TW201116930A - Photosensitive resin composition and method of producing photosensitive resin film - Google Patents

Abstract

The present application provides a photosensitive resin composition which can inhibit a bubble generated at decompression drying and form a photosensitive resin film having an excellent film-thickness uniformity after drying. A photosensitive resin composition comprises: (a) a resin at least one or more selected from polyimide, polybenzoxazole, polyimide precursor and polybenzoxazole precursor; (b) sensitizer; (c) an organic solvent having 100 DEG C to 130 DEG C of the boiling point at atmospheric pressure, (d) an organic solvent which have 150 DEG C or more of the boiling point at atmospheric pressure and the 1.1 to 1.5 mPas of viscosity at 20 DEG C based on the total amount of the organic solvent, and (d) 10 to 60 % by weight of a component content based on the total amount of the organic solvent.

Description

[Technical Field] The present invention relates to a photosensitive resin composition and a method for producing a photosensitive resin film. More specifically, the present invention relates to a photosensitive resin composition and a method for producing a photosensitive resin film, which are suitable for insulation of a surface protective film or an interlayer insulating film of a semiconductor element, and an organic electroluminescence (Electroluminescence: EL) element Film, a flat film of a thin film transistor (hereinafter referred to as TFT) substrate for driving a display device using an organic EL element, a wiring protective insulating film for a circuit board, and an onchip microlens of a solid imaging element Or use of various displays, flattening films for solid imaging devices, and the like. [Prior Art] A resin film composed of polyimine or polybenzoxazole is widely used for a surface protective film, an interlayer insulating film, a planarizing film, or the like of a semiconductor element. Recently, it is also possible to use, for example, an insulating film of an organic EL element or a planarizing film of a TFT substrate. In such applications, since the substrate size is extremely large compared to semiconductor applications, it is a common technique to apply a resin composition by slit coating. The slit coating method using a slit nozzle is different from the previous spin coating, and since it is not necessary to rotate the substrate, it is widely used because of the reduction in the amount of the resin composition used and the safety of the project. 'The film is dissolved and removed.排 术 术 术 术 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干After the amount is used, 201116930 is a photosensitive resin composition suitable for slit coating. A photosensitive resin composition is proposed, which contains a polyimide precursor, a polyhydroxyguanamine, a sensitizer, and a boiling point at atmospheric pressure. In the organic solvent of 100 ° C or more and 140 ° C or less, the content of the organic solvent is 50% by weight or more and 100% by weight or less based on the total amount of the organic solvent (see, for example, Patent Document 1). Further, in the positive-type resist composition containing the alkali-soluble resin represented by the phenol novolak resin, the pattern shape which is different in the solvent evaporation rate between the surface of the coating film and the inside due to the vacuum drying step after the slit coating is poor In order to improve the technique, there is proposed a photosensitive resin composition for a slit coating film comprising: an alkali-soluble resin, a sensitizer, and propylene glycol monomethyl ether acetate; and a vapor pressure of 150 Pa or less at a gas pressure of 20 ° C A solvent mixture of solvents (see, for example, Patent Document 2). Further, in order to reduce the viscosity of the coating liquid, to make high-speed coating by slit coating, and to improve the uniformity of the film thickness and the shape of the pattern, there is proposed a photoresist composition for a slit coating film, which contains: alkali solubility Resin, photosensitive material, and 2 (a low-viscosity solvent having a viscosity of 1.1 cp or less in TC is contained in a solvent in an amount of 10% by weight or more (see, for example, Patent Document 3). PRIOR ART DOCUMENT Patent Document Patent Document 1 '·Japanese Special Open 2004- Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2008-70480. Suppressing streaks caused by adhesion or clogging of foreign matter in the slit nozzle, or suppressing defects such as transfer marks on which the support mark is transferred during drying, but after drying at a reduced pressure, there is foaming after drying. In the case of such a bubble, a polyimide resin, a polybenzoxazole, or a resin composition containing the precursor is used to form a photosensitive resin film having a relatively thick film thickness. In particular, in the case of forming a photosensitive resin film having a film thickness of 5/zm or more, it is remarkable to suppress the occurrence of bubbles. Further, the techniques described in Patent Documents 2 to 3 are applied to polyimine and polyphenylene. And carbazole or a photosensitive resin composition containing the precursors, the propylene glycol methyl ether acetate of the resins (boiling point 146 ° C) or a low viscosity solvent having a viscosity of 1.1 cp or less, lacking dissolution In the photosensitive resin composition, the undissolved resin remains or the film thickness of the photosensitive resin film formed by the slit coating is uneven. The polyimine or polybenzoxazole or the like is contained. When the photosensitive resin composition of the precursor is formed into a thick film by slit coating, it is preferable to suppress the occurrence of bubbles during drying under reduced pressure and to improve the film thickness uniformity after drying. Therefore, the object of the present invention is to provide a photosensitive resin composition. By a combination of organic solvents having specific characteristics, it is possible to suppress the occurrence of bubbles accompanying drying under reduced pressure, and to form a photosensitive resin film having excellent film thickness uniformity after drying. The present invention is a photosensitive resin composition comprising: U) at least one selected from the group consisting of polyimine, polybenzoxazole, polyimine precursor, and polybenzoxazole precursor. 201116930 (b) sensitizer; (c) an organic solvent having a boiling point of 10 CTC or more and 130 ° C or less at atmospheric pressure; and (d) a boiling point of 150 ° C or more at atmospheric pressure, and 2 (TC viscosity greater than l.lmPa) s and an organic solvent of less than 1.5 mPa·s, and the content of the component (c) is 40% by weight or more and 90% by weight or less based on the total amount of the organic solvent, and the content of the component (d) is 10% based on the total amount of the organic solvent. 5% by weight or more and 60% by weight or less. According to the present invention, a photosensitive resin composition can be obtained which can suppress the occurrence of bubbles in a vacuum drying step after the application of the slit, and the film thickness after drying is 5 μm or more. A thick film can also form a photosensitive resin film excellent in film thickness uniformity. [Embodiment] The photosensitive resin composition of the present invention comprises: U) at least one selected from the group consisting of polyimine, polybenzoxazole, polyimine precursor, and polybenzoxazole precursor. (b) sensitizer; (c) an organic solvent having a boiling point of 100 ° C or more and 130 ° C or less at atmospheric pressure and (d) a boiling point of 150 ° C or more at atmospheric pressure, and a viscosity greater than 20 ° C at 20 ° C l. lmPa.s and an organic solvent of less than 1.5 mPa·s, and the content of the component (c) is 40% by weight or more and 90% by weight or less based on the total amount of the organic solvent, relative to the total amount of the organic solvent '(d) component A photosensitive resin composition having a content of 10% by weight or more and 60% by weight or less. The ingredients are described below. The photosensitive resin composition of the present invention contains (a) at least one or more resins selected from the group consisting of polyimine, polybenzoxazole, polyimine precursor, and polybenzoxazole precursor. . These may also contain two or more types, and may also contain a copolymer having these two or more repeating units. Polyimine and polybenzoxazole are resins having a cyclic structure of a quinone ring or a carbazole ring in a main chain structure. The number of repeats of the construction unit is suitably from 10 to 100,000. Polyimide-based tetracarboxylic acid or corresponding tetracarboxylic dianhydride, dichlorotetracarboxylic acid diester, etc.; and diamine or corresponding diisocyanate compound, which can be reacted by alkylating diamine with trimethyl hydrazine It has a tetracarboxylic acid residue and a diamine residue. For example, it can be obtained by subjecting polylysine to dehydration ring-closure by heat treatment, which is one of polyimine precursors obtained by reacting tetracarboxylic dianhydride with a diamine. At the time of the heat treatment, a solvent such as m-xylene or the like which azeotropes with water may be added. Alternatively, a dehydration condensing agent such as carboxylic anhydride or dicyclohexylcarbodiimide or a base such as triethylamine may be added as a ring-closing catalyst, which can be obtained by dehydration ring closure by chemical heat treatment. Alternatively, it may be obtained by adding a weakly acidic carboxylic acid compound to a low temperature of 1 〇〇 ° C or lower and heat-treating to obtain a dehydration ring closure. The polyimine precursor system will be described later. The polybenzoxanthene can be obtained by reacting a bisamine phenol compound with a dicarboxylic acid or a corresponding chlorine diper acid active ester or the like, and has a dicarboxylic acid residue and a bisaminobenzoquinone residue. For example, one type of polybenzoxazole precursor obtained by reacting a bishydroxy guanamine compound with a dicarboxylic acid can be obtained by dehydrating and condensing polyhydroxy decylamine by heat treatment. Alternatively, it may be obtained by adding a phosphoric anhydride, a base, a carbodiimide compound or the like to a dehydration ring by chemical treatment. The polybenzoxazole precursor is as described later. 201116930 In the present invention, the polyiminimide preferably has OR1, S〇3R' 'CONR'R2 in the tetracarboxylic acid residue and/or the diamine residue from the viewpoint of solubility with respect to the aqueous alkali solution. 'COOR1 > S〇2NR>> an acidic group or an acidic group derivative such as R2, more preferably having a hydroxyl group. Further, the polybenzo Dfazole preferably has an acidic group or an acidic group derivative such as OR1' SChR1, CONW, COOR1, SC^NR1, etc. in the residue of the diacid residue and/or the bisamine phenol residue. More preferably, it has a hydroxyl group. Here, R1 and R2 represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. Further, the 'acid group' means that R1 or R2 is all a hydrogen atom, and the acid group derivative means a case where R1 or R2 contains a one-carbon organic group having 1 to 20 carbon atoms. The organic group may, for example, be an alkyl group, an alkoxy group or an ester group. In the present invention, a tetracarboxylic acid residue of a polyiminimide and a dicarboxylic acid residue of a polybenzoxazole (hereinafter referred to as the same) A suitable configuration of the acid residue is exemplified by the following structure, or a part of the hydrogen atoms is carbon-substituted to a 20-alkyl group, a fluoroalkyl group, an alkoxy group, an ester group, a nitro group, and a cyano group. A structure in which one or four fluorine atoms and chlorine atoms are substituted. 201116930 ο

-10- 201116930

201116930 However, 〖indicates direct bond, -COO-, -CONH-, -CH2-, -C2He, -0-> -CsHs-' -C3Fe-' -SO2-' -S-' -Si(CH3) 2-'-0-Si(CH3)2.. > -CM-, -C6H4-〇-C6H4·, -C6H4-C3H6-C6H4- or -C6H4-C3F6-C6h. In the present invention, a suitable structure of a diamine residue of polyimine and a bisamine phenol residue of polybenzoxazole (hereinafter referred to as a diamine residue) may be exemplified by a second structure or the hydrogen. One of the atoms is a structure in which one to four carbon atoms are substituted with a carbon number of 1 to 20 alkyl groups, a fluoroalkyl group, an alkoxy group, an ester group, a nitro group, a cyano group, a fluorine atom or a chlorine atom. -12 - 201116930

-13- 201116930

π

7?R Η ο

However, J represents a direct bond, -C0〇-, -CONH-, -CH2-, -d-, -C3H6-' -C3F6-' -S〇2-' -s-' -Si(CH3)2- '-0-Si(CH3)2-0- '-C6H4-, -C6H4-O-C6H4-, -C6H4-C3H6-C6H4- or -14- 201116930 -CeH - C^Fs-d-. ! ^1 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. In the component (a) used in the present invention, the polyimine precursor and the polybenzoxazole precursor have a resin having a guanamine bond in the main chain, and are subjected to dehydration ring closure by heat treatment or chemical treatment. Polyimine, polybenzoxazole. The number of repetitions of the structural unit is preferably from 1 〇 to 1 〇 0, 〇〇〇. In the polyimine precursor, polyphthalic acid, polyglycolate, polyamidamine, polyisodecimide, etc., preferably poly-proline, polyphthalate . The polybenzoxazole precursor may, for example, be polyhydroxyguanamine, polyamine amide, polyamine or polyamidoximine, and is preferably polyhydroxyguanamine. The polyimine precursor and the polybenzoxazole precursor are preferably made of an acid residue or a diamine residue, such as ON, SChR1, CONW, COOR1, SChNW, etc., from the viewpoint of solubility in an aqueous alkali solution. An acidic group or an acidic group derivative, more preferably having a hydroxyl group. R1 and R2 represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. Further, the acidic group means a case where all of R1 or R2 is a hydrogen atom, and the acid group derivative means a case where a monovalent organic group having 1 to 20 carbon atoms is contained in R1 or R2. Examples of the acid component of the acid residue of the polybenzoxazole precursor, examples of the dicarboxylic acid are citric acid, isodecanoic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, dicarboxylic acid. Biphenyl ester, diphenyl ketone dicarboxylic acid, triphenyl dicarboxylate, etc.; examples of the tricarboxylic acid are 1,2,4-benzenetricarboxylic acid, trimesic acid, diphenyl ether triresidic acid And tribasic acid biphenyl ester; tetracarboxylic acid examples are pyromellitic acid, 3,3,4,V-biphenyltetracarboxylate, -15- 201116930 2,3,3,,4, -biphenyltetracarboxylate, 2,2_,3,3'-biphenyltetracarboxylate, 3,3,4,4,-diphenyl ketone tetracarboxylic acid, 2,2',3 , 3'-diphenyl ketone tetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4·di-residylphenyl)acetamidine, 1,1·bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, double (2,3-dicarboxyphenyl)methane Bis(3,4-dicarboxyphenyl)anthracene, bis(3,4-dicarboxyphenyl)ether, 12,5,6-naphthalenetetracarboxylate, 2,3,6,7-naphthalenetetracarboxylic acid An aromatic tetracarboxylic acid such as an ester, 2,3,5,6-pyridyltetracarboxylic acid ester, 3,4,9,1〇-indenyltetracarboxylic acid ester; or a tetracarboxylic acid butyl ester or a tetracarboxylic acid Cyclobutyl ester, 1,2,3,4-cyclopentane tetracarboxylate, cyclohexyl tetracarboxylate, bicyclo[2.2.1.]heptane tetracarboxylate, bicyclo[3.3.1·]tetracarboxylate Acid, bicyclo [3.1.1.] hept-2-ene tetracarboxylate, bicyclo [2.2.2.] octane tetracarboxylate, adamantyl tetracarboxylate, 2,3,5-tricarboxycyclopentane An aliphatic tetracarboxylic acid or the like such as a vinyl acetate. Further, one of the hydrogen atoms in the above-exemplified dicarboxylic acid, tricarboxylic acid or tetracarboxylic acid is an acidic group or an acidic group derivative such as OR1, SChR1, CONR'R2, COOR1 or SChNW, preferably a hydroxyl group or It is more preferable to substitute 1 to 4 of a sulfonic acid group, a sulfonate sulfonate group, a sulfonate group or the like. These acids can be used as such or used as acid or active esters. Further, these may be used in two or more types. Further, by using a ruthenium-containing tetracarboxylic acid such as dimethyl decanoic acid or 1,3-bis(decanoic acid) tetramethyldioxane, the adhesion to the substrate can be improved, or relative to Resistance to oxygen plasma and UV ozone treatment used for washing and the like. The ruthenium-containing tetracarboxylic acid is preferably used in an amount of from 1 to 30 mol% based on the total acid component. -16 · 201116930 exemplified as a diamine component constituting a polyamine imine precursor and a diamine residue of a polybenzoxazole precursor, bis(3-amino-4-hydroxyphenyl)hexa Fluoropropane, bis(3-amino-4-hydroxyphenyl) maple, bis(3-amino-4-hydroxyphenyl)propane, bis(3·amino-4-hydroxyphenyl)methene, a hydroxyl group-containing diamine such as bis(3-amino-4-hydroxyphenyl)ether or bis(3-amino-4-hydroxy)biphenyl'bis(3.amino-4.hydroxyphenyl)anthracene; a carboxyl group-containing diamine such as 3,5·diaminobenzoic acid or 3-carboxy-4,4-diaminodiphenyl ether; 3-sulfonic acid-4, 4′-diaminodiphenyl ether; Dialkyl sulfonate; dithiol phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane , 4,4'-diaminodiphenylmethane, 3,4, diaminodiphenyl hydrazine, 4,4'-diaminodiphenyl maple, 3,4'-diaminodiphenyl sulfide ( Sulphide), 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzine, meta-phenylenediamine, p-phenylenediamine 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4.aminophenoxy) , bis(3-aminophenoxyphenyl)fluorene, 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·_ Aminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3, diethyl-4,4,diaminobiphenyl, 2,2·,3, 3·-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4-·tetramethyl·4,4·-diaminobiphenyl, bis(trifluoromethyl)- 4,4'-diaminobiphenyl, or a compound in which one of the hydrogen atoms of the aromatic ring is substituted with an alkyl group or a halogen atom, or a fat such as 1,4-cyclohexanediamine or methylene dicyclohexylamine Group of diamines and the like. Further, the diamines may be a part of a hydrogen atom which may be a C 1 to 10 alkyl group such as a methyl group or an ethyl group, a fluoroalkyl group having a carbon number of 1 to 10 such as a trifluoromethyl group, fluorine or chlorine. Substituting bromine, iodine-17- 201116930, etc. Further, the diamine exemplified above preferably has an acidic group or an acidic group derivative such as OR1, SChR1, CONtR2, COOR1, SChNR'R2 or the like, and more preferably has a hydroxyl group. These diamines can be used as they are, or as a corresponding diisocyanate compound or trimethylsulfonium alkylated diamine. Further, two or more of these may be used. In the case where heat resistance is required, it is preferred to use an aromatic diamine of 50 mol% or more of the entire diamine. Further, the diamine component is obtained by using 1,3-bis(3-aminopropyl)tetramethyldioxane or 1,3-bis(4-anilino)tetramethyldioxane. The rhodium-containing diamine can improve the adhesion to the substrate or the resistance to oxygen plasma and UV ozone treatment used for washing or the like. Preferably, the halogen-containing diamines are used in an amount of from 1 to 30 mol% of the total diamine component. Further, it is preferred to use a polyimine, a polybenzoxazole, a terminal of the precursors, a monoamine, an acid anhydride, an acid chloride or a monocarboxylic acid having a hydroxyl group, a carboxyl group, a sulfonic acid group or a thiol group. Closed. These may also be used in two or more types. By having the above-mentioned resin-based end, the dissolution rate of the alkali aqueous solution with respect to the resin can be easily adjusted to an appropriate range. In a suitable example of the monoamine, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-amino group can be exemplified. Naphthalene, hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-3-aminonaphthalene , 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene , 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, -18- 201116930 4-aminobenzoic acid, 4·aminosalicylic acid, 5-aminosalicylide Acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3·amino-4,6-dihydroxypyrimidine '2-amine Phenol, 3-aminophenol, 4-aminophenol, 2-amino-4-tributylbutanol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, and the like. Preferred examples of the acid anhydride, acid chloride, and monocarboxylic acid include anhydrides such as phthalic anhydride, maleic anhydride, nadic acid, cyclohexane dicarboxylic anhydride, and 3-hydroxy hydroxy acid; 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene , 1-Hydroxythio-7-carboxynaphthalene,: [_Hetylthio-6-carboxynaphthalene, ^Hexylthio-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, etc. Carboxylic acid and acid chloride chlorinated monoacid chloride compound; terephthalic acid, decanoic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-di a monocarboxylic acid chloride compound, a monoacid chlorine compound and an N-hydroxybenzotriazole which are acid-chlorinated by a carboxyl group such as a carboxynaphthalene, a 1,7-dicarboxynaphthalene or a 2,6-dicarboxynaphthalene. Or an active ester compound obtained by the reaction of N-hydroxy-5-norkenenyl-2,3-dicarboxy quinone. The content of the terminal blocking agent such as the above monoamine, acid anhydride, acid chloride or monocarboxylic acid is preferably in the range of 0.1 to 60 mol% of the number of moles of the acid component monomer or the diamine component monomer. Good for 5 to 50 moles. By such a range, a resin composition which is moderate in viscosity and excellent in film physical properties when the resin composition is applied can be obtained. -19- 201116930 Further, a polymerizable functional group may be provided at the end of the resin. Examples of the polymerizable functional group include an ethylenically unsaturated bond group, an ethynyl group, a hydroxymethyl group, an alkoxymethyl group and the like. The terminal blocking agent introduced into the resin can be easily detected by the following method. For example, the resin into which the terminal blocking agent is introduced is dissolved in an acidic solution, and is decomposed into a diamine component and an acid component which are constituent units of the resin, and can be easily detected by gas chromatography (GC) or NMR. Blocking agent. In contrast to this, the resin into which the terminal blocking agent is introduced can be directly detected by thermal decomposition gas chromatography (PGC) or infrared spectroscopy and "C-NMR spectroscopy. In the present invention, as the component (a), a polyimide precursor or a polybenzoxazole precursor is preferred, and a polyimide precursor is more preferred. The polybenzamine precursor is subjected to calcination at about 20 (TC) to carry out a ruthenium imidization reaction in which the phthalic acid moiety is closed, and the polybenzoxazole precursor is fired at about 300 ° C. The hydroxy guanamine moiety is subjected to a closed-loop carbazole reaction and has a volume-shrinking property. The photosensitive resin composition using the precursor resin is obtained by firing a fine pattern by an exposure/development step. In the case of using an insulating film which is an organic EL element, the upper electrode has excellent coating properties, prevents disconnection, and improves the reliability of the element. The photosensitive resin composition of the present invention may contain other alkali-soluble resins in addition to the component (a). The alkali-soluble resin refers to a resin having an acidic group which is soluble to a base, and specifically, Acrylic radical polymerizable polymer, phenolic furfural resin, polyhydroxystyrene, polyfluorene-20-201116930 oxane, etc. Further, the acidic groups of the resins can be protected and the alkali solubility can be adjusted. Resin, except In addition to tetramethylammonium hydroxide, it is an aqueous solution of an alkali which is dissolved in a base such as choline, triethylamine, dimethylamine pyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide or sodium carbonate. Although the resin may contain two or more kinds of resins, it is preferable that the ratio of the resin containing the component (a) is 50% by weight or less. The photosensitive resin composition of the present invention contains (b) a sensitizer. The (b-Ι) photoacid generator, (b-2) photopolymerization initiator, and (b-3) a combination of two or more compounds having an ethylenically unsaturated bond may be mentioned. -1) In the photo-acid generator, an acid is generated in the light-irradiating portion, and the solubility in the alkali aqueous solution of the light-irradiating portion is increased, and a relief pattern in which the light-irradiating portion is dissolved can be obtained. When a (b-fluorene) photoacid generator and an epoxy compound or a thermal crosslinking agent to be described later are contained, an acid generated in the light-irradiating portion promotes a crosslinking reaction of an epoxy compound or a thermal crosslinking agent to obtain light. The illuminating portion is a negative-shaped relief pattern of insolubilization. Also, by having two (b-2) A photopolymerization initiator and a compound of (b-3) an ethylenically unsaturated bond are generated by radical polymerization of an ethylenically unsaturated bond generated by a living radical generated in a light-irradiating portion, and a light irradiation portion can be obtained. The photosensitive resin composition of the present invention preferably has a positive photosensitive property of a (b-fluorene) photoacid generator as the photosensitive agent (b). The positive photosensitive resin composition is a positive photosensitive resin composition. After the fine pattern is obtained by the exposure and development steps, a pattern of a tapered shape can be obtained by firing. The upper tapered electrode pattern is used as an insulating film of the organic EL element-21-201116930, and the upper electrode is used. The coating property is excellent and the wire breakage is prevented, and the reliability of the component can be improved. The (bl) photoacid generator may, for example, be a quinonediazide compound, a phosphonium salt, a phosphonium salt, a diazonium salt, an iodine salt or the like. . In the case of the quinonediazide compound, a sulfonate of a quinonediazide group may be exemplified by an ester bond in a polyhydroxy compound; a sulfonate of a quinonediazide group may be obtained in the polyamine compound. Sulfonamide-bonded; sulfonate of a quinonediazide group by ester bonding and/or sulfonamide-bonded _ in a polyhydroxypolyamine compound. More preferably 50 mol% or more of the entire functional group of the polyhydroxy compound or the polyamino compound may be substituted with a quinonediazide group. Further, it is preferred to contain two or more kinds of (b-1) photoacid generators, and a photosensitive resin composition having high sensitivity can be obtained. In the present invention, the quinonediazide group is preferably any one of a 5-naphthoquinonediazidesulfonyl group and a 4-naphthoquinonediazidesulfonyl group. The 4-naphthoquinonediazidesulfonate compound has absorption in the i-line region of the mercury lamp and is suitable for i-line exposure. 5. The naphthoquinonediazidesulfonate compound has an absorption extension to the g-line region of the mercury lamp and is suitable for g-line exposure. In the present invention, it is preferred to select a 4-naphthoquinonediazidesulfonate compound or a 5-naphthoquinonediazidesulfonate compound by the wavelength of exposure. Further, it may contain a naphthoquinonediazidesulfonyl ester compound having a 4-naphthoquinonediazidesulfonyl group or a 5-naphthoquinonediazidesulfonyl group in the same molecule, and may also contain 4 a naphthoquinonediazidesulfonate compound and a 5-naphthoquinonediazidesulfonate compound. -22- 201116930 (b-1) In the photoacid generator, the onium salt, the scale salt, and the diazonium salt are preferably moderately stabilized by an acid component which is formed by exposure. Among them, strontium salt is preferred. Further, a sensitizer or the like can be used as needed. The (b-2) photopolymerization initiator may be exemplified by diethoxyethyl benzene, 2 hydroxy-2-methyl-1-phenylpropan-1-one, and benzyl ketal. Io_(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, heart (2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1 -hydroxycyclohexyl-phenyl ketone, i-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)anthracene, 2-methyl-[4-(methylthio)phenyl]-2 -morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1(4-morpholinophenyl)-butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin Propyl ether, benzoin isobutyl ether, diphenyl ketone, methyl ortho-benzoylbenzoate, 4-phenyldiphenyl ketone, 4,4-dichlorodiphenyl ketone, hydroxydiphenyl hydrazine, 4· Benzamethylene-4'-methyl-diphenyl sulfide, alkylated diphenyl ketone, 3,3|, 4,4, tetrakis(tributyl-oxycarbonyl)diphenyl ketone, bromine 4-Benzylmercapto-fluorene, fluorene-dimethyl-NU-C1-sided oxy-2-propenyloxy)ethyl]benzylammonium chloride, 4-benzylidenebenzyl Trimethylammonium, 2-hydroxy-3(4-benzylidenephenoxy)-indole, hydrazine, hydrazine-trimethyl-1- Propanaminium - hydrate, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichloro Thioxanthone, 2-hydroxy-3 -(3,4-dimethyl-9-oxoethoxy-9 oxime-thioxanthene-2-yloxy)-^1^-trimethyl-1- Propionium ammonium, 2,4,6-trimethylbenzimidylphosphine oxide, 1,2-octanedione-1-[4-(phenylthio)-2-(0-benzylidene) )], ethanone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9Η-indol-3-yl]-, 1-(0-ethylindenyl) ), 2,2,-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-23- 201116930 -1,2-bisimidazole, 10-butyl-2-chloroacridine Ketone, 2-ethylhydrazine, benzyl, 9,10-phenanthrenequinone, camphorquinone, glyoxymethylphenyl ester, 7? 5-cyclopentadienyl-7? 6-isopropylphenyl · Ionic (1+)-hexafluorophosphate (1-), diphenyl sulfide derivative, bis(7? 5-2,4-cyclopentadien-1-yl)-bis(2,6-di Fluorin-3-(111-pyrrol-1-yl)-phenyl)titanium, 4,4-bis(dimethylamino)diphenyl ketone, 4,4-bis(diethylamino)diphenyl ketone , thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 4- Mercapto-4-methylphenyl ketone, dibenzyl ketone, fluorenone, 2,3-diethoxyethyl benzene benzene 2,2-dimethoxy-2-phenyl-2-phenyl Acetylbenzene, 2-hydroxy-2-methylpropiophenone, p-tert-butyl butyl dichloroacetamidine, benzyl methoxyethyl acetal, hydrazine, 2-tertiary butyl hydrazine, 2- Aminoguanidine, 3-chloroindole, anthrone, benzoxanone, dibenzsuberone, methylene ketone, 4-azidobenzylidene benzene, 2,6 - bis(p-azidobenzylidene)cyclohexane, 2,6-bis(p-azidobenzylidene)-4-methylcyclohexanone, 2-phenyl-1,2-butanedione- 2-(o-methoxycarbonyl)anthracene, i,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)anthracene, naphthalenesulfonium chloride, quinoline sulfonium chloride, N-phenylthiopyridinium , 4,4-azobisisobutyronitrile, benzothiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenylhydrazine, benzoyl peroxide, eosine, methylene blue, etc. A combination of a reducing pigment and a reducing agent such as ascorbic acid or triethanolamine. These may contain two or more types. In the case of (b-3) a compound having two or more ethylenically unsaturated bonds, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, and triacrylic acid may, for example, be mentioned. Trimethylol propyl ester, ethoxylated bisphenol A dimethacrylate, glyceryl dimethacrylate, dimethacrylic acid-24- 201116930 tripropylene glycol ester, butylene glycol dimethacrylate, glycerol triacrylate Ester, neopentyl glycol triacrylate, neopentyl glycol tetraacrylate, di pentaerythritol hexaacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated isotrihydrogen acid triacrylate An acrylic monomer such as an ester. These may also contain two or more types. In the present invention, the content of the (b) photosensitive agent is preferably from 0.05 to 50 parts by weight based on 100 parts by weight of the resin of the component (a). From the viewpoint of high sensitivity, the content of the (b-fluorene) photoacid generator is preferably from 0.01 to 50 parts by weight based on 100 parts by weight of the resin of the component (a). Among them, the quinonediazide compound is preferably from 3 to 40 parts by weight. Further, the total amount of the onium salt, the scale salt, and the diazonium salt is preferably from 0.5 to 20 parts by weight. The content of the (b-2) photopolymerization initiator is preferably from 0.1 to 20 parts by weight based on 100 parts by weight of the resin of the component (a). When it is 1 part by weight or more, sufficient radicals are generated by light irradiation, and the sensitivity is improved. In addition, as long as it is 20 parts by weight or less, there is no hardening of the light-irradiated portion due to excessive generation of radicals, and alkali developability can be improved. The content of the compound (b-3) having two or more ethylenically unsaturated bonds is preferably from 5 to 50 parts by weight based on 100 parts by weight of the resin of the component (a). In addition, in order to adjust the solubility and the like, the compound having only one ethylenically unsaturated bond may be contained in an amount of 1 to 50 parts by weight based on 100 parts by weight of the resin of the component (a). Examples of such a compound include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, dimethyl acrylamide, methacrylic acid. Dimethylaminoethyl ester, propylene hydrazinoline, 1-hydroxyethyl α-chloroacrylate, methyl-25-201116930 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl Chloroacrylate, 1-hydroxypropyl methacrylate, 1-hydroxypropyl acrylate, 1-hydroxypropyl α-chloroacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxyl Propyl α-chloroacrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl α-chloroacrylate, 1-hydroxy-1-methylethyl methacrylate, acrylic acid 1-hydroxy-1-methylethyl ester, 1-hydroxy-1-methylethyl α-chloroacrylate, 2-hydroxy-1-methylethyl methacrylate, 2-hydroxy-1-methyl acrylate Ethyl ester, 2-hydroxy-1-methylethyl α-chloroacrylate, 1-hydroxybutyl methacrylate, 1-hydroxybutyl acrylate, 1-hydroxybutyl α-chloroacrylate, methacrylic acid 2-hydroxy Ester, 2-hydroxybutyl acrylate, 2-hydroxybutyl α-chloroacrylate, 3-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl α-chloroacrylate, methacrylic acid 4-hydroxybutyl ester, 4-hydroxybutyl acrylate, 4-hydroxybutyl α-chloroacrylate, 1-hydroxy-1-methyl methacrylate, 1-hydroxy-1-methyl acrylate, 1- Hydroxy-1-methylpropyl α-chloroacrylate, 2-hydroxy-1-methyl methacrylate, 2·hydroxy-1-methyl acrylate, 2-hydroxy-1-methylpropyl α-chloroacrylic acid Ester, 1-hydroxy-2-methyl methacrylate, 1-hydroxy-2-methyl acrylate, 1-hydroxy-2-methylpropyl α-chloroacrylate, 2-hydroxy-2-acrylate Methyl propyl ester, 2-hydroxy-2-methyl acrylate, 2-hydroxy-2-methylpropyl α-chloroacrylate, 2-hydroxy-1,1·dimethyl methacrylate, 2-hydroxy acrylate -1,1-dimethylethyl ester, 2·hydroxy-1,1-dimethylethyl α-chloroacrylate, 1,2-dihydroxypropyl methacrylate, 1,2·dihydroxypropyl acrylate 1,2-Dihydroxypropyl α-chloroacrylate, 2,3-dihydroxypropyl methacrylate, 2,3-dihydroxypropyl acrylate, -26-2 01116930 2,3-Dihydroxypropyl α-chloroacrylate, 2,3-dihydroxybutyl methacrylate, 2,3-dihydroxybutyl acrylate, 2,3-dihydroxybutyl α-chloroacrylate , p-hydroxystyrene, p-isopropenylphenol, phenylethyl methacrylate, phenylethyl acrylate, phenethyl α-chloroacrylate, hydrazine-hydroxymethyl acrylamide, hydrazine-hydroxymethyl methacryl Indoleamine, α-chloroacrylic acid, crotonic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-decanoic acid, 9-decanoic acid, 10-undecyl carbon Alkenoic acid, canola acid, ricinoleic acid, 2-(methacryloyloxy)ethyl isocyanate, 2-(acryloxy)ethyl isocyanate, Κα-chloropropene oxime Ester and the like. The photosensitive resin composition of the present invention contains (c) an organic solvent having a boiling point of 100 ° C or more and 130 ° C or less at atmospheric pressure. When the boiling point is less than 100 ° C at atmospheric pressure, the solubility of the components U) and (b) is lowered, and solids may be analyzed. Therefore, streaking of the coating film due to the foreign matter adhering to the slit nozzle (streaking, stripe thickness) is caused, and the film thickness uniformity of the photosensitive resin film is lowered. On the other hand, since the boiling point is 130 t or less at atmospheric pressure, the organic solvent can be removed from the coating film in a short time due to high volatility. Further, in the vacuum drying step or the heat drying step, occurrence of transfer marks such as pin marks can be suppressed. In the present invention, the content of the component (c) is 40% by weight or more and 90% by weight or less based on the total amount of the organic solvent. When the content of the component (c) is less than 40% by weight, streaks or transfer marks may be formed in the coating film or the photosensitive resin film after drying, and the film thickness uniformity of the photosensitive resin film may be lowered. Further, the drying treatment time under reduced pressure progressed slowly. It is preferably 60% by weight or more. On the other hand, when the content of (c) is more than 90% by weight in the range of -27 to 201116930, the content of the component (d) to be described later is relatively lowered, and the effect of suppressing the occurrence of bubbles accompanying the drying under reduced pressure is not sufficient. Preferably, it is 80% by weight or less. (c) The boiling point is 100 ° C or more at atmospheric pressure of 13 (the organic solvent of TC or less is preferably a resin which dissolves the component (a). Specifically, it can be exemplified. Ethylene glycol monomethyl ether (boiling point 124 ° C), propylene glycol monomethyl ether (boiling point 12 〇. (:) and other alkanediol monoalkyl ethers; propyl acetate (boiling point 102 ° C), butyl acetate (boiling point) 125 ° C), isobutyl acetate (boiling point 1 18 ° C) and other alkyl acetates; methyl ethyl ketone (boiling point 116 ° C), methyl isobutyl ketone (boiling point 116 ° C), methyl acetone (boiling point 102 Ketones such as °C); alcohols such as n-butanol (boiling point: 117 ° C) and isobutanol (boiling point: 108 ° C), etc. From the viewpoints of storage stability and viscosity stability of photosensitive resin compositions More preferably, it is a propylene glycol monomethyl ether. The photosensitive resin composition of the present invention contains (d) a boiling point of 150 ° C or more at atmospheric pressure and a viscosity of more than l.lmPa· s at less than 1.5 mPa·s at 20 ° C. (c) an organic solvent having a boiling point of 100 ° C or more and 130 ° C or less at atmospheric pressure, and an organic solvent having a boiling point of 150 ° C or more at atmospheric pressure, and capable of containing In the pattern processing, the development of the photosensitive resin film is facilitated. Further, the occurrence of bubbles accompanying the drying under reduced pressure can be suppressed. On the other hand, since the residual organic solvent to the film after firing can be suppressed, the boiling point is 230. It is more suitable below °C. Further, the organic solvent of component (d) has a viscosity of more than l.lmPa·s at 20 ° C and less than 1.5 mPa·s. The viscosity in 20 C is less than 1.lmPa·s. There may be a case where the solubility of the polyimide resin or the polybenzoxazole or the precursor resin is insufficient, and the film thickness of the photosensitive resin film is lowered. -28-201116930 Uniformity or photosensitive resin composition On the one hand, in the case of more than 15 mPa·s, the viscosity of the photosensitive resin composition rises, especially in the case of slit coating a thick film having a film thickness of 5 μm or more, and the coating from the bayonet is easy. It causes instability. It is also easy to generate bubbles in the vacuum drying step. In the vacuum drying step, it is easy to remove from the low boiling point component (c), and the ratio of the component (d) is increased, but hereby 201 uses a viscosity less than 1.5mPa' to provide In order to suppress the occurrence of bubbles, a photosensitive resin film having excellent film thickness uniformity can be obtained. In particular, when the film thickness of the photosensitive resin film is thick, it is necessary to increase the amount of the coating liquid. It tends to reduce the film thickness uniformity. Moreover, it is easy to occur because it is necessary to remove more organic solvent during drying under reduced pressure, but the organic solvent is combined by a specific amount of component (c) and component (d). In addition, the occurrence of bubbles accompanying drying under reduced pressure is suppressed, and the effect of improving the film thickness uniformity of the photosensitive resin film can be remarkably achieved. In addition, the foam which has been dried under reduced pressure and which has a diameter of 1 mm or less remains in the photosensitive resin film after drying, and can be confirmed by visually observing the surface of the photosensitive resin film by irradiation with a sodium lamp. The ratio of the total amount of the component (d) to the organic solvent used in the present invention is 10% by weight or more and 60% by weight or less. When the content of the component (d) is less than 10% by weight, the effect of suppressing the occurrence of bubbles accompanying drying under reduced pressure is not sufficient. On the other hand, when it exceeds 60% by weight, a transfer mark is generated to the photosensitive resin film or the film thickness uniformity of the photosensitive resin film is lowered. It is preferably 40% by weight or less, more preferably 20% by weight or less. -29- 201116930 (d) The boiling point is 150 at atmospheric pressure. (In the above, in the case of an organic solvent having a viscosity of more than l.lmPa·s' of less than 1.5 mPa·s at 20 ° C, it is preferred to dissolve the resin of the component (a). Specifically, dipropylene glycol is exemplified. Ether (boiling point 171 ° C, viscosity 1.27 mPa·s), diethylene glycol dimethyl ether (boiling point 162 ° C, viscosity 1.17 mPa·s), diethylene glycol ethyl ether (boiling point 176 ° C, viscosity 1.27 mPa) · s), diethylene glycol diethyl ether (boiling point 189. (:, viscosity 1.47mPa·s) and other dialkylene glycol dialkyl ethers; acetic acid% methoxybutyl ester (boiling point 171 ° C, viscosity 1.21mPa .s), an acetate such as ethylene glycol monoethyl ether acetate (boiling point: 160 ° C, viscosity: 1.25 mPa · s), etc. From the viewpoints of storage stability and viscosity stability of the photosensitive resin composition Preferably, diethylene glycol dimethyl ether, diethylene glycol ethyl ether, diethylene glycol diethyl ether, more preferably diethylene glycol dimethyl ether and diethylene glycol ethyl ether. The intermediate boiling point in the atmospheric pressure of an organic solvent is described in "CRC Handbook of Chemistry and Physics" or "Aldrich Handbook of Fine Chemical and Laboratory Equipment". The boiling point of the organic solvent described in the literature can be measured by a commercially available boiling point measuring device such as FP81HT/FP81C (manufactured by Mettler Toledo Co., Ltd.). Further, the viscosity can be used in an organic solvent at 20 ° C. The viscosity of the photosensitive resin composition of the present invention at 25 ° C is adjusted by the use of the components (c) and (d), and the range suitable for the slit coating can be adjusted. For example, when the solid content concentration is 15% by weight, preferably less than 10 μm·s, it is possible to further suppress streaks during slit coating. More preferably, it is 8 mPa·s or less, and more preferably -30-201116930, and a thick film of 5/zm or more is added. The film thickness uniformity at the time of coating is also measured. The viscosity of the photosensitive resin composition solution can be measured using an E-type viscometer. The photosensitive resin composition of the present invention may further contain (e) having the following general formula (1). A thermal cross-linking agent of the structure or a thermal cross-linking agent of the following general formula (2) (hereinafter referred to as (e) thermal cross-linking agent). The (e) thermal cross-linking agent is a) Polyimine, polybenzoxazole, polyimine precursors, Oxazole fathoms of polybenzoxazole precursor resin is at least one or more other additive components to each other or between a crosslinkable 'improved chemical resistance and hardness of the film after firing or after hardening.

In the above general formula (1), R represents a 2- to 4-valent bond; R3 represents a monovalent organic group having 1 to 20 carbon atoms, chlorine, bromine, or fluorine; ^^ and represents CH2〇R7 (R7) a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms; R6 represents a hydrogen atom, a methyl group or an ethyl group; s is an integer of 0 to 2; u represents an integer of 2 to 4; and a plurality of R3 to R6 may be the same Or different. The bond base r is as shown below. -31 - 201116930

s -

——C—R11

In the above formula, R9 to R27 represent a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms, chlorine, bromine, iodine or fluorine. -N(CH2〇R8), (H)v(2) In the above general formula (2), R8 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms; t represents 1 or 2, and v represents 0 or 1' but t + v is 1 or 2. In the above general formula (1), R4 and R5 represent a CH2〇R7 (R7-based hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms) which is a thermal crosslinking group. R7 is preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms because of moderate reactivity and excellent storage stability. Further, in the photosensitive resin composition containing a photoacid generator, a photopolymerization initiator or the like, R7 is more preferably a methyl group or an ethyl group. -32- 201116930 is preferably 85% or more in the configuration shown in the general formula (i). As long as it is excellent in purity, the water absorption property of the non-reverse fat composition which becomes a water-absorbing base is reduced. In terms of obtaining, it can be obtained by, for example, recrystallization or distillation. It has the configuration shown in the general formula (1). In the thermal crosslinking agent, the purity of the compound is 85% or more, and since the storage stability is reduced, a method of obtaining a high-purity thermal crosslinking agent can be obtained. The purity of the thermal crosslinking agent can be suitably determined by a liquid thermal crosslinking agent as described below -33-201116930 OCH, OH 〇CH; <j>C2HsOH <j)C2H5

In the general formula (2), the r8 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, more preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms. In addition, from the viewpoint of the stability of the compound or the storage stability of the resin composition, R8 is preferably a methyl group in a photosensitive resin composition containing a photoacid generator or a photopolymerization initiator of -34 to 201116930. Or an ethyl group, preferably the number of the (CH2〇R8) group contained in the compound is 8 or less. A suitable example of a thermal crosslinking agent having a group represented by the general formula (2) is as follows: ==/N-CH2OCH3 n-ch, och3 c-n°n-ch2och3 h3coh2c-nVch2och3 H3C〇T〇CH3 H3COH2CH\N_CH2OCH3

,n-ch2och2ch3 T4-CH2〇CH2CHj H H3CH2COH2C-ij^HCH2OCH2CH3

HsC^CO och2ch3

HjC^COHzCHfVcHjOCHaCHa H3CH2COH2C--fQ|-CH2OCH2CH3 h3coh2c-nH^COHzC^XJ H3OOH2C ^ l-CHoOCHa .CH2OCH3 "CHiOCHs h3coh2c-nh h3ch2coh2c - w-CHz (e) The content of thermal crosslinker relative to (a) The component resin is preferably 100 parts by weight or more and 100 parts by weight or less based on 100 parts by weight of the resin. When the content of the (e) thermal crosslinking agent is from 10 parts by weight to 100 parts by weight, the strength of the film after firing or after curing is high, and the storage stability of the photosensitive resin composition is also excellent. The resin composition of the present invention may further contain (f) a thermal acid generator. (f) The thermal acid generator generates an acid by heating after development as described later, and in addition to promoting the crosslinking reaction of the resin of the component (a) and the thermal crosslinking agent of the component (e), the component (a) may be promoted. The cyclization of the quinone ring of the resin and the carbazole ring. Therefore, the chemical resistance of the film after firing can be improved, and the film can be thinned. The acid generated from the (f) thermal acid generator is preferably a strong acid, preferably an arylsulfonic acid such as p-toluenesulfonic acid or benzenesulfonic acid; or an alkane such as methanesulfonic acid, ethanesulfonic acid or butanesulfonic acid; Kefu-35- 201116930 Acid and so on. In the present invention, the thermal acid generator is preferably an aliphatic sulfonic acid compound represented by the general formula (3) or (4), and these may also contain two or more kinds.

In the above general formulas (3) and (4), R28 to R3. It represents an alkyl group having 1 to 10 carbon atoms or a monovalent aromatic group having 7 to 12 carbon atoms. The alkyl group and the aromatic group may be substituted, and examples of the substituent include an alkyl group, a carbonyl group and the like. Specific examples of the compound represented by the general formula (3) include the following compounds

Specific examples of the compound represented by the general formula (4) may be exemplified by the following compounds 201116930

(f) The content of the thermal acid generator is preferably from 5% by weight to 10 parts by weight based on 100 parts by weight of the resin of the component (a), from the viewpoint of further promoting the crosslinking reaction. the following. The purpose is to compensate for the developability of the photosensitive resin composition as needed, and may also contain a compound having a phenolic hydroxyl group. In the case of a compound having a phenolic hydroxyl group, for example, 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,

BisCR-IPZ, BisOCP - IPZ, B is 01P P - CP, B is 2 6 X - IPZ, BisOTBP-CP 'TekP-4HBPA (four P-DO-BPA) ' TrisP-HAP, TrisP-PA, TrisP- PHBA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, BiS236T-OCHP, Methylene ginseng FR-CR, BisRS-26x, BisRS-OCHP, (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, B1P-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP -BIOC-F, 4PC, BIR-BIPC-F, ΤΕΡ-ΒΙΡ·Α (trade name, manufactured by 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-dihydroxyporphyrin, -37- 201116930 2,6-di-based quinoline, 2,3-di-quinoquinone (Quinoxaline), Hui-1,2,10-triol, indole-1,8,9-triol, 8-quinoline Porphyrin and the like. By containing a compound having such an inert diameter group, the obtained photosensitive resin composition 'is hardly dissolved in the alkali developing solution before exposure, and is easily dissolved in the developer solution if exposed. Less' and easy to develop in a short time. Therefore, it is easy to improve the sensitivity. The content of the compound having such a phenolic hydroxyl group is preferably from 3 parts by weight to 40 parts by weight per 100 parts by weight of the resin of the U) component. The photosensitive resin composition of the present invention 'may contain a thermochromic compound exhibiting absorption greatly at 350 nm or more and 700 nm or less in heating coloring; or less than 500 nm in 350 nm or more and having no absorption maximum at 500 nm or more and 7 50 nm. The following are organic pigments or dyes that absorb greatly. The color development temperature of the thermochromic compound is preferably 120 ° C or higher and 150 ° C or higher. The higher the color development temperature of the thermochromic compound, the more excellent the heat resistance under high temperature conditions, and the fading is not caused by the long-term ultraviolet-visible light irradiation, and the light resistance is excellent. The thermochromic compound may, for example, be a thermosensitive dye, a pressure sensitive dye, or a hydroxyl group-containing compound having a triarylmethane skeleton. The photosensitive resin composition of the present invention may further contain a adhesion improving agent. As the adhesion improving agent, ethylene trimethoxy decane, ethylene triethoxy decane, epoxy cyclohexyl ethyl trimethoxy decane, 3 · glycidoxypropyl trimethoxy decane, 3-glycidoxypropyl three Ethoxy decane, p-styrene trimethoxy decane ' 3 -aminopropyl trimethoxy decane ' 3 -aminopropyl triethoxy decane, N - phenyl-3-amine - 38 - 201116930 propyl trimethoxy decane, etc. A decane coupling agent; a titanium chelating agent, an aluminum chelating agent, and the like. These may also contain two or more types. When the photosensitive resin film is developed by the use of the adhesion improving agent, the adhesion to the base material such as ruthenium wafer, ITO, Si〇2, or tantalum nitride can be improved. Further, it is possible to improve the resistance to oxygen plasma treatment and UV ozone treatment used for washing or the like. The content of the adhesion improving agent is preferably from 0.1 to 1 part by weight based on 100 parts by weight of the resin of the U) component. The photosensitive resin composition of the present invention may further contain a subsequent improver. Further, the modifier may, for example, be an alkoxydecane aromatic amine compound, an aromatic guanamine compound or an aromatic decane-free compound. These may also contain two or more types. By including these compounds, the adhesion between the film and the substrate after firing or after curing can be improved. Specific examples of the alkoxydecane-containing aromatic amine compound and the aromatic amidoxime compound are shown below. In addition, a compound obtained by reacting an aromatic amine compound with an alkoxy group-containing compound may, for example, be a compound obtained by reacting an aromatic amine compound with an alkoxysilane compound, or the like, and the alkoxydecane compound. It has a group reactive with an amine group such as an epoxy group or a chloromethyl group. -39- 201116930 H2Ni〇rtr3 h^〇4£ch: h2n.

I2CH3 CH2CH3

〇CH2CH3 SHDCHsCI

Uoc ?CH2CH3 corpse 3 (p〇H3

HzN-4 SHOCH2CK3 W3C〇NHs^s^^°ch3 CH3CONH-\ y-4*-〇CH3 ^ Wh3 l J och3 ^ 6ch3

CpCHzCHa CHaCONH.^^i-OCHaCHa CH3CONI OCH2CH3 OChbCHa PCH3 丨 Η"^^-+ΗΧΗ2(ίΗ3Η2ΪγΪ!γ-号 HO- 7 OCH2CH3 〇CH3 OCH3

IHCOCH3 ch3coni NHCOCH3 OCH3 is preferably 0.01 to 15 parts by weight based on 100 parts by weight of the resin of the component (a). The photosensitive resin composition of the present invention may contain a surfactant to improve the coating property with the substrate. Fluoride (trade name, manufactured by Sumitomo 31⁄2 Co., Ltd.), "megafac (registered trademark)" (made by DIC Corporation), and Sulphurone (trade name, manufactured by Asahi Glass Co., Ltd.) can be exemplified as the surfactant. Interface surfactant; KP3 41 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Co., Ltd.), Glanol (trade name, manufactured by Kyoei Chemical Co., Ltd.), BYK (BYK) An organic oxoxane surfactant such as Co., Ltd.; an acrylic polymer surfactant such as Polyflow (trade name, manufactured by Kyoei Chemical Co., Ltd.). -40-201116930 Next, a method for producing the photosensitive resin composition of the present invention will be described. For example, by dissolving the components U) to (d), the components (e) to (f) as needed, the dissolution adjusting agent, the thermochromic component, the adhesion improving agent, the modifying agent or the surfactant, etc. A photosensitive resin composition can be obtained. As the dissolution method, stirring or heating can be exemplified. In the case of heating, the heating temperature is preferably set within a range not detracting from the performance of the photosensitive resin composition, and is usually room temperature to 80 °C. Further, the order of dissolution of each component is not particularly limited, and for example, a method in which a compound having low self-solubility is dissolved in order is used. In addition, when a surfactant or a part of the adhesion improving agent or the like is stirred and dissolved, the component of the bubble is apt to occur, and after the other component is dissolved, the other component due to the generation of the bubble can be prevented. Poorly dissolved. The resulting photosensitive resin composition is preferably filtered using a filter to remove dust or particles. The filter pore size is, for example, 〇.5//m, 0.2/zm, 0.1#m, 0.07#m, 0.05 ym, etc., but is not limited thereto. The material of the filter is polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., but polyethylene or nylon is preferred. Next, a method of producing a photosensitive resin film using the photosensitive resin composition of the present invention will be described. The coating method of the photosensitive resin composition may, for example, be a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method, or the like, or may be combined, but may be used to form a photosensitive resin composition of the invention. The best method for the effect is the gap coating method. In the slit coating method, there is a problem that appearance defects such as transfer marks and streaks are liable to occur, and the film thickness uniformity of the photosensitive resin film after drying is low. However, the photosensitive resin of the present invention is used in -41 - 201116930. In the case of the composition, even if it is applied by the slit coating method, a photosensitive resin film having a good appearance and excellent film thickness uniformity can be obtained. Moreover, the occurrence of bubbles accompanying drying under reduced pressure can be suppressed. The method for producing a photosensitive resin film of the present invention comprises the steps of: applying a photosensitive resin composition of the present invention to a substrate using a slit nozzle to form a coating film; and (2) a step of drying the coating film under reduced pressure. First, (1) the photosensitive resin composition of the present invention is applied to a substrate using a slit nozzle to form a coating film. There is no particular limitation on the slit nozzle used for coating, and it is also possible to use a product which is marketed by a plurality of manufacturers. Specifically, a "linear coater" manufactured by Dainippon Screen Manufacturing Co., Ltd., "Spinless" manufactured by Tokyo Ohka Kogyo Co., Ltd., and a "TS coater" manufactured by Tor ay Engineering Co., Ltd., "Table coater" manufactured by Chubu Furnace Co., Ltd., "CS series" manufactured by Tokyo Electron Co., Ltd., "CL system 歹 [J", "Online gap coater" manufactured by Cermatronics Trading Co., Ltd., Hirata Machinery Co., Ltd. "Head coater HC series" and the like. The coating speed is generally in the range of 10 mm/sec to 400 mm/sec. The film thickness of the coating film varies depending on the solid content concentration and viscosity of the photosensitive resin composition, but is usually applied to a film thickness after drying to be 0.1 to 20 " m, preferably 0.3 to 10 #m. When the photosensitive resin composition of the present invention is used, good film thickness uniformity can be obtained even when the thickness of the photosensitive resin film of 5 # m or more is obtained. Before the application, the substrate may be treated with the adhesion improving agent in advance to perform pretreatment. For example, a close-contact modifier 〇. 5 to 20% by weight of -42-201116930 can be dissolved in isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene diacetate, propylene glycol monomethyl ether, ethyl lactate, A solution of diethyl adipic acid, which is subjected to a base treatment by spin coating, slot coating, dip coating, spray coating, steam treatment or the like, using the solution. The vacuum drying treatment may be carried out as needed, and the substrate and the adhesion improver may be subjected to heat treatment at 50 ° C to 300 ° C, and (2) the substrate may be dried under reduced pressure to obtain a substrate for forming a coating film of the photosensitive resin film. Press drying is a general matter. For example, the substrate is placed on a proxy pin in a vacuum chamber to be decompressed in a vacuum chamber, and dried under reduced pressure. If the substrate is spaced apart from the top of the vacuum chamber, the substrate is placed on the top of the base chamber. The air between the positions is easily accompanied by the drying under reduced pressure and is prone to haze. Therefore, it is preferable to adjust the height of the agent pin to be narrow. The distance between the substrate and the ceiling of the vacuum chamber is preferably from 2 to the right, more preferably from 2 to 10 mm. The vacuum drying rate varies depending on the volume of the vacuum chamber, the capacity of the vacuum pump, and the piping diameter between the pumps. For example, if the substrate is not coated, the pressure is reduced to 40 Pa after 60 seconds in the vacuum chamber. The general vacuum drying time is usually 60 seconds to the right, and the vacuum chamber internal limit pressure at the time of completion of the vacuum drying is usually 60 Pa or less in the state of the plate. When the ultimate pressure (pressure) is 60 Pa or less, the surface of the coating film can be made dry, and the subsequent application of the substrate can suppress the application of the solvent bar such as surface alcohol monomethyl ether ester or the surface of the plate. By: should. . For each, for example, in a coated film. At this time, the plate flows with vacuum, so that between 20 mm left or the chamber and the state, the condition is 1 0 0 seconds left coated base (ultimate adhesive dry pollution or grain -43- 201116930 On the other hand, the lower the ultimate pressure, the easier it is to cause bubbles on the surface of the coating film. When the photosensitive resin composition of the present invention is used, even when it is dried under reduced pressure, the film thickness of the photosensitive resin is 5 or more. It is also possible to suppress the occurrence of bubbles. After drying under reduced pressure, the coating film is heated and dried in a general procedure. This step is also called prebaking. The drying system uses a hot plate, an oven, infrared rays, etc. In the case of using a hot plate, Directly heat the plate, or keep the coating film on the fixture such as the pin on the board and heat it. The material of the pin is aluminum or stainless steel, or polyimide resin or Teflon (registered) If the synthetic resin such as "trademark" has heat resistance, it is possible to use any kind of material. The height of the agent pin varies depending on the size of the substrate, the type of coating film, the purpose of heating, etc. The heating temperature is about 0.1 to about 1 mm. The heating temperature varies depending on the type or purpose of the coating film, and is preferably from 1 minute to several hours from room temperature to 180 ° C. Next, the self-photosensitive property is obtained. A method of forming a pattern of a resin film is described. A photosensitive mask having a desired pattern is passed through a photosensitive resin film, and a chemical line is irradiated and exposed. The chemical lines used for the exposure are ultraviolet rays, visible light, and electron beams. X-ray or the like, but in the present invention, i-line (365 nm), h-line (405 nm), and g-line (4 36 nm) of a mercury lamp are preferably used. In the case of positive photosensitive, the exposed portion is dissolved in a developing solution. In the case of having a negative photosensitive property, the exposed portion is hardened and insolubilized to the developer. After the exposure, the developer is used, in the case of a positive type, by removing the exposed portion, and in the case of a negative type, by the case of a negative type, The non-exposed portion is removed to form a pattern of the desired period - 44 - 201116930. In the case of a developer, preferably in the case of a positive type or a negative type, an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol , sodium hydroxide, hydrogen and oxygen Potassium, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine An aqueous solution of a compound exhibiting basicity such as ethylene diamine or hexamethylene diamine, and optionally, N-methyl-2-pyrrolidone, N, N-di may be added to the aqueous alkali solution. a polar solvent such as methotrexate, N,N-dimethylacetamide, dimethyl hydrazine, butyrolactone, dimethyl decylamine; alcohols such as methanol, ethanol, isopropanol; ethyl lactate, propylene glycol An ester such as monomethyl ether acetate; a ketone such as cyclopentanone, cyclohexanone, isobutyl ketone or methyl isobutyl ketone, or the like, which may be added alone or in combination, and in a negative form, The above polar solvent or an alcohol, an ester, a ketone or the like which does not contain an aqueous alkali solution may be used alone or in combination of several. Rinsing with water after development is a general step. Here, an alcohol such as ethanol or isopropyl alcohol; an ester such as ethyl lactate or propylene glycol monomethyl ether acetate may be added to water for rinsing treatment. The photosensitive resin film is fired by heat-treating the pattern of the obtained photosensitive resin film. For example, a method of heat treatment at 230 ° C for 60 minutes, a method of heat treatment at 120 to 400 ° C for 1 minute to 10 hours, addition of a hardening catalyst, etc. at room temperature to about 1 ° C A method of heat treatment at a low temperature, a method of hardening at a low temperature of about room temperature to about 1 ° C by ultrasonic or electromagnetic wave treatment, and the like. -45 - 201116930 A film obtained by burning a photosensitive resin composition of the invention can be suitably used for a surface protective film or an interlayer insulating film of a semiconductor device such as LSI, an insulating film of an organic EL device, and a planarizing film of a TFT substrate for a display element. A wiring protective film for a circuit board, an onchip microlens for a solid imaging device, or a display for a flattening film for a solid-state imaging device. EXAMPLES The present invention is illustrated by the following examples and the like, but the present invention is not limited by the examples. Further, the evaluation of the photosensitive resin composition in the examples was carried out in the following manner. (1) Preparation of Photosensitive Resin Film A photosensitive resin composition was applied onto a 1100 mm x 960 mm chromium film-forming substrate using a slit coater (TS coater manufactured by Toray Engineering Co., Ltd.) so that the film thickness after drying became 4/. /m, 5em or 6/zm. The coating speed was 50 mm/sec. After coating, it was placed in a vacuum chamber and dried under reduced pressure for 1 second. Adjust so that the chamber pressure becomes 3 OPa after 100 seconds. When the pressure is reduced, the height of the agent pin is 30 mm, and the distance between the substrate and the ceiling of the chamber is 6 mm. Thereafter, prebaking was performed at 120 ° C for 120 seconds using a hot plate to obtain a photosensitive resin film. The height of the agent pin at the time of pre-baking is 0.5 mm. (2) Evaluation of the appearance of the photosensitive resin film. Under the sodium lamp, the photosensitive resin film obtained by the method of (1) is visually observed, and various streaks from the slit nozzle are observed. Decompression drying agent pin marks (V CD pin marks), hot plate agent pin marks (HP pin marks), uneven haze, bubbles, and the third-order -46-201116930 evaluation. It can be clearly observed that 1, the only one observed is 2, and the one who cannot observe it is 3. (3) Evaluation of the film thickness uniformity of the photosensitive resin film The film thickness of the photosensitive resin film produced by the method of (1) was measured using the film thickness measuring device FTM manufactured by Toray Engineering Co., Ltd. The remaining portion of each side of the substrate was divided into 1 aliquots every 100 mm. The film thickness uniformity was calculated by the following formula: 3.5% or less was good, more preferably 3% or less.値=100 film thickness sum/100 film thickness uniformity (%)=[{(maximum film thickness-minimum film thickness)+ 2}/film thickness average 値]X 1 0 0 (4) Calculation of boiling point of organic solvent Methods The boiling points of the organic solvents used in the examples and comparative examples of the present invention are cited in "CRC Handbook of Chemistry and Physics" and "Aldrich Handbook of Fine Chemical and Laboratory Equipment". (5) The calculation method of viscosity is used in the present invention. The viscosity of the organic solvent of the examples and the comparative examples was measured at 20 Torr using a Ubbelohde viscometer. The viscosities of the varnishes of the photosensitive resin compositions of the examples and comparative examples of the present invention were measured using an E-type viscometer at 251. Synthesis Example 1 Synthesis of hydroxyl-containing diamine compound (HFHA) -47- 201116930 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF, manufactured by Central Glass Co., Ltd.) 18.3 g (0.05 Mo The ear was dissolved in acetone 〇〇mL, propylene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.), 17.4 g (0.3 mol), and cooled to -15 ° C. The 3-nitrobenzhydryl chloride was dropped there. 20.4 g (0.11 mol) of a solution of 100 mL of acetone dissolved in acetone. After the completion of the dropwise addition, the mixture was stirred at -15 ° C for 4 hours, and then returned to room temperature. The precipitated white solid was filtered off at 50 The solution was dried in vacuo. 30 g of the obtained white solid was placed in a 300 mL stainless steel autoclave, and dispersed in 250 mL of cellosolve, and 5% palladium-carbon (manufactured by Wako Pure Chemical Co., Ltd.) was added. Here, hydrogen is introduced into the balloon, and the reduction reaction is carried out at room temperature. After about 2 hours, it is confirmed that the balloon is no longer atrophy, and the reaction is completed. After the reaction is completed, the catalyst is removed, and the catalyst-containing palladium compound is removed to rotate the evaporator. The mixture was concentrated to obtain a hydroxyl group-containing diamine compound (HFHA) represented by the following formula.

Nh2 Synthesis Example 2 Synthesis of quinonediazide compound Under a dry nitrogen stream, 'TrisP-PA (trade name: manufactured by Honshu Chemical Industry Co., Ltd.), 21.22 g (0.05 mol) and 5-naphthoquinonediazide group 26.8 g (0.1 mol) of sulfonic acid chloride (manufactured by Toyo Seisakusho Co., Ltd.) was dissolved in 450 g of 1,4-dioxane and set at room temperature. Here, 12.65 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the inside of the system was no longer 35 °C or higher. After the dropwise addition, the mixture was stirred at 40 ° C for 2 hours. Filtration of triethylamine salt was carried out into water -48 - 201116930. Thereafter, the precipitate which precipitated was collected by filtration, and further washed with 1 L of 1% hydrochloric acid water. Thereafter, the mixture was further washed twice with 2 L of water. The precipitate was dried in a vacuum dryer to obtain a quinonediazide compound represented by the following formula.

Synthesis Example 3 Synthesis of alkoxymethyl group-containing compound (A-1) 1,1,1-paraxyl (4-hydroxyphenyl)ethane (manufactured by Honshu Chemical Industry Co., Ltd., TrisP-HAP) 103.2 g ( 0.4 mol) was dissolved in a solution in which 80 g of sodium hydroxide (2.0 mol) was dissolved in 800 g of pure water. After complete dissolution, 686 g of 36 to 38% by weight aqueous solution of Formalin was dropped at 20 to 25 ° C for 2 hours. Thereafter, it was stirred at 20 to 25 ° C for 17 hours. To this, 98 g of sulfuric acid and 5 5 2 g of water were added for neutralization, and the same was left for 2 days. After standing, the needle-like white crystals produced in the solution were collected by filtration and washed with 100 mL of water. The white crystals were dried under vacuum at 50 ° C for 48 hours. The dried white crystals were prepared by high performance liquid chromatography by Shimadzu Corporation, and the column was subjected to ODS. The solvent was developed using acetonitrile/water = 70/30, and analyzed at 25 4 nm. It is 92%. Further, DMSO-d6 was used as a heavy solvent, and NMR (manufactured by JEOL Ltd., GX-270) was analyzed to find hexamethylolated TrisP-HAP. Then, the compound thus obtained was dissolved in methanol (300 mL), and 2 g of sulfuric acid was added thereto, followed by stirring at room temperature for 24 hours. In this solution, anion ion-49-201116930 was added to the resin (Raw 11111111 (manufactured by 111 & 35 Co., Ltd., person 111561'115111^9638) 15 £, and stirred for 1 hour, and the ion exchange resin was removed by filtration. 500 mL of ethyl lactate was added, and methanol was removed by a rotary evaporator to obtain an ethyl lactate solution. When the solution was allowed to stand at room temperature for 2 days, white crystals were produced. The obtained white crystals were analyzed by high-performance liquid chromatography. It is a hexamethoxymethyl compound (containing an alkoxymethyl compound (A-1)) having a purity of 99% of TrisP-HAP represented by the following formula.

The other thermal crosslinking agents and acid generators used in the examples are as follows.

WPAG-314 Example 1 51.3 g (0.085 mol) of hydroxy-containing diamine obtained in Synthesis Example 1 and 1,3-bis(3-aminopropyl)tetramethyldioxane-50 were obtained under a dry nitrogen stream. - 201116930 (SiDA, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.24g (0.005 mol), 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.18 g (0.02 mol) dissolved in N-methyl hydrazine (NMP) 200g. Here, 31.0 g (0.1 mol) of 3,3',4,4'-dibenzoic acid tetraphthalic acid dianhydride (ODPA, manufactured by Manac Co., Ltd.) was added, and the mixture was stirred at 40 ° C for 2 hours. Thereafter, a solution of 7.14 g (0.06 mol) of dimethylformamide (DFA), which was diluted with nMP 5 g, was added dropwise over 10 minutes. After dripping, the mixture was stirred at 40 ° C for 2 hours. After the completion of the stirring, the solution was poured into 2 L of water to collect a precipitate of the polymer solid by filtration. Further, the mixture was washed three times with 2 L of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C for 72 hours to obtain a polyimide precursor. 1 g of the polyimine precursor, 3 g of the quinonediazide compound obtained in Synthesis Example 2, 2 g of TrisP-PHBA (manufactured by Honshu Chemical Co., Ltd.) as a dissolution adjuster, and BYK33 as a surfactant. 3 (manufactured by BYK Co., Ltd.) 0.04 g was added to propylene glycol monomethyl ether (boiling point 12 (TC) 68 g and diethylene glycol ethyl ether (boiling point 176 ° C, viscosity 1.27 mPa · s) 17 g, and stirred to obtain positive A varnish of a photosensitive polyimide composition having a viscosity of 7.3 mPa·s. Using the obtained varnish, a photosensitive resin film is formed by slit coating by the method (1) so as to be dried. The film thickness was 4 " m. When the appearance of the obtained photosensitive resin film was evaluated, streaks, decompression drying agent pin marks, hot plate agent pin marks, uneven haze, and bubbles could not be observed. The film thickness uniformity was 1.9%. Example 2 -51-201116930 Using the varnish of Example 1, the photosensitive resin film ' was produced by slit coating so that the film thickness after drying was 5 μm. When the appearance of the obtained photosensitive resin film was evaluated, the strip could not be observed. The pressure-drying agent pin mark, hot plate agent pin mark, uneven haze, and bubble type were 3. The film thickness uniformity was 2.5%. Example 3 Using the varnish of Example 1 to be produced by slit coating The photosensitive resin film 'haves a film thickness after drying of 6/m. In the evaluation of the appearance of the obtained photosensitive resin film, streak, decompression drying agent pin marks, hot plate agent pin marks, and Any of the haze unevenness was '3. Only the bubble was observed to be 2. The film thickness uniformity was 2.9%. Example 4 except that the solvent was changed to propylene glycol monomethyl ether (boiling point 120 ° C) 6 8 g and A photosensitive resin film was produced in the same manner as in Example 2 except that diethylene glycol dimethyl ether (boiling point: 162 ° C, viscosity: 1.17 mPa·s) was used. The viscosity of the varnish was 7. ImPa.s. In the evaluation of the appearance of the photosensitive resin film, it was not observed that streaks, decompression drying agent pin marks, hot plate agent pin marks, and haze were 3, and only 2 bubbles were observed. The property was 2.4%. Example 5 In addition to changing the solvent to propylene glycol monomethane (boiling point 120 °C) 68g and - B A photosensitive resin film was produced in the same manner as in Example 2 except that diol diethyl ether (boiling point: 189T: viscosity: 1.47 mPa·s) was used. The viscosity of the varnish was -52 - 201116930 7.6 mPa · s. When the appearance of the resin film was evaluated, streaks, decompression drying agent pin marks, hot plate agent pin marks, uneven haze, and bubbles were not observed, and the film thickness uniformity was 2.9%. 10 g of the polyimine precursor obtained in Example 1, 2.5 g of the quinonediazide compound obtained in Synthesis Example 2, the alkoxymethyl group-containing compound (Al) obtained in Synthesis Example 3, and TrisP-PHBA as a dissolution adjuster (the state) Chemical Industry Co., Ltd. has 1⁄4 company system) 1.5g, as a surfactant BYK333 (BYK Co., Ltd.) 0.04g added to propylene glycol monomethyl ether (boiling point 120 ° C) 59.5g and diethylene glycol ethyl ether (boiling point 176t: viscosity 1.27mPa.s) 17g and r-butyrolactone (boiling point 203 ° C, viscosity 1.90 mPa·s) 8.5g, and stirred to obtain a varnish of positive photosensitive polyimide polyimide precursor composition . The viscosity of the varnish is 7.4 mPa · s. Using the obtained varnish, a photosensitive resin film was formed by slit coating by the method (1), and the film thickness after drying was 5 Mm. When the appearance of the obtained photosensitive resin film was evaluated, it was not observed that the streaks "decompression drying agent pin marks, hot plate agent pin marks, uneven haze, and bubbles were 3". The film thickness uniformity was 2.8%. Example 7 The same procedure as in Example 2 except that the solvent was changed to 51 g of propylene glycol monomethyl ether (boiling point: 120 ° C) and 34 g of diethylene glycol ethyl ether (boiling point: 176 ° C, viscosity: 1.27 mPa·s). A photosensitive resin film was produced. The viscosity of the varnish is 6.8 m P a · s. In the evaluation of the appearance of the obtained photosensitive resin film, it was not observed that any of the streaks and bubbles were observed, and only 3 ° was observed to dry under reduced pressure. -53 - 201116930 Agent pin marks, hot plate agent marks, haze It is 2 because of unevenness. The film thickness uniformity was 3.5%. Example 8 The same procedure as in Example 2 except that the solvent was changed to 51 g of propylene glycol monomethyl ether (boiling point: 12 ° C) and 34 g of diethylene glycol dimethyl ether (boiling point: 162 ° C, viscosity: 1.17 mPa·s). A photosensitive resin film was produced. The viscosity of the varnish is 6.5 mPa · s. In the evaluation of the appearance of the obtained photosensitive resin film, it was not observed that streaks, decompression drying agent pin marks, hot plate agent pin marks, and haze were not observed, and only 3» was observed. 2. The film thickness uniformity was 3.4%. Example 9 In addition to changing the solvent to propylene glycol monomethyl ether (boiling point 120 ° C) 51 g and diethylene glycol ethyl ether (boiling point 176 ° C, viscosity 1.27 mPa · s) 17g and r - butyrolactone (boiling point 203 ° A photosensitive resin film was produced in the same manner as in Example 2 except that the viscosity was 1.90 mPa·s) and 17 g. The viscosity of the varnish is 7.3 m Pa · s. When the appearance of the obtained photosensitive resin film was evaluated, it was not observed that streaks, decompression drying agent pin marks, hot plate agent pin marks, uneven haze, and bubbles were three. The film thickness uniformity was 2.9%. Example 1 except that the solvent was changed to 76.5 g of propylene glycol monomethyl ether (boiling point 120 ° C) and 8.5 g of diethylene glycol ethyl ether (boiling point 176 ° C, viscosity 1.27 mPa · s), and Example 2 A photosensitive resin film was produced in the same manner. The viscosity of the varnish is 7.9 mPa · s. When the appearance of the obtained photosensitive resin film was evaluated, it was found that the streaks, the reduced-pressure drying agent pin marks, the hot plate agent pin marks, and the haze unevenness were observed in the absence of -54-201116930. Only 2 bubbles were observed. The film thickness uniformity was 2.9%. Example 11 Under a dry nitrogen stream, 8.3 g of BAHF (0.05 mol) was dissolved in NMP 50 g, epoxypropyl methyl ether 26.4 g (0.3 mol), and the temperature of the solution was cooled to -15 °C. Here, 7.4 g (0.025 mol) of diphenyl ether dicarboxylic acid dichloride (manufactured by Nippon Pesticide Co., Ltd.) and isophthalic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.1 g (0.025 mol) were dissolved by dropping. A solution of 25 g of τ · butyrolactone (GBL) was used so that the internal temperature did not exceed 0 °C. After the completion of the dropwise addition, stirring was continued at -15 ° C for 6 hours. After the completion of the reaction, the solution was poured into 3 L of water containing 10% by weight of methanol, and a white precipitate was collected. The precipitate was collected by filtration, washed with water three times, and dried in a vacuum dryer at 50 ° C for 72 hours to obtain a polybenzoxazole precursor. To 10 g of the polybenzoxazole precursor, 3 g of the quinonediazide compound obtained in Synthesis Example 2, 2 g of TrisP-PHBA (manufactured by Honshu Chemical Industry Co., Ltd.) as a dissolution adjuster, and BYK333 as a surfactant ( BYK Co., Ltd.) 0.04g of propylene glycol monomethyl ether (boiling point 120 ° C) 51g and diethylene glycol ethyl ether (boiling point 176 ° C, viscosity 1.27mPa · s) 34g, and stirred to obtain positive sensitization A varnish of a polybenzoxazole precursor composition. The viscosity of the varnish is 7.1 mPa*s. Using a varnish, the photosensitive resin film was formed by slit coating in the method described in the above (1) so that the film thickness after drying was 5 μm. -55-201116930 When the appearance of the obtained photosensitive resin film was evaluated, it was not observed that any of the streaks and bubbles was 3. Only the decompression drying agent pin marks, the hot plate agent pin marks, and the uneven haze were observed to be 2. The film thickness is 3.5%. Example 1 2 Under a dry nitrogen stream, 32.9 g of BAHF (0.09 mol) was dissolved in 500 g of NMP. Here, ODPA 31.0 g (0-1 mol) was added together with NMP 50 g, and stirred at 30 ° C for 2 hours. Thereafter, 2.18 g (0.02 mol) of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and stirring was continued at 40 ° C for 2 hours. In addition, 5 g of pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) was diluted with toluene (30 g of Tokyo Chemical Industry Co., Ltd.), and added to the solution, and the water was removed by azeotropy together with toluene. At the same time, the temperature of the solution was changed to 120 ° C for 2 hours, and further, the reaction was carried out at 180 ° C for 2 hours. The temperature of the solution was lowered to room temperature, and the solution was poured into 3 L of water to obtain a white powder. The powder was collected by filtration, and washed again with water three times. After washing, the white powder was dried in a vacuum dryer at 50 ° C for 72 hours to obtain a polyimide. 10 g of the polyimine, 3 g of the quinonediazide compound obtained in Synthesis Example 2, 2 g of TrisP-PHBA (manufactured by Honshu Chemical Industry Co., Ltd.) as a dissolution adjuster, and BYK 3 33 as a surfactant (BYK Limited) 0.04g of propylene glycol monomethyl ether (boiling point 120 ° C) was added to propylene glycol monomethyl ether (boiling point 120 ° C) and diethylene glycol ethyl methyl ether (boiling point 176 ° C, viscosity 1.27 mPa · s) 34g' and stirred to obtain positive photosensitivity A varnish of a polyimide composition. The varnish has a viscosity of -56 - 201116930 6.5 mPa · s; using a varnish. The photosensitive resin film is formed by slit coating by the method described in (1) so that the film thickness after drying is 5 μm. When the appearance of the obtained photosensitive resin film was evaluated, it was not observed that any of the streaks and the bubbles was 3. Only the decompression drying agent pin marks, the hot plate agent pin marks, and the uneven haze were observed to be 2. The film thickness uniformity was 3.3%. Example 1 3 The polyalkylenimine obtained in Example 12 was 〇g, the alkoxymethyl group-containing compound (Al) obtained in Synthesis Example 3 was 2.4 g, and ethylene oxide-modified bisphenol A dimethacrylate (new Nakamura Chemical Industry Co., Ltd., NK ester BPE-100) 2g, trimethylolpropane triacrylate 0.5g, 1,2-octanedione. 1-[4-(phenylthio)-2-(0 - benzamidine)] (manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.1 g, and 0.04 g of BYK3 3 3 (manufactured by BYK Co., Ltd.) as a surfactant, added to propylene glycol monomethyl ether (boiling point i20 ° C) 68 g of 17 g of diethylene glycol ethyl ether (boiling point: 176 ° C, viscosity 1.27 mPa · s) was stirred to obtain a varnish of a negative photosensitive polyimide composition. The viscosity of the varnish is 7.9 mPa · s. Using a varnish, a photosensitive resin film was formed by slit coating by the method described in the above (1) so that the film thickness after drying became 5 / zm. When the appearance of the obtained photosensitive resin film was evaluated, it was not observed that the streaks, the reduced-pressure drying agent pin marks, the hot plate agent pin marks, the haze unevenness, and the bubbles were three. The film thickness uniformity was 2.8%. Example 1 4 The polybenzoxazole precursor obtained in Example 11 was used, and WPAG-314 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) was 0.5 g, and it was produced as a thermal acid-57-201116930. -propylsulfonyloxyimido-5H-thiophene-2-methylphenyl-acetonitrile (trade name: PAG-103, manufactured by Ciba Specialty Chemicals Co., Ltd.) 〇.5g, MW-3OHM (Sanwa Chemical Co., Ltd. 4 g, BYK333 (manufactured by BYK Co., Ltd.) as a surfactant, 0.04 g, added to propylene glycol monomethyl ether (boiling point 120 ° C) 68 g and diethylene glycol ethyl ether (boiling point 176 ° C, viscosity 1.27 mPa · s) 17 g was stirred to obtain a varnish of a negative photosensitive polybenzoxazole precursor composition. The viscosity of the varnish is 7.6 mPa · s. Using the obtained varnish, a photosensitive resin film was formed by slit coating by the method described in the above (1) so that the film thickness after drying was 5 / / m. When the appearance of the obtained photosensitive resin film was evaluated, it was not observed that streaks, decompression drying agent pin marks, hot plate agent pin marks, uneven haze, and bubbles were three. The film thickness uniformity was 2.8%. Example 1 5 The same procedure as in Example 2 except that the solvent was changed to 68 g of ethylene glycol monomethyl ether (boiling point: 124 ° C) and 17 g of diethylene glycol ethyl ether (boiling point: 176 t, viscosity: 1.27 mPa·s). A photosensitive resin film was produced. The viscosity of the varnish is 7.0 mPa · s. When the appearance evaluation of the obtained photosensitive resin film was carried out, it was not observed that streaks, decompression drying agent pin marks, hot plate agent pin marks, haze unevenness, and bubble were all obtained. The film thickness uniformity was 2.3%. Example 1 6 In addition to changing the solvent to 51 g of ethylene glycol monomethyl ether (boiling point 124 ° C) and diethylene glycol ethyl ether (boiling point 176. (:, viscosity 1.27 mPa · s) 34 g) In the same manner as in Example 2, a photosensitive resin film was produced in the same manner. The viscosity of the varnish was -58 to 201116930 and 6.8 mPa·s. When the appearance of the obtained photosensitive resin film was evaluated, it was not observed that any of the streaks and bubbles was 3. Only the decompression drying agent pin marks and the hot plate agent pin marks were observed, and the haze unevenness was 2. The film thickness uniformity was 2.5%. Example 1 7 except that the solvent was changed to propylene glycol monomethyl ether (boiling point 120 ° C) A photosensitive resin film was produced in the same manner as in Example 2 except that 42.5 g of 42.5 g of diethylene glycol ethyl ether (boiling point: 176 t, viscosity: 1.27 mPa·s) was used, and the viscosity of the varnish was 6.6 mPa·s. When the appearance of the obtained photosensitive resin film was evaluated, it was not observed that any of the streaks and the bubbles were 3. Only the decompression drying agent pin marks, the hot plate agent pin marks, and the haze unevenness were observed to be 2. The thickness uniformity was 3.3%. Example 1 8 except that the solvent was changed to n-butanol (boiling point 117 ° C) 68 g and two A photosensitive resin film was produced in the same manner as in Example 2 except that 17 g of diol ethyl ether (boiling point: 176 ° C, viscosity: 1.27 mPa·s) was used. The viscosity of the varnish was 7.6 mPa·s. When the appearance of the film was evaluated, streaks, decompression drying agent pin marks, hot plate agent pin marks, uneven haze, and bubbles were not observed, and the film thickness uniformity was 3 · 5 %. 1 9 A photosensitive method was produced in the same manner as in Example 12 except that the solvent was changed to 51 g of butyl acetate (boiling point: 125 ° C) and 34 g of diethylene glycol ethyl ether (boiling point: 176 ° C, viscosity: 1.27 mPa·s). The varnish has a viscosity of -59 - 201116930 6 · 1 mPa · s. When the appearance of the obtained photosensitive resin film was evaluated, it was not observed that any of the streaks and bubbles was 3. The pressure drying agent pin marks, the hot plate agent pin marks, and the haze unevenness were 2. The film thickness uniformity was 2.5%. Example 20 except that the solvent was changed to isobutanol (boiling point 108 ° C) 51 g and diethyl 2 The same procedure as in Example 12 was carried out except that the alcohol ethyl ether (boiling point: 176 ° C, viscosity: 1.27 mPa · s) was 34 g. In the photosensitive resin film, the viscosity of the varnish was 6.7 mPa·s. When the appearance of the obtained photosensitive resin film was evaluated, only one of the streaks and the bubbles was observed to be 3. Only the decompression drying agent pin was observed. Hot plate agent pin marks, haze unevenness is 2. The film thickness uniformity is 2.7%. Comparative Example 1 except that the solvent was changed to propylene glycol monomethyl ether (boiling point 120 ° C) 68g and ethyl lactate (boiling point 154 °) A photosensitive resin film was produced in the same manner as in Example 1 except that the viscosity was 2.61 mPa·s). The viscosity of the varnish is 10.2 mPa · s. When the appearance of the obtained photosensitive resin film was evaluated, it was found that 3 of the streaks, the reduced-pressure drying agent pin marks, the hot plate agent pin marks, and the haze unevenness were observed. Only 2 bubbles were observed. The film thickness is 4.1%. Comparative Example 2 Using the varnish of Comparative Example 1, a photosensitive resin film was formed by slit coating so that the film thickness after drying became 5 #m. When the appearance of the obtained photosensitive resin film was evaluated, it was not observed that streaks, decompression drying agent pin marks, -60-201116930 hot plate agent pin marks, and uneven haze were three. It can be clearly observed that the bubble is 1. The film thickness uniformity was 6.4%. Comparative Example 3 Using the varnish of Comparative Example 1, a photosensitive resin film was formed by slit coating so that the film thickness after drying was 6 μm. When the appearance of the obtained photosensitive resin film was evaluated, it was found that the streak was not observed, and it was 3, and only 2 pieces of the dehydration drying agent pin mark, the hot plate agent pin mark, and the haze unevenness were observed. It can be clearly observed that the bubble is 1. The film thickness uniformity was 8.1%. Comparative Example 4 Except that the solvent was changed to 68 g of propylene glycol monomethyl ether (boiling point 12 ° C) and 17 g of N-methyl-2-pyrrolidone (boiling point: 204 ° C, viscosity: 1.65 mPa·s), In Example 2, a photosensitive resin film was produced in the same manner. The viscosity of the varnish is 9.5 mPa·s. When the appearance evaluation of the obtained photosensitive resin film was performed, the streak was not observed and it was 3, and only the decompression drying agent pin mark, the hot plate agent pin mark, the haze unevenness, and the bubble were observed. 2. The film thickness uniformity was 6.8%. Comparative Example 5 except that the solvent was changed to 59.5 g of propylene glycol monomethyl ether (boiling point 120 ° C) and r-butyrolactone (boiling point 203. (:: viscosity: 1.9 〇 mPa · s) 25.5 g, and Example 2 The photosensitive resin film was produced in the same manner. The viscosity of the varnish was 9.2 mPa·s. » When the appearance of the obtained photosensitive resin film was evaluated, no streaks were observed and it was 3, and only the decompression drying agent pin marks and heat were observed. The board agent pin marks, the haze is uneven, and the bubble is 2. The film thickness uniformity is 5.1%. -61 - 201116930 Comparative Example 6 except that the solvent is changed to propylene glycol monomethyl ether (boiling point 120 ° C) 51 g and r-butyl A photosensitive resin film was produced in the same manner as in Example 2 except that the lactone (boiling point: 203 ° C, viscosity: 1.90 mPa·s) was used, and the viscosity of the varnish was 9.4 raPa·s». The appearance of the obtained photosensitive resin film was carried out. In the evaluation, no streaks were observed and it was 3, and only the decompression drying agent pin marks, the hot plate agent pin marks, the haze unevenness, and the bubble were observed to be 2. The film thickness uniformity was 5.3%. Example 7 In addition to changing the solvent to propylene glycol monomethyl ether (boiling point 120 ° C) 76.5g and r · butyrolactone (boiling point 2031, sticky A photosensitive resin film was produced in the same manner as in Example 2 except that 1.90 mPa·s) was 8.5 g. The viscosity of the varnish was 8.3 mPa·s. When the appearance of the obtained photosensitive resin film was evaluated, streaks could not be observed. The decompression drying agent pin mark 'hot plate agent pin mark is 3, only the uneven haze is observed, 2, the bubble can be clearly observed to be 1. The film thickness uniformity is 6.6%. Comparative Example 8 Photosensitive was prepared in the same manner as in Example 2 except that the solvent was changed to 25.5 g of propylene glycol monomethyl ether (boiling point: 120 ° C) and 59.5 g of diethylene glycol ethyl ether (boiling point: 176 ° C, viscosity: 1.27 mPa·s). Resin film. The viscosity of the varnish was 6.7 mPa·s. When the appearance of the obtained photosensitive resin film was evaluated, streaks could not be observed, and only the decompression drying agent pin marks, hot plate agent marks, and haze were observed. Non-uniformity or bubble type was 2. The film thickness uniformity was 4.0%. Comparative Example 9 -62- 201116930 except that the solvent was changed to propylene glycol monomethyl ether (boiling point 12 〇t > c) 25.5 g and monoethylene glycol. Diacetic acid (. 189 ° C, viscosity 丨 471 111 gt; 3 · s) 59.5 g, and other examples and A photosensitive resin film was produced in the sample. The viscosity of the varnish was 8.1 mPa·s. In the evaluation of the appearance of the obtained photosensitive resin film, only streaks, decompression drying agent pin marks, hot plate agent pin marks, and fog were observed. The degree of unevenness of the film was 2. The film thickness uniformity was 4.3%. Comparative Example 1 0 The solvent was changed to propylene glycol monomethyl ether (boiling point 120 ° C) 68 g and butyrolactone (boiling point 203 ° C, A photosensitive resin film was produced in the same manner as in Example 11 except that the viscosity was 1.90 mPa·s). The viscosity of the varnish is 8.1 mPa·s. When the appearance of the obtained photosensitive resin film was evaluated, streaks could not be observed, and only the decompression drying agent pin marks, the hot plate agent pin marks, and the haze unevenness were observed, and it was 2, and it was clearly observed. Bubble is 1. The film thickness uniformity was 5.5%. Comparative Example 1 1 -·· In addition to changing the solvent to propylene glycol monomethyl ether acetate (boiling point 146 ° C, 1.18 mPa·s) 59_5 g and ethylene glycol n-butyl ether acetate (boiling point 188 ° C, 1.70 mPa · s Other than 25_5g, a varnish of a positive photosensitive polyimide precursor composition was produced in the same manner as in Example i. The undissolved resin component remained in the varnish, and the coating property evaluation could not be performed. Comparative Example 1 2 Except that it was changed to butyl acetate (boiling point 125) 51 〇g and acetonitrile acetone (boiling point 141 ° C, viscosity 0.75 mPa·s) 34 〇g, otherwise with Example 1-63-201116930 Similarly, a varnish of a positive photosensitive polyimide precursor composition was produced. The coating property was not evaluated because the resin residue remaining in the varnish remained undissolved. Comparative Example 1 3 Photosensitive was produced in the same manner as in Example 12 except that the solvent was changed to 51.0 g of butyl acetate (boiling point: 125 Å) and 34.0 g of ethyl acetonylacetone (boiling point: 141 ° C, viscosity: 0.75 mPa·s). Resin film. The viscosity of the varnish is 5.2 m Pa · s. When the appearance evaluation of the obtained photosensitive resin film was performed, it was not observed that the pressure-reducing drying agent pin marks and the hot plate agent pin marks were 3, and only streaks and haze were observed, and it was 2, and it was clearly observed. Bubble is 1. The film thickness uniformity was 4.8%. The compositions of Examples 1 to 20 and Comparative Examples 1 to 3 are shown in Tables 1 to 3, and the evaluation results are shown in Table 4. -64- 201116930 £ Coating film thickness 4/zm B v〇6βτη B v〇B ur» BBB wo Other ingredients TrisP-PHBA BYK333 TrisP-PHBA BYK333 TrisP-PHBA BYK333 TrisP-PHBA BYK333 TrisP-PHBA BYK333 TrisP-PHBA Synthesis example 3 BYK333 TrisP-PHBA BYK333 TrisP-PHBA BYK333 Other solvents_ <rn 1 1 1 1 1 7-butyrolactone_ tlmi] Ρί| Ο 1 1 Boiling point·viscosity 203〇C/1.90mPa s ι~Ι — OO 13⁄43⁄4义h_<ni Diethylene glycol ethyl ether 20% by weight Diethylene glycol Ethyl ether 20% by weight Diethylene glycol Ethyl ether _ Fine diethylene glycol dimethyl ether 20% by weight m fi ll a 11 bO 11 tons w diethylene glycol ethyl ether 20 liters % diethylene glycol dimethyl ether 40 weight % diethylene glycol dimethyl ether 40% by weight boiling point / viscosity 176 〇 C / 1.27 mPa * s 176 〇 C / 1.27 mPa * s 1 176〇C/1.27 mPa s 162°C/1.17 mPa - s ! 189^/1.47 mPa s 176〇C/1.27 mPa · s 176〇C/1.27 mPa · s 162°C/1.17 mPa * s (C) Organic solvent with a boiling point of 100 ° C or more and 130 ° C or less _ {m propylene glycol monomethyl ether _ _ propylene glycol monomethyl ether ώ ΐΐ ΐΐ 〇 PH d \ propylene glycol monomethyl ether _ fine 1 g g propylene glycol monomethyl Ether _ g Propylene glycol monomethyl ether _ \fmi] \〇Pt| d\ g propylene glycol monomethyl ether _ tlrnll \〇Ptl ό\ o propylene glycol monomethyl ether ¢ 1 <1mti \〇Pl| 0\ s propylene glycol monomethyl ether _ tjmji \ 〇sm 120°C 120°C 120°C 120°C 120°C 120. . 120. . 120 ° C (b) sensitizer synthesis example 2 Synthesis Example 2 Synthesis Example 2 合成 Synthesis Example 2 Synthesis Example 2 Synthesis Example 2 Synthesis Example 2 Synthesis Example 2 (8) Resin Polyimine Precursor Polyimine Precursor Poly Amine precursor I Polyimine precursor Polyimine precursor Polyimine precursor Polyimine precursor Polyimine precursor Ιί IS U ^ li «1 «Ϊ Ιϊ 201116930 ε =1 B ε Sv〇TrisP-PHBA ΒΥΚ333 TrisP-PHBA BYK333 TrisP-PHBA BYK333 TrisP-PHBA BYK333 r-butyrolactone 203〇C/1.90mPa · s 20 窜 %% 1 1 1 Diethylene glycol ethoxylate ιΗ _ 二二Alcohol Ethyl Ether 10 Thunder Amount Diethylene Glycol Ethyl Ethyl Ether Ethyl Ether Ethylene Glycol Ethyl Ether Ethylene Glycol Ethyl Ether _ w 〇 176 〇 C / 1.27 mPa s 176 ° C / 1.27 mPa · s 176 〇 C / 1.27 . mPa si 176〇C/1.27 mPa * s propylene glycol monomethyl ether _ tlmi) \〇Ptl d\ s propylene glycol monomethyl ether _ ilrnll \〇md\ propylene glycol monomethyl ether «Μ ijmil \〇啊&\ S propylene glycol monomethyl Ether Μ _ S 120 ° C 120 ° C 120 ° C 120. . Synthesis Example 2 Synthesis Example 2 Synthesis Example 2 Synthesis Example 2 Polyimine precursor Precursor Polyimine precursor Polybenzoxazole precursor 丨 Polyimine precursors Conventions Example 10 _(莩辑^舾冕,99- 201116930 【tcn¥ Coating film thickness ε ν〇B wn B iTi ε ν〇B v〇Other composition synthesis example 3 ΒΥΚ333 ;_ θ 2 ^ Ώ TrisP-PHBA BYK333 TrisP-PHBA BYK333 TrisP-PHBA BYK333 Others Solvent 1 content 1 1 1 1 1 蘅23⁄4 丄G 〇〇m . n1> Boat cd 13⁄4 r-Η Boiling point/viscosity content diethylene glycol ethyl ether l{Sj fine diethylene glycol ethyl ether _ ilmt] 阙二乙Glycol Ethyl Ether _ W Diethylene Glycol Ethyl Ether 40% by Weight Diethylene Glycol Ethyl Ether 50% by Weight 176〇C/1.27 mPa S 176〇C/1.27 mPa · s ;176^/1.27 ! mPa s 176〇C/1.27 mPa · s 176〇C /1.27mPa · s η occlusion 3.- gg move I 2N pulse t _ {m propylene glycol monomethyl ether 80 milano% propylene glycol monomethyl ether 80% by weight propylene glycol monomethyl ether 80% by weight Propylene glycol monomethyl ether 60% by weight Propylene glycol monomethyl ether 50% by weight έδ am; Cone 120°C 120°C 124. 124. 120°C (6) Sensitizer Ii; ii] g; iife piano slightly; "1 title 旰? 2_§遁氍wK : 擀 & WPAG-314 Synthesis Example 2 Synthesis Example 2 Synthesis Example 2 (a) Resin Polyimine precursor Polybenzopyrene Azole precursor Polyimine precursor 1 Polyimine precursor Polyimine precursor 蜀 2 us Example 14 Reveal IK cough Example 17 — L9 — 201116930 B =1 ε 5_ TrisP-PHBA BYK333 TrisP- PHBA BYK333 TrisP-PHBA BYK333 1 1 1 Diethylene glycol Ethyl ether _ Resin diethylene glycol Ethylene ether Diethylene glycol Ethyl ether 40 Military dizzy% 176〇C/1.27 mPa · s 176〇C/1.27 mPa · s 1 176. /1.27mPa s n-butanol n|e) W g butyl acetate _ isobutanol 60% by weight 117. 125. 1 108 ° C 1 1 j Synthesis Example 2 Synthesis Example 2 Synthesis Example 2 Polyimine precursor 1 Polyimine precursor Polyimine precursor Example 18 Example 19 1 Example 20 -009- 201116930 Coating film thickness 4 "m ε ε VO ε B Other components TrisP- PHBA BYK333 TrisP-PHBA BYK333 1 _1 TrisP-PHBA BYK333 TrisP-PHBA BYK333 TrisP-PHBA BYK333 Other solvent content ethyl lactate 20% by weight m. κι m 20% by weight Ethyl lactate 20% by weight N-methyl-2-pyrrolidone _ 7-butyrolactone 30% by weight Boiling point · Viscosity 154 〇 C / 2.61 mPa · s 154 〇 C / 2.61 mPa · s 1 154〇C/2.61mPa · si 204〇C/1.65mPa · s 203°C/1.90mPa · si 7 class 3 rf P r? God 1 r—* r—ic, 〇g鲥-boiling point content 1 1 1 1 g ΙΦ: 2 ^ Ip s- Boiling point content propylene glycol monomethyl ether 80 milver% propylene glycol monomethyl ether 80% by weight propylene glycol monomethyl ether 80% by weight propylene glycol monomethyl ether 80% by weight propylene glycol monomethyl ether 70% by weight 120. . 120 ° C 120. . 120 ° C 120. . (b) Sensitizer Synthesis Example 2 Synthesis Example 2 Synthesis Example 2 Synthesis Example 2 1 Synthesis Example 2 (8) Resin Polyimine Precursor Polyimine Precursor Polyimide Precursor Polyimine Precursor Poly Amine precursor Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 -69- 201116930 Β BA ε =1 TrisP-PHBA ΒΥΚ333 TrisP-PHBA BYK333 TrisP-PHBA BYK333 7-butyrolactone _ 〇r-丁内Ester 10 Thunder% 1 203〇C/1.90mPa · s 203〇C/1.90mPa · s Diethylene glycol dimethyl ether 70% by weight 176〇C/1.27 mPa · s Propylene glycol monomethyl ether _ Heteropropylene glycol monomethyl ether ilD propylene glycol monomethyl ether _ 120 ° C 120 ° C 120. . Synthesis Example 2 Synthesis Example 2 1 1 ______ 1 Synthesis Example 2 Polyimine precursor Precursor Polyimine precursor Polyimine precursor Comparative Example 6 Comparative Example 7 _ 1 Comparative Example 8 ο 201116930 [ε嗽] Coating film Thick BB =1 1 1 ε Other components TrisP-PHBA ΒΥΚ333 _1 TrisP-PHBA BYK333 TrisP-PHBA BYK333 TrisP-PHBA BYK333 TrisP-PHBA BYK333 Other solvents _ <tQ 1 T -butyrolactone 20 窜%% Kl K) mm ^ h 酹w 氍 M Mil ΕΚ] 70% by weight 30% by weight Ethyl acetonide _ W 〇 Ethyl acetonide _ W 〇m 203°C / 1.90mPa · s 146〇C/1.18mPa · s 188〇C/ 1.70 mPa · s 141 〇 C / 0.75 mPa · s 141 〇 C / 0.75 mPa · s ^ IU 〇 GC / 3 | § 1 t 3 iW <ra Diethylene glycol dimethyl ether 70 military faint % 1 Boiling point / Viscosity 189〇C/1.47 mPa S ' ο Ξ$ —Q Li 33⁄4 ®w <ια Propylene glycol monomethyl ether 30% by weight Propylene glycol monomethyl ether 80% by weight 1 Propyl acetate 60% by weight Propyl acetate. ·. 60 weight % EETTU 揉120. . Just, 125. . 125. . (b) Sensitizer Synthesis Example 2 Synthesis Example 2 Synthesis Example 2 Synthesis Example 2 Synthesis Example 2 (a) Resin Polyimine Precursor Polybenzoxazole Precursor Polyimine Precursor Polyimine Precursor Poly Yttrium imine precursor Comparative Example 10 2 Comparative Example 12 Comparative Example 13 _ u- 201116930 [Table 4] Varnish viscosity (mPa · s) Streak VCD pin mark HP pin mark haze unevenness film thickness uniformity (% Example 1 13 3 3 3 3 3 1.9 Example 2 7.3 3 3 3 3 3 2.5 Example 3 7.3 3 3 3 3 2 2.9 Example 4 7.1 3 3 3 3 2 2.4 Example 5 7.6 3 3 3 3 3 2.9 Example 6 7.4 3 3 3 3 3 2.8 Example 7 6.8 3 2 2 2 3 3.5 Example 8 6.5 3 3 3 3 2 3.4 Example 9 7.3 3 3 3 3 3 2.9 Example 10 7.9 3 3 3 3 2 2.9 EXAMPLES 7.1 3 2 2 2 3 3.5 Example 12 6.5 3 2 2 2 3 3.3 Example 13 7.9 3 3 3 3 3 2.8 Example 14 7.6 3 3 3 3 3 2.8 Example 15 7.0 3 3 3 3 3 2.3 Example 16 6.8 3 2 2 2 3 2.5 Example 6.6 6.6 3 2 2 2 3 3.3 Example 18 7.6 3 3 3 3 3 3.5 Example 19 6.1 3 2 2 2 3 2.5 Example 20 6.7 3 2 2 2 3 2.7 Comparative Example 1 10.2 3 3 3 3 2 4.1 Ratio Comparative Example 2 10.2 3 3 3 3 1 6.4 Comparative Example 3 10.2 3 2 2 2 1 8.1 Comparative Example 4 9.5 3 2 2 2 2 6.8 Comparative Example 5 9.2 3 2 2 2 2 5.1 Comparative Example 9.4 9.4 3 2 2 2 2 5.3 Comparative Example 7 8.3 3 3 3 2 1 6.6 Comparative Example 8 6.7 2 2 2 2 2 4.0 Comparative Example 9 8.1 2 2 2 2 2 4.3 Comparative Example 1 〇 8.1 3 2 2 2 1 5.5 Comparative Example 11 Insoluble — — — — - Comparative Example 12 Insoluble - - - - - - Comparative Example 13 5.2 2 3 3 2 1 4.8 -72- 201116930 INDUSTRIAL APPLICABILITY The photosensitive resin composition of the present invention can be used for a surface protective film for a semiconductor element Or an interlayer insulating film, an insulating film of an organic electroluminescence (hereinafter referred to as EL) element, or a flat film of a driving thin film transistor (hereinafter referred to as TFT) in a display device using an organic EL element A film-protecting insulating film for a film or a circuit board, a microlens on a wafer of a solid-state imaging device, or a display for a flattening film for a solid-state imaging device. [Simple description of the diagram] ίκ. [Main component symbol description] None. -73-

Claims (1)

201116930 VII. Patent application scope: 1. A photosensitive resin composition characterized by: (a) selected from the group consisting of polyimine, polybenzoxazole, polyimine precursor, and polybenzoxazole At least one or more resins of the precursor; (b) a sensitizer; (c) an organic solvent having a boiling point of 100 ° C or more and 130 ° C or less at atmospheric pressure; and (d) a boiling point of 150 ° C or more at atmospheric pressure, The organic solvent having a viscosity at 20 ° C of more than 1. ImPa · s and less than 1 '5 mPa·s, and the content of the component (c) is 40% by weight or more and 90% by weight or less relative to the organic solvent. The total amount of the component (d) is 10% by weight or more and 60% by weight or less. The photosensitive resin composition of the first aspect of the invention, wherein the component (d) is selected from the group consisting of diethylene glycol At least one or more of ether, diethylene glycol ethyl ether, and diethylene glycol diethyl ether. 3. The photosensitive resin composition of claim 1, wherein the content of the component (d) is 10% by weight or more and 20% by weight or less based on the total amount of the organic solvent. A method for producing a photosensitive resin film, comprising: (1) applying a photosensitive resin composition according to any one of claims 1 to 3 on a substrate using a slit nozzle, and forming a coating film And; (2) a step of drying the coated film under reduced pressure. 5. A photosensitive resin film obtained by the method of manufacturing method of the fourth aspect of the invention, which has a film thickness of 5/m or more and a thickness of 1 Å or less, is not specified. - 74 - 201116930 Figure: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: te. j\w V. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: