having only an amine value, and (g) a dispersant having an amine value and an acid value are preferred.

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

  Examples of the dispersant having only the amine value (g) include, for example, “DISPERBYK” (registered trademark) -108, −109, −160, −161, −162, −163, −164, −164, and -166, -167, -168, -182, -184, -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 ( As described above, all are manufactured by Big Chemie Japan Co., Ltd.), “EFKA” (registered trademark) 4015, 4020, 4046, 4047, 4050, 4050, 4055, 060, 4080, 4300, 4330, 4340, 4400, 4401, 4402, 4403, 4403 or 4800 (all of which are manufactured by BASF), “Ajisper” (registered trademark) PB711 (Ajinomoto Fine Techno ( Or “SOLSPERSE” (registered trademark) 13240, 13940, 20000, 71000, or 76500 (all of which are manufactured by Lubrizol).

  Examples of the dispersant (g) having an amine value and an acid value include "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 Big Chemie Japan Co., Ltd.) "Azisper" (registered trademark) PB821, PB880 or PB881 (all of which are manufactured by Ajinomoto Fine Techno Co., Ltd.) or "SOLSPERSE" (registered trademark) 9000, 11200, 13650, 24000, 32000, 32500, 32500, 32600, 33000, 34750, 35100, 35200, the 37500, the 39000, the 56000, or the 76500 (all manufactured by Lubrizol) and the like.

  Examples of the dispersant having only the acid value (g) include "DISPERBYK" (registered trademark) -102, -110, -111, -118, -170, -171, -174, and the like. -2060 or -2096, "BYK" (registered trademark) -P104, -P105 or -220S (all of which are manufactured by Big Chemie Japan) or "SOLPERSE" (registered trademark) 3000, 16000, 17000, 18000, 21000, 26000, 28000, 36000, 36600, 38600, 41000, 41090, 53095, or 55000 (all of which are manufactured by Lubrizol).

  (G) Dispersing agents having neither amine value nor acid value include, for example, “DISPERBYK” (registered trademark) -103, -2152, -2200 or -192 (all of which are described above as Big Chemie Japan ( 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, (f1) pigment dispersion stability 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 here means the mass of potassium hydroxide equivalent to the acid reacting with (g) 1 g of the dispersant, and the unit is mgKOH / g. (G) After neutralizing 1 g of the dispersant with an acid, it can be determined by titrating with an aqueous potassium hydroxide solution. From the value of the amine value, the amine equivalent (unit: g / mol) which is the resin mass per 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, (f1) pigment dispersion stability 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 here means the mass of potassium hydroxide that reacts with (g) per 1 g of the dispersant, and the unit is mgKOH / g. (G) It can obtain | require by titrating 1g of dispersing agents with potassium hydroxide aqueous solution. From the value of the acid value, the acid equivalent (unit: g / mol) which is the resin mass per 1 mol of acidic groups can be calculated, and (g) the number of acidic groups in the dispersant can be determined.

  Examples of the dispersant having a polymer chain (g) include acrylic resin dispersants, polyoxyalkylene ether dispersants, polyester dispersants, polyurethane dispersants, polyol dispersants, polyethyleneimine dispersants or polyallylamine dispersants. A dispersing agent is mentioned. From the viewpoint of pattern processability with an alkali developer, an acrylic resin dispersant, a polyoxyalkylene ether dispersant, a polyester dispersant, a polyurethane dispersant, or a polyol dispersant is preferred.

  When the photosensitive resin composition of the present invention contains a disperse dye as the (f1) pigment and / or (f2) dye, the content ratio of the (g) dispersant in the photosensitive resin composition of the present invention is (f1 ) When the total of pigment and / or (f2) dye and (g) dispersant is 100% by mass, 1% by mass or more is preferable, 5% by mass or more is more preferable, and 10% by mass or more is more preferable. . When the content ratio is within the above range, (f1) the dispersion stability of the 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 further 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.

  A sensitizer is a compound that absorbs energy from exposure, generates excited triplet electrons by internal conversion and intersystem crossing, and can undergo energy transfer to the photopolymerization initiator (b2) described above. Say.

  The sensitivity at the time of exposure can be improved by containing a sensitizer. This is because (b2) the photopolymerization initiator or the like has no absorption, the sensitizer absorbs light having a long wavelength, and the energy is transferred from the sensitizer to (b2) the photopolymerization initiator or the like. Thus, it is presumed that the photoreaction efficiency can be improved.

  As the sensitizer, a thioxanthone sensitizer is preferable. Examples of the thioxanthone sensitizer include thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, or 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 radical polymerizable compound is 100 parts by mass. Preferably, 0.1 part by mass or more is more preferable, 0.5 part by mass or more is more preferable, and 1 part by mass or more is particularly preferable. The sensitivity at the time of exposure can be improved as content is in the said range. On the other hand, the content is preferably 15 parts by mass or less, more preferably 13 parts by mass or less, further 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.

  The chain transfer agent refers to a compound that can receive a radical from a polymer growth end of a polymer chain obtained by radical polymerization at the time of exposure and can undergo radical transfer to another polymer chain.

  By containing a chain transfer agent, the sensitivity at the time of exposure can be improved. This is presumed to be because radicals generated by exposure undergo radical crosslinking to the deep part of the film by radical transfer to other polymer chains by the chain transfer agent. In particular, for example, when the resin composition contains (f3) a black agent as the colorant (f) described above, light from exposure is absorbed by the (f3) black agent, so that the light does not reach the deep part of the film. There is a case. On the other hand, when it contains a chain transfer agent, radical crosslinking is carried out to the deep part of the film by radical transfer by the chain transfer agent, so that the sensitivity during exposure can be improved.

  Moreover, the pattern shape of a low taper can be obtained by containing a chain transfer agent. This is presumed to be because the molecular weight of the polymer chain obtained by radical polymerization at the time of exposure can be controlled by radical transfer by a chain transfer agent. That is, by containing a chain transfer agent, formation of a remarkable high molecular weight polymer chain due to excessive radical polymerization during exposure is inhibited, and an increase in the softening point of the resulting film is suppressed. Therefore, it is considered that the pattern reflow property at the time of thermosetting is improved and a low taper pattern shape is obtained.

  As the chain transfer agent, a thiol chain transfer agent is preferable. Examples of the thiol chain transfer agent include β-mercaptopropionic acid, β-mercaptopropionic acid methyl, β-mercaptopropionic acid ethyl, β-mercaptopropionic acid 2-ethylhexyl, β-mercaptopropionic acid n-octyl, β- Methoxybutyl mercaptopropionate, stearyl β-mercaptopropionate, isononyl β-mercaptopropionate, β-mercaptobutanoic acid, methyl β-mercaptobutanoate, ethyl β-mercaptobutanoate, 2-ethylhexyl β-mercaptobutanoate, β -N-octyl mercaptobutanoate, methoxybutyl β-mercaptobutanoate, stearyl β-mercaptobutanoate, isononyl β-mercaptobutanoate, methyl thioglycolate, n-octyl thioglycolate, thioglycolic acid Toxibutyl, 1,4-bis (3-mercaptobutanoyloxy) butane, 1,4-bis (3-mercaptopropionyloxy) butane, 1,4-bis (thioglycroyloxy) butane, ethylene glycol bis (thioglyco) Rate), trimethylolethane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate) Rate), trimethylolpropane tris (thioglycolate), 1,3,5-tris [(3-mercaptopropionyloxy) ethyl] isocyanuric acid, 1,3,5-tris [(3-mercaptobutanoyloxy) ethyl ] Isocyanuric acid, pentae Rithritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (thioglycolate), dipentaerythritol hexakis (3-mercaptopropionate) or dipentaerythritol hexa A kiss (3-mercaptobutyrate) is mentioned. From the viewpoint of improving sensitivity at the time of 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), trimethylol ethane tris (3-mercaptopropionate), trimethylol ethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopro) Pionate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (thioglycolate), 1,3,5-tris [(3-mercaptopropionyloxy) ethyl] isocyanuric acid, 1,3, 5-Tris [(3-Mercaptobutanoy Oxy) ethyl] isocyanuric acid, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (thioglycolate), dipentaerythritol hexakis (3-mercaptopropio) Nate) or dipentaerythritol hexakis (3-mercaptobutyrate).

  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) alkali-soluble resin and (d) radical polymerizable compound is 100 parts by mass. Preferably, 0.1 part by mass or more is more preferable, 0.5 part by mass or more is more preferable, and 1 part by mass or more is particularly preferable. When the content is within the above range, the sensitivity at the time of exposure can be improved, and a low taper pattern shape 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, further 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.

  A polymerization inhibitor is a radical that stops radical polymerization by capturing radicals generated during exposure or radicals at the polymer growth end of polymer chains obtained by radical polymerization during exposure and holding them as stable radicals. A possible compound.

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

  As the polymerization inhibitor, a phenol polymerization inhibitor is preferable. Examples of phenol polymerization inhibitors include 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 (All 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) alkali-soluble resin and (d) radical polymerizable compound is 100 parts by mass. Preferably, 0.03 parts by mass or more is more preferable, 0.05 parts by mass or more is more preferable, and 0.1 parts by mass or more is particularly preferable. 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, further preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less. The sensitivity at the time of exposure can be improved as content is in the said range.

<Adhesion improver>
The photosensitive resin composition used in the present invention may contain an adhesion improving agent. As adhesion improvers, 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 groups Examples thereof include compounds obtained by reacting silicon compounds. Two or more of these may be contained. By containing these adhesion improving agents, adhesion to an underlying substrate such as a silicon wafer, ITO, SiO ₂ , or silicon nitride can be enhanced when developing a photosensitive resin film. Further, resistance to oxygen plasma and UV ozone treatment used for cleaning or the like can be increased. The content of the adhesion improving agent is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the (a) alkali-soluble resin.

<Surfactant>
The photosensitive resin composition used in the present invention may contain a surfactant for the purpose of improving the wettability with the substrate or improving the film thickness uniformity of the coating film, if necessary. As the surfactant, commercially available compounds can be used. Specifically, as the silicone surfactant, SH series, SD series, ST series of Toray Dow Corning Silicone, “BYK” series of Big Chemie Japan, Shin-Etsu Silicone's KP Series, Nippon Oil & Fats 'Disform Series, TOSHIBA Silicone's TSF Series, etc. are listed. Fluorosurfactants include Dainippon Ink Industries'"MegaFac (registered trademark)" series, Examples include Sumitomo 3M's Florad series, Asahi Glass's "Surflon (registered trademark)" series, "Asahi Guard (registered trademark)" series, Shin-Akita Kasei's EF series, and Omninova Solution's Polyfox series. , Acrylic and / or methacrylic polymerization The surface active agent comprising, Kyoeisha Chemical Co. Poly flow series, manufactured by Kusumoto Chemicals, Inc. "DISPARLON (registered trademark)" series, and the like, but each available from companies, but are not limited to.

  The content of the surfactant is preferably 0.001 part by mass or more and 1 part by mass or less with respect to 100 parts by mass of the (a) alkali-soluble resin. By setting it as the above-mentioned range, wettability with a board | substrate and the film thickness uniformity of a coating film can be improved, without producing malfunctions, such as a bubble and a pinhole.

<Compound having phenolic hydroxyl group>
The photosensitive resin composition used by this invention may contain the compound which has a phenolic hydroxyl group for the purpose of supplementing the alkali developability of the photosensitive resin composition as needed. Examples of the compound having a phenolic hydroxyl group include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ. Bis26X-CP, BisP-PZ, BisP-IPZ, BisCRIPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (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-O HP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP, Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP (above, trade name, 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 (above, trade name, available from Asahi Organic Materials Co., Ltd.) 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,4-dihydroxyquinoline, 2,6-dihi Rokishikinorin, 2,3-dihydroxy quinoxaline, anthracene -1,2,10- triol, anthracene -1,8,9- triols, such as 8-quinolinol, and the like. By containing these compounds having a phenolic hydroxyl group, the resulting photosensitive resin composition hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer upon exposure. Less film loss and easy development in a short time. Therefore, the sensitivity is easily improved.

  The content of the compound having such 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, while maintaining high heat resistance, the alkali developability of the photosensitive resin composition can be improved.

<Inorganic particles>
The photosensitive resin composition used in the present invention may contain inorganic particles for the purpose of improving the relative dielectric constant of the cured film, improving the hardness, and reducing the thermal expansion coefficient. Preferable specific examples include silicon oxide, titanium oxide, barium titanate, barium sulfate, barium oxide, zirconium oxide, hafnium oxide, tantalum oxide, tungsten oxide, yttrium oxide, alumina, talc and the like. 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) having a relative dielectric constant (εr) of 20 or more, or Hafnium oxide (εr = 25) is a particularly preferable 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. Each particle diameter of the inorganic particles was measured with a scanning electron microscope (a scanning electron microscope manufactured by JEOL Ltd., JSM-6301NF). The primary particle diameter of the inorganic particles used in the present invention can be calculated by measuring the diameters of 100 particles randomly selected from a scanning electron micrograph and calculating the arithmetic average thereof.

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

<Heat acid generator>
The photosensitive resin composition used in the present invention may contain a thermal acid generator. The thermal acid generator generates an acid by heating and accelerates the crosslinking reaction of the thermal crosslinking agent. (A) When the alkali-soluble resin has an unclosed imide ring structure or oxazole ring structure, Cyclization can be promoted and the mechanical properties of the cured film can be further improved.

  The thermal decomposition starting 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 during drying (pre-baking: about 70 to 140 ° C.) after applying the photosensitive resin composition of the present invention to the substrate, and final heating (curing: about) after patterning by subsequent exposure and development. It is preferable to select one that generates an acid at the time of 100 to 400 ° C., since a decrease in sensitivity during development can be suppressed.

  The acid generated from the thermal acid generator used in the present invention is preferably a strong acid. For example, arylsulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid Alkyl sulfonic acids such as haloalkyl sulfonic acids such as trifluoromethyl sulfonic acid are preferred. These are used as salts such as onium salts or as covalently bonded compounds such as imidosulfonates. Two or more of these may be contained.

  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 it as the above-mentioned range, while maintaining high heat resistance, the effect by addition of the above-mentioned thermal acid generator can be expressed.

<(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 at least one compound selected from the group consisting of (i) cyclic amide, cyclic urea and derivatives thereof in the cured film, the compound (i) functions as an acid gas quencher, It is estimated that deterioration and pixel shrinkage can be suppressed, and sufficient long-term reliability as an organic EL device can be given.

  (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 May be.

(In General Formula (11), u represents an integer of 1 to 4, Y represents CH or a nitrogen atom. R ¹⁸ and R ¹⁹ each independently represent 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 easily remaining in the film after heat treatment. Moreover, it is preferable that a boiling point is 400 degrees C or less from a viewpoint of suppressing the nonuniformity at the time of application | coating. When 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 amide, cyclic urea 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-ca Examples include prolactam. Among these, N-cyclohexyl-2-pyrrolidone (boiling point: 154 ° C./7 mmHg, normal pressure boiling point conversion: 305 ° C.), N- (2-hydroxyethyl) -2-pyrrolidone (boiling point: 175 ° C./10 mmHg, normal (Pressure boiling point conversion: 313 ° C.) is preferable because it has a high boiling point and tends to remain in the film 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. Moreover, in the photosensitive resin composition which forms a cured film, the addition amount of a compound (i) becomes like this. Preferably it is 0.1 mass part or more with respect to 100 mass parts of (a) alkali-soluble resin, More preferably, it is 1 mass part. It is above, Preferably it is 15 mass parts or less, More preferably, it is 10 mass parts or less. The long-term reliability of an excellent organic EL device can be improved by setting the amount of compound (i) to be 0.1 parts by mass or more, and patterning can be performed with excellent sensitivity by setting it to 15 parts by mass or less. Can do.

<Method for producing resin composition>
Next, the manufacturing method of the photosensitive resin composition of this invention is demonstrated. For example, by dissolving the components (a) to (c) and, if necessary, a thermal crosslinking agent, an adhesion improver, a surfactant, a compound having a phenolic hydroxyl group, inorganic particles, a thermal acid generator, etc. Resin composition can be obtained. Examples of the dissolution method include stirring and heating. In the case of heating, the heating temperature is preferably set in a range that does not impair the performance of the photosensitive resin composition, and is usually room temperature to 80 ° C. In addition, the dissolution order of each component is not particularly limited, and for example, there is a method of sequentially dissolving compounds having low solubility. In addition, for components that tend to generate bubbles when stirring and dissolving, such as surfactants and some adhesion improvers, by dissolving other components and adding them last, poor dissolution of other components due to the generation of bubbles Can be prevented.

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

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

  A method for producing a cured film using the photosensitive resin composition of the present invention includes a step of coating the photosensitive resin composition on a substrate to form a photosensitive resin film, a step of 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 will be described below.

  The photosensitive resin composition of the present invention is applied by spin coating, slit coating, dip coating, spray coating, printing, or the like to obtain a coating film of the photosensitive resin composition. Of these, the slit coat method is preferably used. The slit coating method can be applied with a small amount of coating liquid, and is advantageous for cost reduction. The amount of coating liquid required for the slit coating method is, for example, about 1/5 to 1/10 as compared with the spin coating method. There is no restriction | limiting in particular about the slit nozzle used for application | coating, The thing marketed from the some manufacturer can be used. Specifically, Dainippon Screen Mfg. Co., Ltd. “Linear Coater”, Tokyo Ohka Kogyo Co., Ltd. “Spinless”, Toray Engineering Co., Ltd. “TS Coater”, Chugai Furnace Industry Co., Ltd. “Table Coater” "CS series" "CL series" manufactured by Tokyo Electron Ltd., "Inline slit coater" manufactured by Thermotronics Trading Co., Ltd., "Head coater HC series" manufactured by Hirata Kiko Co., Ltd., and the like. The coating speed is generally in the range of 10 mm / second to 400 mm / second. The thickness of the coating film varies depending on the solid content concentration, viscosity, etc. of the photosensitive resin composition, but is usually applied so that the film thickness after drying is 0.1 to 10 μm, preferably 0.3 to 5 μm. The

  Prior to the application, the substrate on which the photosensitive resin composition is applied may be pretreated with the adhesion improving agent described above in advance. For example, a solution obtained by dissolving 0.5-20% 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, diethyl adipate, etc. And a method of treating the substrate surface. Examples of the substrate surface treatment method include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.

  After application, a vacuum drying treatment is performed as necessary. In general, the substrate on which the coating film is formed is dried under reduced pressure. For example, a substrate on which a coating film is formed is placed on proxy pins arranged in a vacuum chamber, and the inside of the vacuum chamber is decompressed and dried under reduced pressure. At this time, if the distance between the substrate and the vacuum chamber top plate is large, the air located between the substrate and the vacuum chamber top plate flows in a large amount along with the reduced pressure drying, and it becomes easy to generate moire. Therefore, it is preferable to adjust the proxy pin height so as to narrow the interval. The distance between the substrate and the vacuum chamber top is preferably about 2 to 20 mm, more preferably 2 to 10 mm.

  The vacuum drying speed depends on the vacuum chamber volume, the vacuum pump capacity, the pipe diameter between the chamber and the pump, etc., for example, under conditions where the pressure in the vacuum chamber is reduced to 40 Pa after 60 seconds in the absence of a coating substrate. Set and used. The general vacuum drying time is often about 30 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. By setting the ultimate pressure to 100 Pa or less, the coating film surface can be brought into a dry state without stickiness, whereby surface contamination and generation of particles can be suppressed in subsequent substrate transport.

  In general, after coating or drying under reduced pressure, the coating film is dried by heating. This process is also called pre-baking. Drying uses a hot plate, oven, infrared rays and the like. When a hot plate is used, the coating film is heated directly on the plate or on a jig such as a proxy pin installed on the plate. As the material of the proxy pin, there is a metal material such as aluminum or stainless steel, or a synthetic resin such as polyimide resin or “Teflon (registered trademark)”. Any material can be used as long as it has heat resistance. . 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 it is preferably performed in the range of 50 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. Exposure is performed by irradiating actinic radiation on a photosensitive resin film through a mask having a desired pattern. As the actinic radiation used for exposure, there are ultraviolet rays, visible rays, electron beams, X-rays and the like. 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. . When it has positive photosensitivity, the exposed portion is dissolved in the developer. When it has negative photosensitivity, the exposed area is cured and insolubilized in the developer.

  After exposure, a desired pattern is formed using a developer by removing an exposed portion in the case of a positive type and a non-exposed portion in the case of a negative type. As a developer, in both positive and negative types, tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, An aqueous solution of a compound exhibiting alkalinity such as dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine is preferred. In some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added singly or in combination. Good. As a developing method, methods such as spraying, paddle, dipping, and ultrasonic waves are possible.

  Next, it is preferable to rinse the pattern formed by development with distilled water. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to distilled water for rinsing treatment.

  Next, heat curing is performed. Since components having low heat resistance can be removed by heat curing, 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 and a polybenzoxazole precursor, a copolymer thereof, or a copolymer of polyimide with them, heating When an imide ring or an oxazole ring can be formed by curing, heat resistance and chemical resistance can be improved, and when it contains a compound having at least two alkoxymethyl groups, methylol groups, epoxy groups, or oxytanyl groups The thermal crosslinking reaction can be advanced by heat curing, and the heat resistance and chemical resistance can be improved. This heat curing is carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. As an example, heat treatment is performed at 150 ° C. and 250 ° C. for 30 minutes each. Alternatively, a method such as linearly raising the temperature from room temperature to 300 ° C. over 2 hours can be mentioned. The heat curing conditions in the present invention are preferably 300 ° C. or higher and more preferably 350 ° C. or higher in terms of reducing the amount of outgas generated from the cured film. Moreover, 500 degrees C or less is preferable at the point which gives sufficient film toughness to a cured film, and 450 degrees C or less is more preferable.

  Next, the manufacturing method of the cured film using the photosensitive sheet | seat formed from the photosensitive resin composition of this invention is demonstrated. Here, the photosensitive sheet is defined as a sheet obtained by applying a photosensitive resin composition on a peelable substrate and drying it.

  When using the photosensitive sheet | seat formed from the photosensitive resin composition of this invention, when it has a protective film in the said photosensitive sheet | seat, this is peeled, the photosensitive sheet | seat and a board | substrate are made to oppose, and it bonds together by thermocompression bonding. A photosensitive resin film is obtained. The photosensitive sheet can be obtained by applying and drying the photosensitive resin composition of the present invention on a support film composed of polyethylene terephthalate or the like which is a peelable substrate.

  The thermocompression bonding can be performed by a heat press process, a heat laminating process, a heat vacuum laminating process, or the like. The bonding temperature is preferably 40 ° C. or higher from the viewpoint of adhesion to the substrate and embedding. Further, when the photosensitive sheet has photosensitivity, the bonding temperature is preferably 140 ° C. or lower in order to prevent the photosensitive sheet from being cured at the time of bonding and reducing 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 heating and curing. Thus, a cured film can be formed.

  The cured film obtained by curing the photosensitive resin composition or photosensitive sheet of the present invention can be used for electronic components such as organic EL display devices, semiconductor devices, and multilayer wiring boards. Specifically, an insulating layer of an organic EL element, a planarization layer of a substrate with a driving circuit of a display device using the organic EL element, an interlayer insulating film between rewirings of a semiconductor device or a semiconductor component, a semiconductor passivation film, a semiconductor Suitable for applications such as protective films for devices, interlayer insulation films for multilayer wiring for high-density mounting, wiring protection insulation layers for circuit boards, on-chip microlenses for solid-state imaging devices, and flattening layers for various displays and solid-state imaging devices It is done. Examples of the electronic device having a surface protective film, an interlayer insulating film, or the like on which the cured film of the present invention is disposed include MRAM having low heat resistance. That is, the cured film of the present invention is suitable for a surface protective film of MRAM. In addition to MRAM, polymer memory (Polymer Ferroelectric RAM: PFRAM) and phase change memory (Phase Change RAM: PCRAM, or Ovonics Unified Memory: OUM), which are promising as next-generation memories, are also more heat resistant than conventional memories. There is a high probability of using low new materials. Therefore, the cured film of the present invention is also suitable for these surface protective films. In addition, a display device including a first electrode formed on a substrate and a second electrode provided to face the first electrode, specifically, for example, an LCD, an ECD, an ELD, an organic electroluminescent element It can be used for an insulating layer of the display device (organic electroluminescence device) used. Hereinafter, an organic EL display device will be described as an example.

<Organic EL display device>
The organic EL display device of the present invention has a 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 cured according to the present invention. It consists of a membrane. Taking an active matrix display device as an example, it has a TFT on a substrate such as a glass or a resin film, and a wiring located on a side portion of the TFT and connected to the TFT, and covers the unevenness thereon. Thus, the planarization layer is provided, and the 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, in recent years, organic EL display devices have become mainstream, and it is preferable that the substrate having the above drive circuit is an organic EL display device made of a resin film. When the 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 excellent flexibility. From the viewpoint of improving the adhesion with the cured film obtained by curing the photosensitive resin composition or photosensitive sheet of the present invention, polyimide is particularly preferable as the resin film.

  FIG. 1 shows a cross-sectional view of an example of a TFT substrate. On the substrate 6, bottom-gate or top-gate TFTs (thin film transistors) 1 are provided in a matrix, and the insulating layer 3 is formed so as 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. A contact hole 7 reaching the wiring 2 is provided in the planarization layer 4. An ITO (transparent electrode) 5 is formed on the planarizing layer 4 while being connected to the wiring 2 via the contact hole 7. Here, ITO5 becomes an electrode of a display element (for example, organic EL element). And the insulating layer 8 is formed so that the periphery of ITO5 may be covered. The organic EL element may be a top emission type that emits emitted light from the side opposite to the substrate 6 or a bottom emission type that extracts light from the substrate 6 side. In this manner, an active matrix organic EL display device in which each organic EL element is connected with the TFT 1 for driving the organic EL element is obtained.

  As described above, the insulating layer 3, the planarizing layer 4, and / or the insulating layer 8 are a step of forming a photosensitive resin film made of the resin composition or resin sheet of the present invention, a step of exposing the photosensitive resin film, It can form by the process of developing the exposed photosensitive resin film, and the process of heat-processing the developed photosensitive resin film. An organic EL display device can be obtained from the manufacturing method having these steps.

  The photosensitive resin composition of the present invention is also suitably used for a fan-out wafer level package (fan-out WLP). The fan-out WLP is provided with an extended portion using a sealing resin such as epoxy resin around the semiconductor chip, rewiring from the electrode on the semiconductor chip to the extended portion, and mounting a solder ball on the extended portion. This is a semiconductor package that secures the necessary number of terminals. In the fan-out WLP, wiring is installed so as to straddle the boundary line 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 provided with metal wiring and a sealing resin, and wiring is formed on the interlayer insulating film. In addition to this, in a semiconductor package of a type 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 composed of two or more materials, and wiring is formed on the interlayer insulating film. The cured film formed by curing the photosensitive resin composition of the present invention has high adhesion to a semiconductor chip provided with metal wiring, and also has high adhesion to an epoxy resin or the like and a sealing resin. It is suitably used as an interlayer insulating film provided on a substrate composed of more than one kind of material.

  Hereinafter, the present invention will be described with reference to examples and the like, but the present invention is not limited to these examples. In addition, evaluation of the photosensitive resin composition in an Example was performed with the following method.

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

<Measurement of number average particle diameter of pigment>
Using a zeta potential / particle diameter / molecular weight measuring device (Zeta Sizer Nano ZSP; manufactured by Sysmex Corporation), using PGMEA as a diluent solvent, the pigment dispersion is adjusted to a concentration of 1.0 × 10 ⁻⁵ to 40% by volume. After dilution, the refractive index of the diluted solvent was set to PGMEA, the refractive index of the measurement target was set to 1.8, and laser light with a wavelength of 633 nm was irradiated to measure the number average particle size of the pigment in the pigment dispersion.

(1-1) Sensitivity evaluation of positive photosensitive resin composition The photosensitive resin composition (varnish) produced in the examples and comparative examples was spin-coated on an 8-inch silicon wafer, and then a 120 ° C hot plate ( This was baked for 3 minutes using a coating and developing apparatus Act-8 manufactured by Tokyo Electron Co., Ltd. to prepare a pre-baked film having a thickness of 2.5 μm. The membrane was exposed at 10 mJ / cm ² steps by the exposure amount of 0~1000mJ / cm ² using an i-line stepper (NIKON NSR i9). After the exposure, development is performed with a 2.38 mass% aqueous solution of tetramethylammonium (TMAH) (manufactured by Mitsubishi Gas Chemical Co., Ltd., ELM-D) for 90 seconds, followed by rinsing with pure water, and development with an isolated pattern of 10 μm. Membrane A was obtained.

  Using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation), the resolution pattern of the produced post-development film is observed, and an exposure amount for forming a 10 μm line-and-space pattern in a one-to-one width Sensitivity was defined as (optimum exposure amount Eop).

(1-2) Evaluation of sensitivity of negative photosensitive resin composition The photosensitive resin composition (varnish) produced in Examples and Comparative Examples was spin coated on an ITO substrate (MS-A100; manufactured by Mikasa Corporation). Is applied by spin coating at an arbitrary number of revolutions, and then prebaked at 100 ° C. for 120 seconds using a hot plate (SCW-636; manufactured by Dainippon Screen Mfg. Co., Ltd.), and prebaked with a film thickness of about 2.0 μm. A membrane was prepared. The prepared pre-baked film was subjected to a gray scale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International) using a double-sided alignment single-sided exposure apparatus (mask aligner PEM-6M; manufactured by Union Optics). ) Through patterning exposure with i-line (wavelength 365 nm), h-line (wavelength 405 nm) and g-line (wavelength 436 nm) of an ultra-high pressure mercury lamp. After exposure, using a small photolithographic developing device (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), develop with a 2.38 mass% TMAH aqueous solution for 60 seconds, rinse with water for 30 seconds, and form an isolated pattern of 10 μm. A development film having the same was produced.

  Using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation), the resolution pattern of the produced post-development film is observed, and an exposure amount for forming a 10 μm line-and-space pattern in a one-to-one width Sensitivity was defined as (optimum exposure amount Eop).

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

(3) Evaluation of bendability After applying varnish on a PI film substrate by spin coating at an arbitrary rotational speed using a spin coater (MS-A100; manufactured by Mikasa Co., Ltd.), a hot plate (SCW-636; Was prebaked at 120 ° C. for 120 seconds using a Dainippon Screen Mfg. Co., Ltd. to prepare a prebaked film having a thickness of about 3.0 μm. Using a high temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo System Co., Ltd.), this pre-baked film was heated to 250 ° C. at an oxygen concentration of 20 ppm or less at a rate of 5 ° C./minute, and then heated at 250 ° C. for 1 hour. Then, a cured film of the composition was produced.

  After thermosetting, the PI film substrate having the prepared cured film was cut into a length of 50 mm and a width of 10 mm. The PI film substrate was held for 30 seconds in a state where the PI film substrate was bent at 180 ° on a line of 25 mm in length with the surface of the cured film facing outside. After 30 seconds, the folded PI film substrate is opened, and the bent portion on the 25 mm vertical line on the surface of the cured film is observed using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation). Changes were evaluated. The case where there was no peeling of the cured film from the PI film substrate and there was no change in appearance such as cracks or deformation on the surface of the cured film was regarded as acceptable (A), and the others were regarded as unacceptable (B).

(4) Evaluation of long-term reliability of organic EL display device FIG. 1 is a schematic view of a manufacturing procedure of an organic EL display device. First, an ITO transparent conductive film 10 nm was formed on the entire surface of a 38 mm mm × 46 mm non-alkali glass substrate 9 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 subjected to ultrasonic cleaning with Semico Clean 56 (trade name, manufactured by Furuuchi Chemical Co., Ltd.) for 10 minutes, and then washed 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 through a photomask and then developed with a 2.38 mass% TMAH aqueous solution to dissolve unnecessary portions and rinsed with pure water. The obtained 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 System Co., Ltd.). In this way, openings having a width of 70 μm and a length of 260 μm are arranged with a pitch of 155 μm in the width direction and a pitch of 465 μm in the length direction, and the insulating layer 12 having a shape in which each opening exposes the first electrode is formed on the substrate. It was limited to the effective area. In this way, an insulating layer having an insulating layer aperture ratio of 25% was formed in the effective area of the substrate having a square of 16 mm on one 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. In addition, the vacuum degree at the time of vapor deposition was 1 * 10 < ^-3 > Pa or less, and the board | substrate was rotated with respect to the vapor deposition source during vapor deposition. First, 10 nm of the compound (HT-1) was deposited as a hole injection layer and 50 nm of the 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 so that the doping concentration was 10%. Next, the compound (ET-1) and the compound (LiQ) as an electron transporting material were laminated in a volume ratio of 1: 1 to a thickness of 40 nm. The structure of the compound used in the organic EL layer is shown below.

  Next, after depositing a compound (LiQ) by 2 nm, Mg and Ag were deposited by 10 nm at a volume ratio of 10: 1 to form a second electrode (transparent electrode) 14. Lastly, a cap-shaped glass plate is sealed by bonding with an epoxy resin adhesive in a low-humidity nitrogen atmosphere, and a top emission type organic EL that is a square with a side of 5 mm on one substrate. Four display devices were produced. In addition, the film thickness said here is a display value in 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 upward, 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), after 250 hours, 500 hours, and 1000 hours, light was emitted by direct current driving of the organic EL display device 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. If the pixel light emission area ratio after 1000 hours by this evaluation method is 80% or more, it can be said that long-term reliability is excellent, and 90% or more is more preferable.

The names of the abbreviations of acid dianhydrides, diamines, and other reagents shown in the following examples and comparative examples are as follows.
6FDA: 4,4′-hexafluoroisopropylidenediphthalic 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 having 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; metaaminophenol 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).

  The alkoxymethyl group-containing thermally crosslinkable compound (e-1), Nicalac MX-270 (e-2), VG-3101L (e-3) and phenol compound BisP-AF (h-) used in each Example and Comparative Example 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 dropping, the mixture was reacted at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

  30 g of the obtained 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 by confirming that the balloons did not squeeze any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration, and the mixture was 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 dry nitrogen stream, TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 21.22 g (0.05 mol), 5-naphthoquinone diazide sulfonyl chloride 26.86 g (0.10 mol), 4-naphtho 13.43 g (0.05 mol) of quinonediazidesulfonyl chloride was dissolved in 50 g of 1,4-dioxane and brought to room temperature. Here, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (b1-1) represented by the following formula.

<Synthesis Example 3 Synthesis of Quinone Diazide Compound (b1-2)>
Under a dry nitrogen stream, TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 15.31 g (0.05 mol) and 5-naphthoquinonediazidosulfonyl acid chloride 40.28 g (0.15 mol) -Dissolved in 450 g of dioxane and brought to room temperature. Using 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane, a quinonediazide compound (b1-2) represented by the following formula was obtained in the same manner as in Synthesis Example 2.

<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 Chemical Industry Co., Ltd.) and 13.43 g (0.125 mol) of 5-naphthoquinone diazide sulfonyl chloride were used. -Dissolved in 450 g of dioxane and brought to room temperature. Using 20.24 g of triethylamine mixed with 50 g of 1,4-dioxane, a quinonediazide compound (b1-3) represented by the following formula was obtained in the same manner as in Synthesis Example 2.

[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; 0.62 g (0.0025 mol) of SiDA Dissolved in 200 g of NMP. TMEG 20.51g (0.05mol) was added with NMP50g here, and it stirred at 40 degreeC for 1 hour. Thereafter, 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 obtained by diluting 11.9 g (0.1 mol) of DFA with 5 g of NMP was added dropwise over 10 minutes, and then stirring was continued at 40 ° C. for 1 hour. After stirring, the solution was poured into 2 L of water, and a solid precipitate was collected by filtration. Further, it was washed 3 times with 2 L of water, and the collected polymer solid was dried with a vacuum dryer at 50 ° C. for 72 hours to obtain a 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 an alkoxymethyl group-containing thermal cross-linking agent (e-1) are added to 50 g of GBL, and positive photosensitive. A varnish A1 was obtained. Using the obtained varnish A1, as described above, the sensitivity evaluation, the remaining film rate evaluation, the bending property evaluation, and the long-term reliability evaluation of the organic EL display device were performed. The evaluation results are shown in Table 2.

[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 was used as the end-capping agent to 4.13 g (0.025 mol) of ABP. Surprisingly, a 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) are added to 50 g of GBL and positive photosensitive property is obtained. A varnish B1 of the resin composition was obtained. Using the obtained varnish B1, as described above, evaluation of sensitivity evaluation, residual film ratio evaluation, bendability, and long-term reliability evaluation of the organic EL display device was performed. The evaluation results are shown in Table 2.

[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. TMEG 20.51g (0.05mol) was added with NMP10g here, and it was made to react at 60 degreeC for 1 hour. Thereafter, 1.09 g (0.01 mol) of MAP was added as a terminal blocking agent, and stirring was further continued at 60 ° C. for 1 hour. Subsequently, it stirred at 180 degreeC for 4 hours, and after completion | finish of stirring, the solution was thrown into 2 L of water, and white precipitation was obtained. This precipitate was collected by filtration, washed three times with water, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (C).

  10 g of the obtained resin (C), 3.0 g of a quinonediazide compound (b1-1), 1.0 g of an alkoxymethyl group-containing thermal crosslinking agent (e-1), and 1.0 g of a phenol compound BisP-AF (h-1) In addition to 50 g of GBL, a positive photosensitive resin composition varnish C1 was obtained. As described above, evaluation of sensitivity evaluation, remaining film rate evaluation, bendability, and long-term reliability evaluation of an organic EL display device was performed using the obtained varnish C1. The evaluation results are shown in Table 2.

[Example 4]
BAHF 15.56 g (0.0425 mol) is 10.98 g (0.03 mol), MAP 1.09 g (0.01 mol) is ABP 1.65 g (0.01 mol), and hydroxyl group-containing diamine compound (α) 6 A closed ring polyimide resin (D) was obtained in the same manner as in Example 3 except that .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 crosslinking agent VG-3101L (e-3) are added to 50 g of GBL to obtain a varnish D1 of a positive photosensitive resin composition. It was. Using the obtained varnish D1, as described above, sensitivity evaluation, residual film rate evaluation, bending property evaluation, and long-term reliability evaluation of the organic EL display device were performed. The evaluation results are shown in Table 2.

[Example 5]
Under a dry nitrogen stream, BAHF 11.9 g (0.0325 mol), BIS-AT-AF 5.43 g (0.015 mol), SiDA 0.62 g (0.003 mol) were dissolved in NMP 100 g. TMEG 15.39g (0.0375mol) was added here with NMP10g, and it was made to react at 60 degreeC for 1 hour. Thereafter, 2.45 g (0.025 mol) of MA was added as a terminal blocking agent, and stirring was further continued at 60 ° C. for 1 hour. Subsequently, it stirred at 180 degreeC for 4 hours, and after completion | finish of stirring, the solution was thrown into 2 L of water, and white precipitation was obtained. This precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a closed ring polyimide resin (E).

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

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

  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 Nicalac MX-270 (e-2) are added to 50 g of GBL, and positive photosensitive properties are obtained. A varnish F1 of the resin composition was obtained. Using the obtained varnish F1, as described above, sensitivity evaluation, residual film ratio evaluation, bending property evaluation, and long-term reliability evaluation of an organic EL display device were performed. The evaluation results are shown in Table 2.

[Example 7]
Instead of BAHF 15.56 g (0.0425 mol), BIS-AT-AF 7.25 g (0.02 mol), DAE 4.0 g (0.02 mol), MAP 1.09 g (0.01 mol) 1.64 g ( A closed ring polyimide resin (G) was obtained in the same manner as in Example 3 except that the amount 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 an alkoxymethyl group-containing thermal crosslinking agent (e-1) are added to 50 g of GBL, and the varnish G1 of the positive photosensitive resin composition. Got. Using the obtained varnish G1, as described above, sensitivity evaluation, residual film rate evaluation, bending property evaluation, and long-term reliability evaluation of an organic EL display device were performed. The evaluation results are shown in Table 2.

[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. Dissolved in 200 g. TMEG 20.51g (0.05mol) was added with NMP50g here, and it stirred at 60 degreeC for 1 hour. Thereafter, 2.73 g (0.025 mol) of MAP was added as a terminal blocking agent, and stirring was further continued at 60 ° C. for 1 hour. Subsequently, it stirred at 180 degreeC for 4 hours, and after completion | finish of stirring, the solution was thrown into 2 L of water, and white precipitation was obtained. This precipitate was collected by filtration, washed with water three times, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a 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 crosslinking agent VG-3101L (e-3) are added to 50 g of GBL to obtain a varnish H1 of a positive photosensitive resin composition. It was. Using the obtained varnish H1, as described above, sensitivity evaluation, residual film ratio evaluation, bending property evaluation, and long-term reliability evaluation of an organic EL display device were performed. The evaluation results are shown in Table 2.

[Example 9]
A closed ring polyimide resin (I) was prepared in the same manner as in Example 3 except that 15.56 g (0.0425 mol) of BAHF was changed to 10.07 g (0.0275 mol) and 3.0 g (0.015 mol) of DAE was added. Obtained.

  10 g of the obtained resin (I), 3.0 g of a quinonediazide compound (b1-3), 1.0 g of an alkoxymethyl group-containing thermal crosslinking agent (e-1), 1.0 g of a phenol compound BisP-AF (h-1) In addition to 50 g of GBL, a positive photosensitive resin composition varnish I1 was obtained. As described above, the obtained varnish I1 was used for sensitivity evaluation, residual film ratio evaluation, evaluation of bendability, and long-term reliability evaluation of the organic EL display device. The evaluation results are shown in Table 2.

[Example 10]
10 g of the resin (C), 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 C2 of a positive photosensitive resin composition. Using the obtained varnish C2, as described above, sensitivity evaluation, residual film ratio evaluation, bending property evaluation, and long-term reliability evaluation of the organic EL display device were performed. The evaluation results are shown in Table 2.

[Example 11]
10 g of resin (D), 3.0 g of quinonediazide compound (b1-3), 1.0 g of alkoxymethyl group-containing thermal crosslinking agent (e-1), 1.0 g of phenol compound BisP-AF (h-1) are added to 50 g of GBL. Thus, a varnish D2 of a positive photosensitive resin composition was obtained. As described above, evaluation of sensitivity evaluation, remaining film rate evaluation, bendability, and long-term reliability evaluation of an organic EL display device was performed using the obtained varnish D2. The evaluation results are shown in Table 2.

[Example 12]
10 g of resin (G), 3.0 g of quinonediazide compound (b1-1), and 1.0 g of a cross-linking agent VG-3101L (e-3) were added to 50 g of GBL to obtain varnish G2 of a positive photosensitive resin composition. As described above, the obtained varnish G2 was used for sensitivity evaluation, residual film rate evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device. The evaluation results are shown in Table 2.

[Example 13]
Resin (A) 10 g, quinonediazide compound (b1-1) 3.0 g, alkoxymethyl group-containing thermal crosslinking agent (e-1) 1.0 g, cyclic amide compound N-methyl-2-pyrrolidone (NMP) 0. 5 g was added to 50 g of GBL to obtain varnish A2 of a positive photosensitive resin composition. Using the obtained varnish A2, as described above, the sensitivity evaluation, the remaining film rate evaluation, the bendability evaluation, and the long-term reliability evaluation of the organic EL display device were performed. The evaluation results are shown in Table 2.

  Using a coating and developing apparatus Mark-7 (manufactured by Tokyo Electron Co., Ltd.), varnish was applied on an 8-inch silicon wafer by spin coating, and baked on a hot plate at 120 ° C. for 3 minutes to obtain a film thickness of 3 A 2 μm pre-baked film was prepared. Thereafter, using the Mark-7 developing device, development was performed with 2.38% TMAH for a time when the film loss during development was 0.5 μm, rinsed with distilled water, shaken off, dried, and developed. The solid film was baked at 250 ° C. for 60 minutes in an oven at a predetermined temperature in a nitrogen atmosphere to obtain a cured film.

The film thickness of the obtained cured film was measured, and 1 × 5 cm was cut out and was adsorbed and trapped by the purge and trap method. Specifically, the collected 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. The collected components were thermally desorbed using a thermal desorption apparatus at a primary desorption condition of 260 ° C. for 15 minutes, a secondary adsorption desorption condition of −27 ° C. and 320 ° C. for 5 minutes, and then a GC-MS apparatus 7890 / 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 generation was calculated by creating a calibration curve by GC-MS analysis of NMP under the same conditions as above. The obtained value (μg) was divided by an area of 5 cm ² to obtain μg / cm ² . The value was divided by 100 times the specific gravity of the alkali-soluble resin (a) multiplied by the film thickness, and the total content of NMP in the cured film was calculated to be 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; 0.62 g (0.0025 mol) of SiDA Dissolved in 200 g of NMP. TMEG 10.26g (0.025mol) and 6FDA 11.11g (0.025mol) were added with NMP50g here, and it stirred at 40 degreeC for 1 hour. Thereafter, 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 obtained by diluting 11.9 g (0.1 mol) of DFA with 5 g of NMP was added dropwise over 10 minutes, and then stirring was continued at 40 ° C. for 1 hour. After stirring, the solution was poured into 2 L of water, and a solid precipitate was collected by filtration. Further, it was washed 3 times with 2 L of water, and the collected polymer solid was dried with a vacuum dryer at 50 ° C. for 72 hours to obtain a polyamic acid ester resin (J).

  Varnish J1 of positive photosensitive resin composition by adding 10 g of the obtained resin (J), 3.0 g of quinonediazide compound (b1-1), and 1.0 g of alkoxymethyl group-containing thermal crosslinking agent (e-1) to 50 g of GBL. Got. As described above, the obtained varnish J1 was used for sensitivity evaluation, residual film ratio evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device. The evaluation results are shown in Table 2.

[Comparative Example 2]
Under a dry nitrogen stream, BAHF 10.07 g (0.0275 mol), BIS-AT-AF 7.25 g (0.02 mol), SiDA 0.62 g (0.0025 mol) were dissolved in NMP 200 g. TMEG 14.36g (0.035mol) and CBDA 2.94g (0.015mol) were added here with NMP50g, and it stirred at 40 degreeC for 1 hour. Thereafter, a solution obtained by diluting 11.9 g (0.1 mol) of DFA with 5 g of NMP was added dropwise over 10 minutes, and then 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 a solid precipitate was collected by filtration. Further, it was washed with 2 L of water three times, and the collected polymer solid was dried with a vacuum dryer at 50 ° C. for 72 hours to obtain a polyamic acid ester resin (K).

  10 g of the obtained resin (K), 3.0 g of the quinonediazide compound (b1-2), and 1.0 g of an alkoxymethyl group-containing thermal crosslinking agent (e-1) are added to 50 g of GBL, and the varnish K1 of the positive photosensitive resin composition. Got. Using the obtained varnish K1, as described above, the sensitivity evaluation, the remaining film ratio evaluation, the bending property evaluation, and the long-term reliability evaluation of the organic EL display device were performed. The evaluation results are shown in Table 2.

[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. Here, 22.21 g (0.05 mol) of 6FDA was added together with 10 g of NMP, and reacted at 60 ° C. for 1 hour. Subsequently, it stirred at 180 degreeC 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 three times with water, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a powder of a closed ring polyimide resin (L).

  10 g of the obtained resin (L), 3.0 g of the quinonediazide 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 a varnish L1 of the positive photosensitive resin composition. Obtained. As described above, the obtained varnish L1 was used for sensitivity evaluation, residual film rate evaluation, bendability evaluation, and long-term reliability evaluation of the organic EL display device. The evaluation results are shown in Table 2.

[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. TMEG8.21g (0.02mol) and 6FDA13.33g (0.03mol) were added with NMP10g here, and it was made to react at 60 degreeC for 1 hour. Then, MAP1.64g (0.015mol) was added as terminal blocker, and also stirring was continued at 60 degreeC for 1 hour. Subsequently, it stirred at 180 degreeC for 4 hours, and after completion | finish of stirring, the solution was thrown into 2 L of water, and white precipitation was obtained. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a powder of a closed ring polyimide resin (M).

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

[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. Dissolved in 100 g of NMP. CBDA 9.81g (0.05mol) was added here with NMP10g, and it was made to react at 60 degreeC for 1 hour. Thereafter, 2.18 g (0.02 mol) of MAP was added as a terminal blocking agent, and stirring was further continued at 60 ° C. for 1 hour. Subsequently, it stirred at 180 degreeC for 4 hours, and after completion | finish of stirring, the solution was thrown into 2 L of water, and white precipitation was obtained. This precipitate was collected by filtration, washed with water three times, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (N).

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

[Comparative Example 6]
Under a dry nitrogen stream, BAHF 17.39 g (0.0475 mol) SiDA 0.62 g (0.0025 mol) was dissolved in NMP 200 g. TMEG 20.51g (0.05mol) was added with NMP50g here, and it stirred at 40 degreeC for 1 hour. Thereafter, a solution obtained by diluting 11.9 g (0.1 mol) of DFA with 5 g of NMP was added dropwise over 10 minutes, and then 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 a solid precipitate was collected by filtration. Further, it was washed 3 times with 2 L of water, and the collected polymer solid was dried with a vacuum dryer at 50 ° C. for 72 hours to obtain a polyamic acid ester resin (O).

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

  About Examples 1-13 and Comparative Examples 1-6, each composition is shown in Table 1, and each evaluation result is shown in Table 2, respectively.

<Preparation Example 1>
As a resin, 138.0 g of a 30% by weight MBA solution of the resin (C) obtained in Example 3 was used as a dispersant, 13.8 g of S-20000, 685.4 g of MBA as a solvent, and 685.4 g of a colorant. , 82.8 g of Bk-S0100CF 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 Industries Co., Ltd.) comprising a centrifugal separator filled with 75% 0.30 mmφ zirconia balls (YTZ; manufactured by Tosoh Corporation) as ceramic beads for pigment dispersion The pre-dispersed liquid obtained was supplied to the product and processed at a rotor peripheral speed of 7.0 m / s for 3 hours to obtain a solid content concentration of 15% by mass, colorant / resin / dispersant = 60/30/10 ( (Mass ratio) pigment dispersion (Bk-1) was obtained. The number average particle diameter of the pigment in the obtained 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 lamp, 0.25 g of NCI-831 was weighed, 10.0 g of MBA was added, and dissolved by stirring. Next, 3.5 g of a 30% by mass MBA solution of the resin (A) obtained in Example 1 and 1.5 g of an 80% by mass MBA solution of DPHA were added and stirred to prepare a mixed solution as a uniform solution. Obtained. Next, 16.67 g of the pigment dispersion (Bk-1) obtained in Preparation Example 1 was weighed, and the above-prepared preparation was added thereto and stirred to obtain a uniform solution. Then, the obtained solution was filtered with a 0.45 μmφ filter to obtain a varnish BA of a negative photosensitive resin composition. As described above, the obtained varnish BA was used for sensitivity evaluation, residual film ratio evaluation, bendability evaluation, and long-term reliability evaluation of an organic EL display device. The composition is shown in Table 3, and the evaluation results are shown in Table 4.

[Examples 15 to 17 and Comparative Examples 7 to 11]
In the same manner as in Example 14, varnishes BB to BN of the photosensitive resin composition were prepared with the compositions shown in Table 3. Using each of the obtained compositions, in the same manner as in Example 14, evaluation of sensitivity, evaluation of the remaining film rate, evaluation of bendability, and long-term reliability of the organic EL display device were performed. The evaluation results are shown in Table 4.

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

1: TFT (Thin Film Transistor)
2: Wiring 3: TFT insulating layer 4: Planarizing 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 (21)

(A) an alkali-soluble resin, (b) 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 a monoamine or at least one terminal of the polymer molecular chain in the (a) alkali-soluble resin A photosensitive resin composition having an organic group derived from an acid anhydride.

(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 represent Independently represents a linear or branched alkylene group having 2 to 20 carbon atoms, a 1,3-phenylene group or a 1,4-phenylene group, wherein R ¹ , X ¹ and X ² each represent a plurality of repeating units; M and n are each an integer of 0 to 100,000, and m + n ≧ 3.) X ¹ and X ² in the general formula (1) is an ethylene group, a propylene group or butylene group, a photosensitive resin composition of claim 1. The said (a) alkali-soluble resin has 10-100 mol% of organic groups derived from a monoamine or an acid anhydride with respect to 100 mol% of structural units represented by General formula (1). The photosensitive resin composition as described in 2. The photosensitive resin composition in any one of Claims 1-3 whose said monoamine is a compound which has a structure represented by General formula (2).

(In the general formula (2), R ⁴ represents a saturated hydrocarbon group having 1 to 6 carbon atoms, and r represents 0 or 1. A and B may be the same as or different from each other, and may be a hydroxyl group, a carboxyl group or Represents a sulfonic acid group, and s and t each represents 0 or 1, and s + t ≧ 1. The photosensitive resin composition in any one of Claims 1-4 whose said (b) photosensitive compound is (b1) photo-acid generator. The photosensitive resin composition according to any one of claims 1 to 4, wherein the (b) photosensitive compound is (b2) a photopolymerization initiator and further contains (d) a radical polymerizable compound. Furthermore, (e) The photosensitive resin composition in any one of Claims 1-6 containing a thermal crosslinking agent. Furthermore, the photosensitive resin composition in any one of Claims 1-7 containing a coloring agent (f). The photosensitive resin composition according to claim 8, wherein the colorant (f) is a colorant other than (f3) black agent and / or (f4) black. The photosensitive resin composition according to claim 8 or 9, wherein the (f) colorant is (f1) a pigment or (f2) a dye. The photosensitive sheet | seat which consists of the photosensitive resin composition in any one of Claims 1-10. The cured film which consists of hardened | cured material of the photosensitive resin composition in any one of Claims 1-10. A cured film comprising a cured product of the photosensitive sheet according to claim 11. The cured film according to claim 12 or 13, comprising (i) one or more compounds selected from the group consisting of cyclic amides, cyclic ureas and derivatives thereof. The total content of one or more compounds selected from the group consisting of (i) cyclic amide, cyclic urea, and derivatives thereof in the cured film is 0.005% by mass or more and 5% by mass or less. The cured film as described. The element which comprises the cured film in any one of Claims 12-15. An organic EL display device comprising a planarizing layer comprising the cured film according to claim 12 and / or an insulating layer on the first electrode on a substrate having a drive circuit. The organic EL display device according to claim 17, wherein the substrate having the drive circuit is made of a resin film. The semiconductor electronic component which comprises the interlayer insulation film between the rewiring which consists of a cured film in any one of Claims 12-15. The semiconductor device which comprises the interlayer insulation film between the rewiring which consists of a cured film in any one of Claims 12-15. The process of apply | coating the photosensitive resin composition in any one of Claims 1-11 to a board | substrate, or laminating the photosensitive sheet | seat of Claim 11 on a board | substrate, and forming the photosensitive resin film, The said photosensitive property A method for producing an organic EL display device, comprising: a step of drying a resin film; a step of exposing a dried photosensitive resin film; a step of developing an exposed photosensitive resin film; and a step of heat-treating the developed photosensitive resin film.

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