TW200903163A - Positive photosensitive resin composition - Google Patents

Abstract

The purpose of the present invention is to provide a positive photosensitive resin composition which may form a pattern excellent in chemical resistance after a heat treatment and having a low taper angle. The positive photosensitive resin composition comprises (a) a polyamic acid and/or a polyamic acid ester having a structural unit represented by general formula (1), (b) a quinodiazide compound, and (c) a polyfunctional acrylate-based compound. wherein R1 represents an organic group having 2 or more carbon atoms and the valance of 3 to 8, R2 represents an organic group having 2 or more carbon atoms and the valance of 2 to 8, R3 and R4 may be the same or different and represent a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, p and q represent an integer of 0 to 4, r represents 1 or 2, and s represents a integer of 0 to 2, but p+q > 0.

Description

200903163 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a positive photosensitive resin composition. More specifically, 'the insulating layer or the spacer layer applicable to the surface protective film of the semiconductor element, the interlayer insulating film, the organic electroluminescent element (organic EL element), the planarization layer of the thin film transistor substrate (TFT substrate), The exposed portion of the insulating layer or the like of the organic transistor is dissolved in the positive photosensitive resin composition of the aqueous alkali solution. [Prior Art] Conventionally, as a positive photosensitive resin composition, a photosensitive polyamido containing a polyamidamine precursor, that is, a polyamidomate and/or a polylysine and a quinonediazide compound is known. An amine precursor composition, or a photosensitive polybenzoxazole precursor composition containing a polybenzoxazole precursor and a quinonediazide compound. After the photosensitive resin composition is patterned, the film obtained by heat treatment is applied to an insulating layer of an organic EL element or a planarization layer of a TFT substrate. In particular, in the low molecular light-emitting organic EL device, the pattern shape of the low taper angle is suitable as the insulating layer pattern from the viewpoint of preventing disconnection of the upper electrode. Further, even in the planarization layer of the TFT substrate, the pattern shape of the low taper angle is suitable from the viewpoint of preventing disconnection of the electrodes of the display element. Therefore, it is preferable to use such a positive photosensitive resin composition as compared with a negative type in which the pattern is easily rectangular. In the production of an organic EL device, in recent years, as the size of the substrate is increased, the substrate may be divided by the size of the vapor deposition machine before vapor deposition of the light-emitting layer. In this case, since the photoresist is applied after the formation of the insulating layer, and the photoresist is peeled off after the dicing, the chemical resistance of the insulating layer to the peeling liquid is required. Further, 200903163 Even in the planarization layer of the TFT substrate, the electrode of the display element is patterned, and etching is performed using the photoresist as a mask. In this case, since the photoresist is peeled off after the etching, the flattening layer of the TFT substrate is required to have chemical resistance to the peeling liquid. As a method for improving the chemical resistance of a positive photosensitive resin composition, there is a thermal crosslinkable compound containing a methylol group substituted with an organic group in a positive photosensitive polyimide precursor composition. (for example, refer to Patent Document 1) or a method of containing an epoxy compound (for example, refer to Patent Document 2). These compositions can improve the chemical resistance of the thermosetting film by the reaction of a thermally crosslinkable compound or an epoxy compound. However, there is a problem that the pattern shape of the low taper angle required for the insulating layer of the organic EL element or the planarization layer of the TFT substrate is not obtained. Further, it has been proposed to contain a polyimide, a diazonaphthoquinone-based sensitizer, and an epoxy compound or a monofunctional acrylate such as a cross-linking reaction or an autothermal polymerization reaction with a polyimine precursor. A positive photosensitive resin composition (see, for example, Patent Document 3). In this technique, there is also a problem that the pattern shape of the low taper angle required for the insulating layer of the organic EL element or the planarization layer of the TFT substrate is not obtained. Further, if the content of the monofunctional acrylate is increased, there is a problem in that the acrylate polymer is liable to undergo phase separation during heat treatment. In addition, a positive photosensitive resin composition containing a hydroxypolyamine, an acrylate-based compound, and a photosensitive diazonium compound is proposed (see, for example, Patent Documents 4 and 5). These compositions are incapable of obtaining a pattern shape of a low taper angle required for an insulating layer of an organic EL element or a planarization layer of a TFT substrate, and further, since high temperature treatment of 280 ° C or higher is required, it is difficult to use The insulating layer of the organic EL element or the planarization of the TFT substrate is 200003163. [Patent Document 1] U.S. Patent No. 693 3 0 8 (Patent Document 2) JP-A-2000-3 97 1 4 (Application No. j to 4) [Patent Document 3] Special Opening 200 0 - [Patent Document No. 2] [Patent Document 4] Japanese Laid-Open Patent Publication No. Hei 2-6-473.77 (Patent Application No. 1) r ' [Patent Document 5] Special Opening 2007 - 1 93 3 22 (Patent No. 1 of the Patent Application) [Disclosure] The problem to be solved is in view of the above problems, and an object of the present invention is to provide a positive photosensitive resin composition which can be shaped after heat treatment Excellent chemical resistance and low cone angle pattern

The present invention relates to a positive photosensitive resin composition comprising (a) a polylysine having a structural unit represented by the formula (1) and/or a polyamidomate, and (b) a quinonediazide compound, ( c) a polyfunctional acrylate compound; (〇H)p (〇H)q 1 (1)

CO-R1—CONH-R2—NH—(COOR\ (COOR4)s J (In the general formula (1), R1 represents a 3-8 valent organic group having a carbon number of 2 or more, and R2 represents a high carbon number of 2 or more. ～8-valent organic group. R3 and R4 may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. p and q represent an integer of 0 to 4, r represents 1 or 2, and s represents an integer of 0 to 2. However, according to the present invention, a positive photosensitive resin composition capable of forming a pattern excellent in chemical resistance after heat treatment and having a low taper angle can be obtained by using the present invention. In the positive photosensitive resin composition, a low-cone-point heat-resistant resin pattern having excellent chemical resistance can be obtained. [Embodiment] The positive-type photosensitive resin composition of the present invention contains (a) has a pass. Poly-proline and/or polyphthalate of the structural unit shown in formula (1). (1) (〇H)p (〇H)q ] -CO-R1—CONH-R2—NH—(iooR3^ (COOR4)s In the formula (1), R1 represents a 3 to 8-valent organic group having 2 or more carbon atoms, and R2 represents a 2 to 8-valent organic group having 2 or more carbon atoms. R3 and R4 may be the same or different. Hydrogen atom or carbon a hydrocarbon group of 1 to 20, P and q represent an integer of 〇~4, r represents 1 or 2, and s represents an integer of 0 to 2. However, p+q> 〇 The above formula (1) represents a group having a hydroxyl group a structural unit of proline or polylysine. Since it has a hydroxyl group, it can improve the solubility in an aqueous alkali solution. Among the hydroxyl groups, a phenolic hydroxyl group is preferred. Also, due to polyamic acid or polylysine Even if the ester is subjected to a dehydration ring-closure reaction of 90% or more of 200,903,163 by a heat treatment of 2500 T: or less to form a polyimide resin, it has an advantage of being able to be cured at a low temperature. The polyhydroxy decylamine having a hydroxyl group is a polybenzoxazole resin in order to carry out a dehydration ring-closure reaction of 90% or more in the same manner, and a heat treatment of 280 ° C or higher is required. Therefore, a low temperature of 250 ° C or lower is required. In the structural unit represented by the general formula (1), it is preferable to have a fluorine atom of 1% by weight or more. The fluorine atom having 10% by weight or more can be used in the hardening system. The interface of the membrane imparts moderate water repellency and is imaged with an aqueous alkali solution. In addition, the fluorine atom content is preferably 20% by weight or less in the structural unit represented by the formula (1). By setting the fluorine atom content to 20% by weight or less, the high alkali aqueous solution can be maintained. The solubility can further improve the chemical resistance of the polyimine obtained after the heat treatment, especially the resistance to the organic solvent. Further, the solubility of the polyimine obtained after the heat treatment for the fuming nitric acid can be maintained. R1 in the formula (1) shows that the structural component ' of the acid' represents a 3- to 8-valent organic group having 2 or more carbon atoms. R1 is preferably a trivalent or tetravalent organic group having 6 to 30 carbon atoms which contains an aromatic ring or an aliphatic ring, and more preferably a tetravalent organic group. Further, two or more kinds of R1 may be combined. As an example of the acid constituting R^OHMCOOR3; ^, when p = 0, pyromellitic dianhydride, 3, 3, 4, 4, -biphenyltetracarboxylic dianhydride, 2, 3 may be mentioned. ,3,,4'-biphenyltetracarboxylic dianhydride, 2,2,3,3'-biphenyltetracarboxylic dianhydride, 3,3,' 4,4,-benzophenone IV Carboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)malonate, 2,2·bis ( 2,3·dimercaptophenyl)malonic anhydride, 1,1-bis(3,4-difluorenyl)acetic anhydride, 1,1-bis10-200903163 (2,3-didecylphenyl) Ethylene dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-di residue phenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfonate , bis(3,4-dicarboxyphenyl)ether dianhydride, 2,2-bis(4-(4-aminophenoxy)phenyl)propyl, 1,2,5,6-naphthalenetetracarboxylic acid Desic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9, 〇·茈tetracarboxylic dianhydride, 2 , 2-bis(3,4-di residuephenyl)hexafluoropropanehydride, 2,2-bis(4-(3,4-diphenylphenoxy)phenyl)hexafluoropropanehydride' 2 , 2_bis(4_(3,4_dicarboxybenzyl oxime) Phenyl)hexafluoropropanehydride, 2,2,-bis(tetrafluoromethyl)-4,4,-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, "Rikacid" Registered trademark), an aromatic tetracarboxylic dianhydride such as TMEG-i00 (trade name, manufactured by Nippon Chemical and Chemical Co., Ltd.), or cyclobutylene tetracarboxylic dianhydride, 1,2,3,4-cyclopentane Alkanetetracarboxylic dianhydride, 2,3,5,6-cyclohexanetetracarboxylic dianhydride, "E pic 1 ο η (registered trademark)" B - 4 4 0 0 (trade name, Dainippon Ink Chemical Industry (share) system and "Rikacid" TDA-100, ΒΤ-1〇〇 (above, trade name, New Japan Physicochemical Co., Ltd.), etc., such as aliphatic tetracarboxylic dianhydride. Good is 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'- Biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2 ,2-bis(3,4-dicarboxyphenyl)propanehydride, 2,2-bis(2,3-dicarboxyphenyl)malonate, 1,1-bis(3,4-dicarboxybenzene Ethylene dianhydride, 1,1-bis(2,3-dicarboxyphenyl) ethylene , bis(3,4-dicarboxyphenyl)methane dianhydride bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl) sulphthalic anhydride, bis (3, 4-dicarboxyphenyl)ether dianhydride, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 2,2-bis(3,4-dicarboxyphenyl)hexafluoro Malon anhydride, 2,2-bis(4-(3,4-dicarboxybenzyloxy)phenyl)hexafluoropropanehydride, 2,2'-bis(tetrafluoromethyl)-~11- 200903163 4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride These may be used alone or in combination of two or more. In the case of pgl, R^OHLCCOOR3) is exemplified by the structure shown below, but is not limited thereto. Further, in the following formula, R3 may be the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ( -12- 200903163 r3ooc

COOR3 r3o〇c

/OH, J ~N h3c ch3 H H

COOR

R3ooc r3ooc r3ooc

COOR3 COOR CO〇Rw 3

-13- 200903163 R2 in the above formula (1) shows that the structural component ' of the diamine' represents a 2 to 8-valent organic group having 2 or more carbon atoms. R2 is preferably a divalent to tetravalent organic group having 6 to 30 carbon atoms and containing an aromatic ring or an aliphatic ring. It is more preferable to have an aromatic ring from the viewpoint of heat resistance of the obtained polymer. Further, two or more kinds of R2 may be combined in combination. Examples of the diamine constituting R2(〇H)q(COOR4)s, when q = 〇, 3,4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl Base, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4,-diaminodiphenylanthracene, 4,4'-diamino Diphenylanthracene, 3,4'-diaminodiphenyl sulfide '4,4'-diaminodiphenyl sulfide, iota, 4-bis(4-aminophenoxy)benzene, benzene Alkyne, meta-phenylenediamine, p-phenylenediamine, 3,5-diaminobenzoic acid, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxybenzene) , bis(3-aminophenoxyphenyl)anthracene, bis(4-aminophenoxy)biphenyl, bis{4_(4 -1 female basic oxy)phenyl}ether, 1 , 4-bis(4-aminophenoxy)benzene, 2,2,·dimethyl-4,4'-diaminobiphenyl, 2,2,_diethyl_4,4,- Diaminobiphenyl, 3,3'-dimethyl-4,4,diaminobiphenyl, 3,3,-diethyl-4,4,-diaminobiphenyl, 2 ,2,,3,3,-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4,-diaminobiphenyl , 2, 2, - two ( Fluoromethyl)-4,4'-monoaminobiphenyl, or a compound in which a hydrogen atom of such an aromatic ring is substituted with an alkyl group or a halogen atom, or an aliphatic cyclohexyldiamine or methylene bicyclol Hexylamine and the like are not limited by these. When qg 1 ', 2,2_bis(4_amino-3-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2_bis[4_(4-amino-3-hydroxyphenoxy)phenyl]hexafluoropropane, diaminodihydroxypyrimidine, di-14- 200903163-based dihydroxypyridine, hydroxy-diamino- Pyrimidine, diaminophenol, dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)cyclohexane, 2,2-bis(3-amino-4-hydroxyphenyl) A compound such as hydrazine. Further, examples of R2(〇H)q(COOR4)s include the structures shown below, but are not limited thereto. f

-15- 200903163

-16- 200903163 R3 and R4 of the formula (I) represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. From the viewpoint of the stability of the obtained positive photosensitive resin composition, R3 and R4 are preferably a hydrocarbon group. On the other hand, from the viewpoint of solubility in an aqueous alkali solution, a hydrogen atom is preferred. In the present invention, a hydrogen atom may be mixed with a hydrocarbon group. By adjusting the amounts of the hydrogen atoms and the hydrocarbon groups of R3 and R4, the dissolution rate with respect to the aqueous alkali solution can be changed, so that a positive photosensitive resin composition having a moderate dissolution rate can be obtained by this adjustment. A preferred range is from 10 mol% to 90 mol% of hydrogen atoms of R3 and R4. When the carbon number of R3 and R4 exceeds 20, the alkali solubility is lowered. It is preferable that the above-mentioned 'R3 and R4 contain one or more hydrocarbon groups having 1 to 16 carbon atoms', and the others are hydrogen atoms. Further, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure of the formula (1) or r2 may be copolymerized in a range not to lower the heat resistance. The content thereof is preferably from 1 to 10 mol% in R1 or in R2. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldioxane and bis(p-aminophenyl)octamethylpentoxide. (a) The weight average molecular weight of the polyamic acid or polyglycolic acid hydrate having the structural unit represented by the general formula (1), preferably 2, more than 〇〇〇, more preferably 3,000 or more, particularly preferably 5,000 or more It is preferably 100,000 or less, more preferably 5,000 or less, and particularly preferably 30,0 or less. When the weight average molecular weight is 2,0 0 or more, the resolution and developability are improved, and the chemical resistance is further improved. Further, when it is at most 100 Å or less, the development and sensitivity are improved, and a pattern having a lower conical shape can be obtained. Further, the weight average molecular weight in the present invention means the amount of the molecule -17-200903163 obtained by conversion of polystyrene using gel permeation chromatography. In the present invention, the poly-proline or polylysine of the component (a) may be composed only of the structural unit represented by the general formula (1), or may be a structural unit represented by the general formula (1) and other structures. Unit of copolymer. In the present invention, the structural unit represented by the formula (1) is preferably contained in an amount of 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 90 mol% or more. The type and amount ' of the structural unit used in the copolymerization is preferably selected within the range in which the heat treatment does not impair the heat resistance of the obtained polyimine. Examples of the other structural unit include a phenol-novolac varnish, a cresol novolac, and a structural unit of a radically polymerizable polymer having an alkali-soluble group. Further, in the present invention, in addition to the polyamic acid or polysodium amide of the component (a), the phenol-novolac and cresol may be contained in the range in which the heat treatment does not impair the heat resistance of the obtained cured film. a resin such as a novolak, a polyhydroxystyrene, or a radically polymerizable polymer having an alkali-soluble group. When the resin is contained, the content thereof is preferably 1 part by weight or less for the total amount of the poly (a) component of the (a) component of the (a) component, and more preferably 30 parts by weight or less, particularly preferably 10 parts by weight. Further, (a) a polylysine or a polyphthalate having a structural unit represented by the formula (1) may be a reaction between a terminal and a blocking agent. As the blocking agent, a monoamine, an acid anhydride, a monocarboxylic acid, a chlorinated monoacid compound, a mono-active ester compound or the like can be used. The molecular weight can be easily adjusted within a preferred range by reaction with a blocking agent. Further, by reacting with a blocking agent, various organic groups as terminal groups can be introduced. Preferable examples of the monoamine used as the blocking agent include 5-amino--18-200903163 8 -hydroxyindole, hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, and 1 -hydroxy-5-aminonaphthalene, hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6 an aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1- Carboxyl-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxyl 5-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylide Acid, 2-aminobenzene acid extension, 3-aminobenzene acid extension, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol , 4-aminophenol, 2-aminothiophene, 3-aminothiophene, 4-aminothiophene, 3-ethynylaniline '4-ethynylaniline, 3,4-diethynylaniline, 3,5- Preferable examples of the acid anhydride used as the blocking agent such as diethynyl aniline include phthalic anhydride, maleic anhydride 'nad丨c anhydride, cyclohexane dicarboxylic anhydride, and 3-hydroxy phthalic anhydride. Wait. Preferred examples of monodecanoic acid include 3-resin oxime, 4-carboxy phenol, 3-mercaptothiophene, 4-mercaptothiophene hydroxy-7-carboxynaphthalene, and ketone-6-carboxynaphthalene. , 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-sulfo-6-carboxynaphthalene, thio--5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzene Sulfonic acid, 3-ethynyl 4-benzoic acid 'ethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynylbenzoic acid, and the like. Preferred examples of the chlorinated monoacid compound include a compound in which the carboxyl group of the above-described monoterpene acid is halogenated, or a combination of citric acid, citric acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-di. A compound in which one carboxyl group of a dicarboxylic acid such as carboxynaphthalene, 1,6-dicarboxynaphthalene' anthracene, 7-dicarboxynaphthalene or 2,6-dicarboxynaphthalene is halogenated or the like. Preferred examples of the mono-active ester compound are exemplified by the aforementioned chlorinated monoacid compound and N-hydroxy-19-200903163-based benzotriazole or N-hydroxy-5-formylene-2,3-di. A compound obtained by the reaction of a carboxy quinone imine. The introduction ratio of the monoamine used as the terminal blocking agent is preferably in the range of 0.1 to 60 mol% for the entire amine component of the polyamic acid or the polyamidomate of the component (a). More preferably 5 to 50 mol%. The ratio of introduction of the acid anhydride, the monocarboxylic acid, the chlorinated monoacid compound, and the mono-active ester compound used as the blocking agent to all the diamine components in the polyamine or polyglycolate of the component (a) Preferably, it is in the range of 0.1 to 100 mol%, more preferably 5 to 90 mol%. A plurality of different terminal groups can also be introduced by reaction with a plurality of blocking agents. The blocking agent introduced in polylysine or polyamidolate can be easily detected by the following method. For example, the polymer into which the terminal blocking agent is introduced is dissolved in an acidic solution, and is decomposed into a constituent unit of the polymer, that is, an amine component and an acid anhydride component, which are easily detected by gas chromatography (GC) or NMR. Sealing agent. Further, the polymer into which the terminal blocking agent is introduced can be easily detected directly by thermal decomposition gas chromatography (PGC), infrared spectroscopy, and 13 C-NMR spectrometry. The polyamino acid or polyglycolate having the structural unit represented by the formula (1) used in the present invention can be synthesized by the following method. For example, 'the method of reacting tetrakisonic acid dioxins with a diamine compound at a low temperature to obtain a diester from a tetracarboxylic acid and an alcohol to react a diester in the presence of a condensing agent with a diamine compound The method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol and then subjecting the residual dicarboxylic acid to hydrazine chlorination to react with a diamine compound. The reaction solvent used in such well-known methods can be exemplified by -20-200903163 N-methyl-2-pyrrolidone, N,N-dimethylacetamide, γ-butane vinegar and the like. The positive photosensitive resin composition of the present invention contains (b) quinonediazide. As the roller diazide compound, it can be exemplified that the polyhydroxy compound is a sulfonate bond with a quinone dihalide sulfonate bond. The hydroxypolyamine compound is a sulfonate bond of a quinonediazide and/or a sulfonamide bond or the like. The entire functional group of these polyhydroxy compounds or polyamine compounds may not be substituted by quinonediazide, but it is preferably substituted by more than 50 mol% of the entire functional group via quinonediazide. By using 50% by mole or more of the quinonediazide compound, the affinity of the quinonediazide compound to the aqueous alkali solution can be lowered, and the solubility of the resin composition in the unexposed portion to the aqueous alkali solution can be greatly reduced. On the other hand, since the quinonediazidesulfonyl group is converted into an anthracene carboxylic acid by exposure, the dissolution rate of the resin composition of the exposed portion to the aqueous alkali solution becomes high. As a result, the ratio of the dissolution rate of the exposed portion of the composition to the unexposed portion is increased, and a high resolution pattern can be obtained. By using such a quinonediazide compound, a positive photosensitive resin composition which is sensitive to i-rays (365 nm), h-line (405 nm), and g-line (436 nm) of a general ultraviolet ray, i.e., a mercury lamp, can be obtained. Further, it may contain two or more kinds of quinonediazide compounds. Examples of the polyhydroxy compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, Tris P-PA, Tris P-SA, T ris OCR-PA, BisOCHP-Z, and BisP-MZ. , BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tri-FR-CR, BisRS-26X, DML - Μ BPC, DML - Μ BOC, DM L-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, -21- 200903163 DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML- PSBP, DML-MTrisPC, TriML-P, TriML-3 5XL 'TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (above is the trade name, Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BI RB IP C - F, TEP - B IP - A 46DMOC '46DMOEP, TM-BIP-A (above, trade name, Asahi Organic Industry Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-di Methoxymethyl-P-cresol, 2,6-diethoxymethyl-P-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, Phenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry (shares) Ltd.) and the like, but these are not defined. Examples of the polyamine-based compound include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl. Methane, 4,4'-diaminodiphenylphosphonium, 4,4,-diaminodiphenyl sulfide, etc., but are not limited by these. Examples of the polyhydroxy polyamine-based compound include 2,2-bis(3-amino-4-phenyl)hexafluoropropane and 3,3,-dihydroxybenzidine, but are not limited thereto. . In the present invention, the quinonediazide sulfonate is preferably one of 5-naphthoquinonediazidesulfonyl group and 4-naphthoquinonediazidesulfonyl group. The 4-naphthoquinone diazide sulfonate compound absorbs in the i-line range of a mercury lamp and is suitable for 1-line exposure. The absorption of the 5-naphthoquinonediazide sulfonate compound extends to the g-line range of the mercury lamp and is suitable for g-line exposure and full-wavelength exposure. In the invention of the present invention, it is preferred to select a 4-naphthalene diazide-blocking ester compound or a 5-naphthoquinonediazide sulfonate compound in accordance with the wavelength of exposure. Further, a naphthoquinonediazide sulfonate compound having a 4-n-azulidine azide group or a 5-naphthoquinonediazide aramid base may be used in the same molecule, and 4-naphthoquinone divalent compound may also be used. Azide oxime ester compound and 5-naphthoquinonediazide sulfonate compound. The molecular weight of the quinonediazide compound is preferably 3 Å or more, more preferably 305 or more, and preferably 3, 0 from the viewpoint of heat resistance, mechanical properties, and adhesion of the film obtained by the heat treatment. 0 0 or less, better! , 5 〇 〇 below. The content of the V (b) quinone diazide compound is preferably 1 part by weight or more, more preferably 3 parts by weight based on 100 parts by weight of the poly (meth) acid or polyglycolate of the component (a). The amount is preferably 50 parts by weight or less, more preferably 40 parts by weight or less. The quinonediazide compound can be synthesized, for example, by reacting 5-naphthoquinonediazide sulfonium chloride with a polyhydroxy compound such as a phenol compound in the presence of triethylamine. The method for synthesizing a phenol compound is a method for reacting an α-(hydroxyphenyl)styrene derivative with a polyvalent phenol compound under an acid catalyst. Further, as needed, it is possible to further contain a polyhydroxy compound for the purpose of supplementing the alkali developability of the photosensitive resin composition. The photosensitive resin composition containing a polybasic compound is hardly dissolved in the alkali developing solution before exposure, but is easily dissolved in the alkali developing solution upon exposure. Therefore, the film thinning due to 'development is small, and the short-time development system is easy. In this case, the content of the polyhydroxy compound is preferably 1 part by weight or more and more preferably 3 parts by weight or more based on the total amount by weight of the poly (a) component of the poly (a) component or the polyphthalate. And preferably 50 parts by weight or less 'more preferably 40 parts by weight -23-200903163 or less. When it is 1 to 50 parts by weight, film thinning in the unexposed portion can be suppressed, and high sensitivity can be achieved. The positive photosensitive resin composition of the present invention contains (c) a polyfunctional acrylate-based compound. The positive photosensitive resin composition of the present invention is subjected to heat treatment after pattern processing, whereby the polyfunctional acrylate-based compound is thermally polymerized to improve the chemical resistance of the cured film, and at the same time, a pattern having a low conical shape can be formed. . In the present invention, the component (C) is an acrylate compound and is multifunctional. The reaction initiation temperature of the thermal polymerization reaction of the acrylate-based compound is as high as 20 0 in comparison with the conventional reaction temperature of the thermal crosslinking agent having a methylol group or an epoxy group of 120 ° c to 180 ° C. (TC or more. Therefore, the shrinkage or reflow of the film by heating is not hindered. Therefore, the acrylate-based compound is thermally polymerized in a state where reflow by heating is performed, so that a pattern having a low conical shape can be obtained. However, the monofunctional acrylate-based compound is inferior in compatibility with the poly-proline and polyphthalate resins of the component (a), and phase separation often occurs. Therefore, the content of the monofunctional acrylate-based compound is limited. In a small amount, it is difficult to effectively obtain the effect of reducing the taper angle I. Further, in the case of a monofunctional acrylate-based compound, hardening of the film by thermal polymerization cannot be sufficiently performed, and improvement in chemical resistance and insulation properties cannot be obtained. In the present invention, the acrylate-based compound means a compound having an acryloyl group or a methacryloyl group. Examples thereof include acrylate, methacrylate, and acrylonitrile. , Methyl acrylamide and the like. In addition, multifunctional acrylate-based compound means a compound having two or more groups of Bingxi Xi and / or methacrylamide having acyl. -24-200903163

Preferred examples of the polyfunctional acrylate-based compound include NK ester series 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, HD, NPG, 9PG, and 701 manufactured by Shin-Nakamura Chemical Co., Ltd. , BPE-100, BPE-200 'BPE-500, ΒΡΕ-1300' Α-200, Α-400 > Α-600, A-HD, A-NPG, APG-200, APG-400, APG-700, Α-ΒΡΕ-4, 70 1 A 'TMPT, A-TMPT, A - T Μ Μ - 3, A - T Μ Μ - 3 L, A-ΤΜΜΤ, Α-93 00, ΑΤΜ-4Ε, ΑΤΜ-35Ε, ΑΤΜ-4Ρ, AD-TMP, AD-TMP-L, A-DPH, etc. Further, Light Ester ester series 共-1Μ, Ρ-2Μ, EG, 2EG, 3EG, 4EG, 9EG, 14EG, 1.4BG, NP, 1 · 6 Η X, 1.9 ND can be cited by Kyoeisha Chemical Co., Ltd. , 1 _ 1 0 DC, G-1 01 P, G-201P 'DCP-M, BP-2EM 'BP-4EM, BP-6EM 'TMP, etc. Further, a Light Acrylate system made by Kyoeisha Chemical Co., Ltd. [J 3EG-A, 4EG-A, 9EG-A, 14EG-A' TMGA-250, ΝΡ·A, MPD-A > 1 6HX-A, BEPG-A, 1.9 ND - A, Μ OD - A, DCP-A, BP-4EA, BP-4PA, BA-134, BP-10EA, HPP-A, TMP-A, TMP- 3EO-A, TMP-6EO-3 A 'PE-3 A, PE-4A, DPE-6A, etc. Further, an epoxy ester series 40EM, 70PA, 200PA > 80MFA, 3 0 02M, 3 002A, 3 000M, 3000A, etc., which are produced by Kyoeisha Chemical Co., Ltd., may be mentioned. Further, the "Aronix (registered trademark)" system of the East Asia Synthetic Co., Ltd. system U M-203, M-208, M-210, M-211B, M-215, M-220, M-22 5, M-240 'M-243, M-245, M-2 60, M-27 0, M-305, M-3 09, M-310, M-313, M-315, M- 3 20, M- 3 2 5, M-350, Μ-360, Μ-402, Μ·408' M_450, etc. Further, the "KAYARAD (registered trademark)" series R-526, NPGDA, -25-200903163 PEG400DA, MAND A, R-1 67, HX-22 0, HX-620, R can be cited by Nippon Kayaku Co., Ltd. R-712, R-604, R-684, GPO-3 03, TMPTA, THE TPA-3 20, TPA-3 30, PET-30, T-1420(T), RP-1040, etc. "Blenmer" (registered trademark: GMR-H, GAM, PDE-50, PDE-100, PDE-150, PDE PDE-400, PDE-6 00, PDE-1 000, ADE-200, ADE) PDP-400, ADP-200, ADP-400, PDT-650, ADT PDBE-200, PDBE-250, PDBE-45 0, PDBE- 1 3 00 '200, ADBE-2 5 0, ADBE-4 5 0, etc. Also, it can be cited

Unitec (share) system MBAA and so on. Further, among these polyfunctional acrylate compounds, two or more of these polyfunctional acrylate compounds may be contained, and more preferably one or more propylene fluorenyl groups and/or methacryl oxime groups. Any one of three or more acryloyl fluorenyl groups and methacryl fluorenyl groups may be used, and both propylene fluorenyl groups and methacryl fluorenyl groups may be used, and the total of these is three. By performing thermal polymerization at the time of heat treatment having three or more acrylonitrile groups and/or methacrylium oxime patterns, a mesh-like structure is formed to further improve the chemical resistance and insulation properties of the cured film. More preferably, it is preferably 5 or more, and more preferably 6 or more. Further, the (c) polyfunctional acrylate-based compound may have a thermal polymerizable group other than a methacryl fluorenyl group, a thermally crosslinkable acryl fluorenyl group, or a thermal polymerizable group other than the acryl fluorenyl group. Ethyl ethynyl, allyl, oxetanyl, epoxy and the like are mentioned. Further, a thermocrosslinkable group may, for example, be a hydroxymethyl 'alkoxymethylol group. For -55 1, -3 3 0, and so on. Another >" series - 2 00, 400, 250 ' ADBE-MRC compounds have 3 for having more than one base, in the build, and above, especially acryl. As a suspicion, as effective -26- 200903163 The number of the thermally polymerizable groups or the thermally crosslinkable groups is preferably one or less in the compound. Further, in the present invention, the polyfunctional acrylate compound has a plurality of olefins. The propyl group and/or the vinyl group are also classified as (C). Examples of the acrylate-based compound having a thermopolymerizable group include 2-(2-vinyloxyethoxy)ethyl acrylate. 2-(2-vinyloxyethoxy)ethyl methacrylate, etc. Further, examples of the acrylate-based compound having a heat crosslinkable group include NMAA, NMMA, and NBMA manufactured by MRC Untec Co., Ltd. IBMA, NMMM, NEMM, NBMM, IBMM, NEMA (trade name above), etc. (c) Content of polyfunctional acrylate-based compound, for a total amount of 100 parts by weight of the poly-proline and the poly(a) component The guanamine ester is preferably 1 part by weight or more, more preferably 5 parts by weight or more, and It is preferably 100 parts by weight or less, more preferably 30 parts by weight or less. When the content of the acrylate-based compound is 1 part by weight or more, the chemical resistance is further improved. When the content is 1 part by weight or less, the product is improved. The storage stability of the obtained composition is not less than 3 parts by weight, and it is not related to the standing time until the development after exposure, and a stable sensitivity can be obtained. The positive photosensitive resin composition of the present invention Preferably, it further contains (d) a compound having a plurality of allyl groups and/or a vinyl group. If (d) a compound having a plurality of allyl groups and/or a vinyl group, it not only polymerizes itself when heated. The copolymerization with the acrylate-based compound improves the chemical resistance. Examples of such a compound include diallyl phthalate, diallyl maleate, diallyl fumarate, and succinic acid. Allyl ester, isocyanuric acid, allene-27-200903163 ester, phenyltricarboxylic acid diallyl ester, bisallyl nadiimide (Bis-ally 1-nadi-imide) compound, etc. a compound, or a divinyl compound such as divinylbenzene. Among them, from the viewpoint of chemical resistance and heat resistance, it is preferably triallyl isocyanurate, bisallyl nadiimide, divinylbenzene, etc., more preferably bisallyl nadi In particular, from the point of view of chemical resistance, heat resistance, and low cone, BANI-M and BANI-X (the above are trade names) manufactured by Jiushan Petrochemical Co., Ltd. may be contained. Two or more of these compounds. (d) A content of a compound having a plurality of allyl groups and/or a vinyl group, and for a total amount of 100 parts by weight of the polyamine or polyglycolate of the component (a) In other words, it is preferably 1 part by weight or more, more preferably 5 parts by weight or more, and more preferably 30 parts by weight or less, still more preferably 1 part by weight or less. When the content of the compound having a plurality of allyl groups and/or a vinyl group is 1 part by weight or more, the film after heat curing can obtain higher chemical resistance, and if it is 30 parts by weight or less, it is further improved. Sensitivity and preservation stability of the composition. The positive photosensitive resin composition of the present invention preferably contains (e) a thermally crosslinkable compound having a group represented by the general formula (2).

In the formula (2), R5 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Examples of such a thermally crosslinkable compound include (e1) a hydrogen atom in the ortho and/or para position of a phenolic hydroxyl group of a compound having a halogenated hydroxyl group, which is substituted with a group represented by the formula (2). (e2) A compound having a urea bond represented by the formula (3). -28- 200903163

~20 hydrocarbon groups. Specifically, 'as a base having one formula (2), 1^1^-26Χ, ML-24X, ML-23 6TMP, 4-hydroxymethyl 3M6C, ML-MC, ML-TBC (The above is the trade name, the Honshu Chemical Industry Co., Ltd.), etc.; as two, DM-BI25X-F '46DMOC '46DMOIPP ' 46DMOEP (the above is the trade name, Asahi Organic Industry Co., Ltd.) ), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, dimethylol-Bis-C , dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z ' DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML - B is 2 5 X - 3 4 XL ' DML - B is 2 5 X - PC Η P (The above is the trade name, manufactured by Honshu Chemical Industry Co., Ltd.), and "Nikalac (registered trademark)" MX-2 9 0 (trade name, Sanwa Chemical Co., Ltd.) , 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-P-cresol, 2,6-diethyloxymethyl-P- For example, TriML-P, TriML-35XL, and TriML-TrisCR-HAP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.) As a person who has four, TM-BIP-A (trade name, Asahi Organic Industry Co., Ltd.), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (The above is the trade name, Honshu Chemical -29-200903163 Industrial (share) system), "Nikalac" MX-2 80, MX-2 70 (above is the trade name, Sanwa Chemical Co., Ltd.), etc.; For example, HML-TPPHBA, HML-TPHAP, HMOM-TPHAP (above, trade name, Honshu Chemical Industry Co., Ltd.), "Nikalac" MW-30HM, MW-100LM (above, trade name, Sanwa) Chemical (share) system, etc. It is also possible to contain two or more of these compounds. Among these, the present invention preferably contains at least two groups represented by the formula (2). More preferably, as the base represented by the two general formulas (2), 46DMOC, 46DMOEP, DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML are exemplified. -34X,

DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, "Nikalac,, MX-290, 2,6-dimethoxymethyl-4- Third butyl phenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diethoxymethyl-P-cresol, etc.; as having three, TriML -P, THML-35XL, etc.; as having four, Ding "-BIP-A, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, "Nikalac" MX-280, MX-270, etc.; as six, HML-TPPHBA, HML-TPHAP, HMOM-TPHAP, "Nikalac, MW-30HM, MW-100LM#" are mentioned. Further, it is preferably an R5-based hydrocarbon of the formula (2). When R5 is a hydrocarbon, the progress of thermal crosslinking becomes slower than that of the hydrogen atom. After hardening, a pattern having a low taper angle is easily obtained. The content of the thermally crosslinkable compound of the component (e) is preferably from 1 to 30 to 200903163 parts for a total of 1 part by weight of the polyamine or polyamine derivative of the component (a). The above 'more preferably 5 parts by weight or more. Further, it is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and the content of the component (c) is preferably equal to or less. When the content of the (e) component is (e), the content of the thermally crosslinkable compound is 1 part by weight or more, the chemical resistance of the thermosetting film is further improved. In addition, when it is 50 parts by weight or less and ((the content of the 〇 component is equal to or less than the same amount), the reflow at the time of heating can be effectively promoted, and a pattern having a lower taper angle can be formed. The positive photosensitive resin composition of the present invention The polymerization inhibitor may be contained, if necessary, a polymerization inhibitor, a thermal radical generator, a surfactant, a subsequent modifier, etc. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, and hydroquinone such as p-benzoquinone. A polymerization inhibitor, 2,2-diphenyl-1-picrylhydrazyl or nitrobenzene, etc. It may contain two or more of these. The positive photosensitive resin composition can be obtained by containing a polymerization inhibitor. The storage stability is not related to the standing time until the development after exposure, and the sensitivity is stable. The content of the polymerization inhibitor is 100 parts by weight of the (C) polyfunctional acrylate compound and (d) The number of allyl and/or vinyl compounds is preferably 0.001 to 1 part by weight. Examples of the thermal radical generator include hydroperoxides, dialkyl peroxides, and ketone peroxides. , peroxyketal, dimercapto peroxide, peroxygen An organic peroxide such as a carbonate or a peroxyester, or an azo compound. Two or more kinds of these may be contained. By containing a thermal radical generating agent, radicals are generated upon heating, which promotes (c). The polymerization of a polyfunctional acrylate-based compound or (d) a compound having a plurality of allyl groups and/or a vinyl group improves the chemical resistance of the cured film. 200903163 The content of the thermal radical generating agent, for a total amount of 100% The (c) polyfunctional acrylate-based compound and (d) a compound having a plurality of allyl groups and/or a vinyl group are preferably from 1 to 50 parts by weight. As a further improving agent, three a decane coupling agent such as oxyaminopropyl decane, trimethoxy oxy decane, trimethoxyvinyl decane or trimethoxy thiopropyl decane, a titanium chelating agent, an aluminum chelating agent, an aromatic amine compound and A compound obtained by reacting an alkoxy group-containing ruthenium compound, etc. It may contain two or more of these. By including these compounds, it is possible to further improve the adhesion to the underlying substrate of ruthenium wafer, ITO, SiO 2 , SiN x or the like. Sex while improving for washing The resistance of the oxygen plasma and the UV ozone treatment used for the net, etc. Next, the content of the modifier is preferably 1 part by weight of the poly (a) component of the polyamine or polyglycolate. 5%. 5 parts by weight. As the surfactant, Flo: rad (trade name, Sumitomo 3M (share)), and "Megafac (registered trademark)" (made by Dainippon Ink Chemical Industry Co., Ltd.) , a fluorine-based surfactant such as Sulfron (trade name, Asahi Glass Co., Ltd.), KP341 (trade name, Shin-Etsu Chemical Co., Ltd.), DBE (trade name, Chisso), Glanol (trade name) , Kyoeisha Chemical Co., Ltd., BYK (B 1C Chemical Co., Ltd.), etc., organic oxirane surfactant, P〇refl〇W (trade name, Kyoeisha Chemical Co., Ltd.), etc. Acrylic polymer surfactant. It is also possible to contain two or more of these. If a surfactant is contained, the coating property with a substrate can be improved. The content of the surfactant is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the poly (methionine) or polyphthalate of the component (a). The positive photosensitive resin composition of the present invention contains a solvent in general, in addition to these components, -32-200903163. Examples of the solvent include N-methyl _ 2 _ π pyrrole D 嗣, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethylene. a polar aprotic solvent such as selenium, an ether such as tetrahydrofuran, dioxane, propylene glycol monomethyl ether or propylene glycol monoethyl ether; acetone, methyl ethyl ketone, diisobutyl ketone or diacetone alcohol Ketones, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate An ester such as an ester, an aromatic hydrocarbon such as toluene or xylene, or the like. It can also contain two or more of these. The content of the solvent is preferably '50 parts by weight or more', more preferably 1 part by weight or more, and more preferably 1 part by weight or more, based on the total amount of 100 parts by weight of the poly (a) component of the (a) component. It is preferably 2,000 parts by weight or less, more preferably 1,500 parts by weight or less. When it is in the range of 50 to 2,000 parts by weight, the viscosity is suitable for coating, and the film thickness after coating can be easily adjusted. The viscosity of the positive photosensitive resin composition of the present invention is preferably from 3 to 500 mPa·s. By setting the viscosity to 3 mPa·s or more, it is possible to easily form a film having a desired thickness. On the other hand, by setting the viscosity to 50 OmPa·s or less, a coating film having a uniform film thickness can be easily formed. The viscosity of the positive photosensitive resin composition can be adjusted to a desired range by adjusting the solid content concentration'. In the resin composition obtained by the present invention, the exposed portion has a positive type photosensitive property dissolved in an aqueous alkali solution. Next, a method of producing a heat resistant resin pattern using the positive photosensitive resin composition of the present invention will be described. In the present invention, a heat-resistant resin pattern can be formed by (1) a step of patterning the positive photosensitive resin composition of the present invention -33-200903163, and (2) a step of heat treatment. The step (1) of the patterning process preferably has the following steps: (1 -1) applying the positive photosensitive resin composition of the present invention to a substrate to obtain a photosensitive resin composition film, (1 - 2) The step of exposing the photosensitive resin composition film by a chemical line, and (1-3) the step of developing the photosensitive resin composition film after exposure using a developing solution. The steps are explained below. First, the positive photosensitive resin composition of the present invention is applied onto a substrate. As the substrate, for example, a germanium wafer, a ceramic, gallium arsenide, sodium glass, quartz glass or the like is used, but it is not limited thereto. The coating method may be, for example, a method such as a slit coating method, a spin coating method, a spray coating method, a roll coating method, or a bar coating method, or may be carried out by combining these methods. Further, before the application of the positive photosensitive resin composition, the substrate may be pretreated by a chemical liquid containing the above-mentioned improving agent. Specifically, it is preferably dissolved in isopropanol by using a subsequent modifier at 5% to 5% by weight of ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate. A solution obtained by using a solvent such as diethyl adipate or the like is subjected to surface treatment by spin coating, slit coating, bar coating, dip coating, spray coating, steam treatment or the like. If necessary, heat treatment at 5 to 300 ° C may be performed to react the substrate with the subsequent modifier. Then, the substrate coated with the positive photosensitive resin composition was dried to obtain a photosensitive resin composition film. The drying system can be carried out using a hot plate, a supply box, an infrared ray, a vacuum chamber, or the like. When the hot plate is used, the heated body -34 - 200903163 is heated on the plate directly or on a jig such as a pin provided on the board. As a material for the proximity pin, a metal material such as aluminum or stainless steel, or a polyimide resin or a synthetic resin such as "Teflon (registered trademark), etc." may be used as a proximal pin of any material. There are various types of photosensitive resin compositions coated on a glass substrate heated to 300 mm x 350 mm x 7 7 mm depending on the size of the substrate, the type of the resin layer to be heated, and the purpose of heating. The height of the pin is preferably about 2 to 12 mm. The heating temperature is various, depending on the type or purpose of the object to be heated, preferably from room temperature to 180. (1: 1 minute) Then, on the photosensitive resin composition film, a chemical mask is irradiated through a mask having a desired pattern, and exposure is performed. As a chemical line for exposure, there are ultraviolet rays, visible rays, electron beams, and X-rays. In the present invention, it is preferred to use ultraviolet rays. It is particularly preferable to use i-line (3 65 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp. To form a pattern of a photosensitive resin, after exposure, The developing solution is used to remove the exposed portion. As the developing solution, an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol 'sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and triethyl is preferred. Amine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylene An aqueous solution of a compound which exhibits basicity such as a diamine, and, as the case may be, may also contain N-methyl-2-pyrrolidone, hydrazine, hydrazine-dimethyl dimethyl or the like in the aqueous alkali solution. A polar solvent such as carbamide, hydrazine, hydrazine dimethyl dimethyl phthalamide, dimethyl sulfoxide, γ-butyrolactone or dimethyl methacrylate, alcohol such as methanol, ethanol or isopropanol, or lactic acid B-35-200903163 esters such as esters, propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone, etc., preferably after development The rinsing treatment is carried out in water. Here, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be used. It is added to water for rinsing treatment. After development, it is converted into a heat-resistant resin film by heat treatment. The heat treatment temperature is generally 180 ° C or higher and 400 ° C or lower, and in the present invention, preferably 180 ° C or higher ' 3 00 When the heat treatment is carried out at a temperature of 180 ° C or higher, (a) a polyaminic acid having a structural unit represented by the formula (1) and/or a polyamidomate is subjected to a ruthenium imidization reaction. The low taper angle improves the chemical resistance and the insulating property. Further, the acrylate compound of the component (c) is melted to have a low taper angle, and a thermal polymerization reaction is carried out to further improve chemical resistance and insulation. Further, by heat treatment at a temperature of 30 or less, the thermal decomposition of the (c) acrylate-based compound can be suppressed, and the chemical resistance and the insulating property can be further improved. When the positive photosensitive resin composition of the present invention is used as an insulating layer and/or a planarizing film of an organic EL device, it is preferable to consider the stability of the operation including the design temperature of the TFT or the resistance of the ITO. The heat treatment is performed in a range of °C or more and 250 °C or less. When the taper angle of the heat-resistant resin pattern formed of the positive-type photosensitive resin composition of the present invention is used as an insulating layer of an organic EL device, the film thickness Ιμηι is preferably 45° or less, more preferably 40° or less. Very good is below 30°. When the taper angle is 45° or less, when the first electrode of the organic light-emitting layer is formed, the organic light-emitting layer or the second electrode is not locally thinned or stepped at the boundary portion between the insulating layer and the first electrode. It can be smoothly formed into a film, -36-200903163, so that stable light without uneven brightness can be obtained. Further, when the flattening layer is used as the TFT substrate, the taper angle of the heat-resistant resin pattern is preferably 45 or less, more preferably 40 or less, in terms of a film thickness of 2 μm. By setting the taper angle to 45 or less, the first electrode formed on the upper portion of the planarizing layer is not locally thinned, and the film can be smoothly formed. Further, the taper angle in the present invention means an angle formed by the side surface of the pattern and the surface of the substrate, and is referred to as an angle indicated by Θ in Fig. 1 . The measurement of the taper angle was carried out by electron microscopic observation of the pattern cross section. The insulating breakdown voltage 値 of the heat-resistant resin pattern formed of the positive photosensitive resin composition of the present invention is preferably 2500 ν/μπι or more, more preferably 30 〇ν/μιη, particularly preferably It is 35〇ν/μιη or more. When the heat resistant resin pattern obtained by the present invention is used as an insulating layer of an organic EL device, the thickness between the electrodes of the light-emitting layer is about 200 nm, and a voltage of about 10 V is applied. The insulating layer must have sufficient reliability of insulation at this 200 nm. When the insulating property of 25 〇 ν / μ η is 200 nm, the insulation is 50 V, and the reliability of the practical voltage is estimated to be 5 times. If it is this range, the insulation reliability of long-term stability can be maintained.

The organic EL device of the present invention has, in order, a first electrode, a hole transport layer, an organic light-emitting layer, an electron transport layer, and a second electrode, and has a heat-resistant resin pattern formed by the heat-resistant resin pattern of the present invention on the surface of the first electrode. Insulation. The insulating layer is formed around the organic light-emitting layer to form a predetermined light-emitting region. Since the heat resistant resin pattern of the present invention has a small taper angle, it is suitable for an insulating layer of an organic EL element. That is, when the organic light-emitting layer or the first electrode is formed, the film can be smoothly formed at the boundary portion between the insulating layer and the first electrode, so that the organic EL-37- of stable light emission without unevenness in brightness can be obtained. 200903163 Components. The display device of the present invention has a planarization layer and a display element formed of the heat resistant resin pattern of the present invention on the substrate on which the TFT is formed. For example, a liquid crystal display device, an organic EL display device, etc. are mentioned. As an example of the active matrix type display device, a TFT for driving a display element, a wiring, and a flattening layer covering the display element are provided on the substrate, and a display element is provided on the flattening layer. The display element and the wiring are connected via a contact hole formed in the planarization layer. Since the resin pattern of the present invention has a small taper angle, the electrode can be smoothly formed on the planarization layer. Therefore, the resin pattern of the present invention is suitable as a planarization layer of a TFT substrate. Fig. 2 is a cross-sectional view showing a TFT substrate on which a planarization layer and an insulating layer are formed. A bottom-gate type or top-gate type TFT 4 in a matrix is provided on the substrate 1, and an insulating film 5 made of an inorganic material is formed to cover the TFT 4. Further, a wiring 6 connected to the T F T 4 is provided on the insulating film 5. Further, a planarization layer 7 is provided on the insulating film 5 so as to embed the wiring 6. A contact hole 8 reaching the wiring 6 is provided in the flattening layer 7. Then, in a state where the wiring 6 is connected via the contact hole 8, a display element (for example, an organic EL element) is provided on the planarization layer 7. The organic EL element is formed by forming the first electrode 2 so as to connect the wiring 6, and then covering the contact hole 8 and the end surface of the first electrode 2 with the insulating layer 3. A hole transport layer, a light-emitting layer, an electron transport layer, and a second electrode (not shown) are sequentially formed on the first electrode opening. The organic EL element may be a top emission type which emits light from the opposite side to the substrate 1, or a bottom emission type which extracts light from the side of the substrate 1. Thus, an organic EL display device of -38 to 200903163 active matrix type to which T F T 4 for driving each organic EL element element is connected is obtained. [Examples] Hereinafter, the present invention will be described by way of Examples and the like, but the present invention is not limited by the examples. Further, the evaluation of the positive photosensitive resin composition was carried out by the following method. (1) Measurement of weight average molecular weight of polymer The weight average molecular weight in terms of polystyrene was determined by gel permeation chromatography (Waters 2690, manufactured by WATERS, Japan). For the column, TOSOH TXK-GEL α-2500 and α-4000 were used in tandem, and 移-methyl-2-pyrrolidone was used as the mobile phase. (2) Preparation of heat-resistant resin pattern for evaluation and preparation of pre-baked film A positive-type photosensitive resin composition (hereinafter referred to as varnish) was applied onto a 4-inch wafer. Subsequently, a hot plate D-SP IN (manufactured by Dainippon SCREEN Co., Ltd.) was used, and prebaked at 1 10 ° C for 2 minutes to obtain a prebaked film. The film thickness was adjusted so that the film thickness of 1 μη ° after hardening was measured using LAMBDA ACE STM-602 manufactured by Otsuka SCREEN. The refractive index is 1.629. Exposure Using a exposure machine (CANA (manufactured by CANON), PLA-501F), a gray-scale mask that cuts a wire and gap pattern is attached to the pre-baked film to illuminate the GH blending line of the mercury lamp. The exposure amount is irradiated so as to be 50 to 200 mJ/cm 2 per 5 mJ/cm 2 by the gray scale mask. -39- 200903163 Development After 5 minutes of exposure, the prebaked film was subjected to immersion development for 6 sec. with tetramethylammonium hydroxide 2.3 8% aqueous solution, and rinsed with pure water for 3 sec. Calculation of sensitivity The lowest exposure amount when the film thickness of the exposed portion after development is 〇μηη is obtained. Preparation of cured film For the developed film, heat treatment was carried out at 220 ° C for 40 minutes under a nitrogen flow (oxygen concentration of 20 Ppm or less) using an Inert oven INH-21CD manufactured by Koyo Thermo Scientific Co., Ltd. (Comparative Example 7 at 300 °) C 40 minutes) to prepare a cured film (heat resistant resin film). (3) Evaluation of the taper angle The electric field emission electron microscope S-4 8 00 manufactured by Hitachi High-Tech Co., Ltd. was used to observe the cross section of the 30 μπι line after hardening. In this section, the angle formed by the side of the pattern of the line and the surface of the substrate is taken as a taper angle. When the taper angle is 10 to 40, it is possible to determine an insulating layer suitable for the organic EL element or a planarization layer of the TFT substrate. (4) Evaluation of chemical resistance The cured film produced by the method described in the above (2) was immersed in a Nagase Chemtex (manufactured) peeling liquid N-3 00 at 60 ° C for 1 minute. The film thickness before and after the treatment was measured to determine the amount of film reduction caused by the immersion treatment. When the amount of film reduction is 0.3 μm or less, it can be judged that the chemical resistance is good. If it is below 0.1 μm, it can be judged to be excellent. (5) Evaluation of the sensitivity stability In the method described in the above (2), the sensitivity (1 hour sensitivity) when the time from the exposure to the time of the exposure -40 to 200903163 was changed to 1 hour was obtained. The sensitivity (inductance within 5 minutes) obtained by the method described in the above (2) was compared. If the sensitivity changes (((1 time sensitivity within -5 minutes sensitivity) / within 5 minutes sensitivity) X 1 0 0 ) within 5 %, stability can be judged. (6) Evaluation of the insulating property A heat-resistant resin film having a film thickness of about 1 μm was formed on the high top 矽 wafer in the same manner as the method described in the above (2) except that the exposure was not performed. The heat-resistant resin film was subjected to a voltage withstand voltage/insulation resistance tester TO S 92 0 1 manufactured by Kikusui Electronics Co., Ltd., and the DC W was boosted at a pressure increase rate of 0.1 kV/4 seconds to measure the dielectric breakdown. The voltage at the time. The obtained voltage was divided by the film thickness to obtain an insulation breakdown voltage per unit film thickness. If it is 3 00 V / μιη or more, it can be judged that the insulation property is good. If it is 3 5 OV/μιη or more, it can be judged to be excellent. Synthesis Example 1 Synthesis of a hydroxyl group-containing acid anhydride (a) under a dry nitrogen stream '18.3 g (〇.〇5 mol) 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (central Glass (manufactured by BAHF) and 34.2 g (〇.3 mol) allyl glycidyl ether were dissolved in gram gamma-butyrolactone and cooled to -1 5 t. 22.1 g (0.11 mol) of chlorinated trimellitic anhydride in 50 g of γ-butyrolactone was dropped therefrom in such a manner that the temperature of the reaction liquid did not exceed 〇 °C. After the completion of the dropping, the reaction was allowed to proceed for 4 hours at 〇〇C. This solution was concentrated by a rotary evaporator and charged into 1 liter of toluene to obtain a hydroxyl group-containing acid anhydride (a) represented by the following formula. 41- 200903163

Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound (b) 18.3 g (0.05 mol) of BAHF was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide (manufactured by Tokyo Chemical Co., Ltd.). Cool to -151. A solution obtained by dissolving 20.4 g (0.11 mol) of 3 nitrobenzimid chloride (manufactured by Tokyo Chemical Co., Ltd.) in 1 mL of acetone was added dropwise thereto. After the completion of the dropwise addition, the reaction was allowed to proceed at -1 5 ° C for 4 hours, and then returned to room temperature. The precipitated white solid was separated by filtration and dried under vacuum at 50 °C. 30 g of the solid was placed in a 300 mL stainless steel autoclave, and dispersed in 25 mL of methyl cellosolve, and 2 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Hydrogen was introduced into the balloon therein, and the reduction reaction was carried out at room temperature. After about 2 hours, confirm that the balloon is no longer shrinking and end the reaction. After completion of the reaction, the catalyst is removed to remove the catalyst, i.e., a palladium compound, and concentrated by a rotary evaporator to obtain a crystal of the hydroxyl group-containing diamine compound (b) represented by the following formula.

Synthesis Example 3 Synthesis of quinonediazide compound (c) Under a dry nitrogen stream, '9.21 g (0.05 mol) methyl gallate and 40.3 0 g (〇_15 mol) 5-naphthoquinonediazide The sulfonium chloride was dissolved in 45 () g -42 - 200903163 I,4-dioxane to give room temperature. Thereto, 12.65 g (0.15 mol) of triethylamine mixed with 50 g of L4-dioxane was dropped in a manner of not more than 35 in the system. After dripping, it was stirred at 30 ° C for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. The precipitate which precipitated was then collected by filtration. This precipitate was dried by a vacuum dryer to obtain a cold diazide compound (c) represented by the following formula.

Synthesis Example 4 Synthesis of polyphthalate (A) under a dry nitrogen stream '5. 克 1 g (0.02 5 mol) 4,4'·diaminophenyl ether, 1.24 g (0.005 mol) 1 3 -Bis(3-aminopropyl)tetramethyldioxane was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). Thereto, 21.4 g (〇. 〇3 mol of the hydroxyl group-containing acid anhydride (a) obtained in Synthesis Example 1) and 14 g of NMP were added, and the reaction was allowed to proceed at 2 ° C for 1 hour, followed by 5 ° ° C was allowed to react for 2 hours. Thereto, 0.703 g (0_0 0 6 mol) of 4-ethynylaniline as a blocking agent was added, and the reaction was further carried out at 60 ° C for 2 hours. Then, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethyl acetal diluted with 5 g of NMP was dropped at 10 minutes. After dripping, it was stirred at 50 ° C for 3 hours. After the reaction is completed, the solution is poured into 2 liters of water, and the polymer solids are collected by filtration. The true S dryer at 8 〇 ° C is dried for 20 hours to obtain poly-proline. Vinegar (Α) ° The polyglycolic acid vinegar has a weight average molecular weight of 24,000° and a fluorine content of -43 to 200903163 in the structural unit represented by the formula (1) is 12% by weight. Synthesis Example 5 Synthesis of Polyphthalate (B) Under a dry nitrogen stream, 12.1 g of a hydroxyl group-containing diamine (b) obtained in Synthesis Example 2 and 1.24 g (〇.005) were obtained under a dry nitrogen stream. Mole), 3-bis(3-aminopropyl)tetramethyldioxane was dissolved in 50 g of NMP. 7.76 g (0.025 mol) of 3,3,4,4'-diphenyl ether tetracarboxylic dianhydride was added thereto at 20 ° (: the reaction was allowed to stand for 1 hour, followed by the reaction at 50 ° C for 2 hours). 1.3 g (0.0 125 mol) of 3-aminophenol as a blocking agent was added thereto, and the reaction was further carried out at 6 ° C for 2 hours. Then, it took 5 96 ml to drip for 10 minutes (〇 〇5 mol) A solution of N,N-dimethylformamide dimethyl acetal diluted with 5 g of NMP. After dripping, it was stirred at 50 ° C for 3 hours. The precipitate of the polymer solid was collected by filtration in 2 liters of water, and the polymer solid was dried in a vacuum dryer of 80 T: for 20 hours to obtain a polyphthalate (B). The weight average molecular weight is 26, 〇〇〇. Further, the gas content occupied by the unit of the formula (1) is 10% by weight. / Synthesis. Synthesis of Polyhydroxyguanamine (C) of Synthesis Example 6 In a 2 liter separable flask, mix and dissolve 197.8 g (0-54 mol) of BAHF, 75.9 g (0_96 mol) of shaky steepness, and 692 g of monomethylacetamide at room temperature (25 rpm). ' 19.7 g (0.12 旲) of 5-norbornene-2,3-dicarboxylic anhydride was dissolved in 88 g of dimethylglycol monomethyl acid (DM DG) by dropping from a dropping funnel. The time required is 40 minutes, and the temperature of the reaction solution is at most 28 ° C. Next, it is cooled by a water bath, in which 142.3 g (0.48 mol) 4, 4, and 2 are dropped by a dropping funnel. 44- 200903163 The compound was dissolved in 392 g of DMDG. The time required for dropping was 80 minutes, and the temperature of the reaction solution was at most 12 ° C. After 3 hours from the end of the dropwise addition, the above reaction was dropped under high-speed stirring. The polymer was dispersed and precipitated in 12 liters of water, recovered, washed with water, dried, and then vacuum dried to obtain polyhydroxyguanamine (C). The weight average molecular weight of the polyhydroxyguanamine was 14,000. 1 10 g (100 parts by weight) of polyphthalate (A), 2.5 g (25 parts by weight) of quinonediazide compound (c), 3.5 g (35 parts by weight) of Light Acrylate TMP-A (Kyoeisha) Chemical (manufactured by the company) is dissolved in 20 g (200 parts by weight) of γ-butyrolactone, 20 g (200 parts by weight) of lactic acid The varnish was used as a varnish. The varnish was used to evaluate the taper angle, chemical resistance, sensitivity stability, and insulation. Examples 2 to 1 2. Comparative Examples 1 to 7 A varnish was prepared by the compositions described in Tables 1 and 2. The taper angle, chemical resistance, sensitivity stability, and insulation were evaluated in the same manner as in Example 1. The Light Acrylate TMP-A, MTG-A, PE-4A, and DPE used in the examples and the comparative examples are shown below. -6A (above is Kyoeisha Chemical Co., Ltd.), triallyl isocyanurate (ALDRICH), BANI-M (Kowloon Petrochemical Co., Ltd.), and Nikalac (registered trademark) Structure of MX-2 70 (manufactured by Sanwa Chemical Co., Ltd.), HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.), and NC-6000 (manufactured by Sakamoto Chemical Co., Ltd.). -45- 200903163 h2c=chc〇o-h2c' h2c=chcoo-h2( h2c=chcoo—h2c’ H2C=CHC00-^C2H40-^CHc

MTG-A

TMP-A h2c=chcoo-h2c h2c=chcoo-h2c h2c=chcoo-h2c

Ch2—〇c〇ch=ch2

PE-4A

H2C=CHCOO-H2C h2c=chcoo-h2c h2c=chc〇〇一 h2c

,ch2-ococh=ch2 ch2-〇coch=ch2 ch2-ococh=ch2

DPE-6A

Triisocyanurate

Ch2 46- 200903163 h3c〇v

"^och3 〇ch3 MX-270

Och3 OH OCH3

NC-6000 cone angle, Tables 1 to 2, the results of evaluation of chemical resistance and sensitivity stability were summarized in Examples 1 to 2 2 and Comparative Examples 1 to 7. -47- 200903163 [I撇] Insulation (v_) 〇OJ CO CO CO Ο CO 00 00 〇C0 CO 〇in CO s CO Ο ΙΩ CO 〇00 C0 Sensitivity 褂^ a ^ Bu 〇ο 〇〇ο ο o Ο 感 sensitivity after 1 hour (mJ/cm2) 〇T— 〇T— 〇T- ο X— τ— ια τ~ τ—in CM T— o T— x— ο τ— LO τ— r— 〇 T - 5 minutes or less sensitivity (mJ / cm2) ΙΛ T - LO 00 T - 〇 T - τ ~ ο τ - τ - if) V τ - 〇CNI τ - LO CN or - Ο V- LO τ - τ - 〇 〇T- Nailability (μ〇Ί) LO Csl d Art dd Ο 卜 d CM τ- Ο gdod 〇d S ο 〇d 〇d Cone angle (degrees) ID CO LO 00 ΙΟ CO σ> C\J 00 (NJ 00 CM CN CN Another 1Λ Other compound destroys the damage line φ "丨I _ 氍_ 13⁄4° if one brewed BANI-M (10 parts by weight) HMOM-TPHAP (10 parts by weight) ΒΑΝΙ-Μ (10 Parts by weight ΜΧ-270 (10 parts by weight) BANI-M (10 parts by weight) HMOM-TPHAP (10 parts by weight) ΒΑΝΙ-Μ (10 parts by weight) ΗΜ0Μ-ΤΡΗΑΡ (15 parts by weight) TMP-A (35 weights) Servings TMP-A (30 parts by weight) j TMP-A (10 parts by weight) TMP-A (10 parts by weight) PE-4A (10 parts by weight) DPE-6A (10 parts by weight) DPE-6A (10 parts by weight) DPE-6A (10 parts by weight) DPE-6A (10 parts by weight) DPE- 6A (10 parts by weight) I DPE-6A (10 parts by weight) DPE-6A (10 parts by weight) 醌diazide compound c (25 parts by weight); c (25 parts by weight) 丨c (25 parts by weight) c ( 25 parts by weight) W parts by weight) C (25 parts by weight) C | (25 parts by weight) (25 mW) c (25 parts by weight) c (25 parts by weight) C (25 parts by weight) C (25 parts by weight) Resin A (100 parts by weight) A (100 parts by weight) A (100 parts by weight) B (100 parts by weight) B (100 parts by weight) B (100 parts by weight) B (100 parts by weight) B (100 parts by weight) B ( Loo parts by weight B (100 parts by weight) B (100 parts by weight) Β (1 〇〇 parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Series ^ 驷 - 8 inch - 200903163 [(Nt(] Insulation (V/μητ) 320 200 250 300 1 300 i_ 230 320 Sensitivity change rate (%) 〇ο 〇ο 〇ο ο 1 hour Post-sensitivity (mJ/cm2) ON ο calving σ\ >" Η 〇rn ο ο r 5 Sensitivity within minutes (mJ/cm2) IT) Os ο On Ο ο Ο Chemical resistance (μιη) >1.00 mm 晅撇44-1 >1.00 0.05 1 0.45 ,>1.00 1 1 _ ί 0.15 1 ! (degrees) \〇<11 mm VO 00 Ο (Ν Other compounds 壊 摧 NC NC-6000 (10 parts by weight) 1 ΜΧ-270 (20 parts by weight) i 1 丙烯酸 丙烯酸 acrylate compound 揉 MTG-A | ( 5 parts by weight) MTG-A (2 parts by weight) 壊 ΤΜΡ - Α (1 parts by weight) ΤΜΡ - Α (1 parts by weight) 醌 diazide c (25 parts by weight) C (25 parts by weight) c (25 parts by weight) C (2 parts by weight) 1 c ! (20 parts by weight) c (25 parts by weight) C (2 parts by volume) Resin A (100 parts by weight) A (100 parts by weight) A ( 100 military dim) A (100 parts by weight) B (100 parts by weight) C (100 Wei parts) C (100 parts by weight) Comparative Example 1 Comparative Example 2| i Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 - 6 inch - 200903163 Example 1 3 Prepared on a surface of 730 mm x 920 mm x 〇. 5 mm of non-glass (Corning 曰, manufactured by #1737), formed by a thickness of 1 3 by sputtering evaporation. Onm's I TO transparent electrode film Glass substrate. On this glass substrate, the photoresist was applied by a spin coater, and patterned by exposure and development by a normal lithography method. After removing the unnecessary portion of the ITO by etching, the photoresist was removed to form a stripe shape having a length of 90 mm and a width of 80 μm. This stripe-shaped first electrode is 1 〇 〇 μ m pitch. The varnish prepared in Example 6 was applied onto the glass substrate patterned with ITO by a spin coating method so that the film thickness after soft baking was 1.5 μm. Then, using a hot plate, the glass substrate was held at a height of 5 mm from the height of the hot plate with a proximity pin, and a positive photosensitive resin coating film was obtained by heating at 12 (TC for 3 minutes. The film was coated by a photomask) After UV exposure, it was developed with 2.38 % aqueous solution of tetramethylammonium and rinsed with pure water. The obtained resin pattern was heated in an air atmosphere of a clean oven at 250 ° C for 60 minutes to form an insulation. The thickness of the insulating layer is about 1 μm. The opening of the insulating layer has a width of 70 μm and a length of 250 μm, and the central portion of the first electrode is exposed from the insulating layer. The end portion is covered by the insulating layer. The cross section of the boundary portion of the insulating layer It has a conical shape as shown in Fig. 1, and the taper angle 2 is 28. The electrode substrate with the insulating layer is spin-coated with a photoresist so that the film thickness becomes about 2 μηη ' at 1 〇〇 ° C. The film was heated for 3 minutes to form a protective film. The substrate with the protective film was cut into 4 pieces to form a protective film of 365 mm x 460 mm x 0.5 mm. Next, a photoresist stripping solution (monoethanolamine and diethylene glycol monobutyl) was used. a mixture of ethers) to peel off the protective film. After the substrate is washed with -50-200903163, and heated and dehydrated at 200 °C for 30 minutes, a plate with an insulating film is obtained. The film thickness of the insulating layer changes, and the film is peeled off before the protective film is formed and heated and dehydrated. After that, it is less than 15%. Next, an organic electric device is produced using an electrode substrate with an insulating layer. The thin film layer containing the light-emitting layer is formed by a resistance wire heating method, and the effective area of the substrate is fully utilized. By vapor-depositing the hole transport layer, a shadow mask is used to form the light-emitting layer and the electron-transferring second electrode. At the boundary portion of the insulating layer, the film layer or the f-th is not thinned or stepped, and the smooth formation is performed. The film is taken out from the vapor deposition machine, and the substrate and the glass plate for sealing are bonded and sealed with an ultraviolet epoxy resin. A patterned light-emitting layer is formed on the first electrode of the grain to be first. In a quadrature manner, a stripe-shaped second electrode was arranged to fabricate a simple matrix organic EL display device. The display device was linearly driven to obtain good display characteristics. No bright light was observed in the light-emitting region. C, Example 1 4 Using the TFT shown in Fig. 2, a display device was fabricated by the following method: A TFT 4 of a bottom gate type was formed on the glass substrate 1, and formed under a covered state. The insulating film 5 made of Si3N4. Next, after the contact hole which is omitted in the drawing is formed in the film 5, the wiring 6 (several 1 · Ο μ m) connected via the contact hole is formed on the insulating film 5. The organic EL electrode base formed between the wiring TFTs 4 or for connecting the subsequent steps may be uneven when the field-emitting vacuum is formed to form the carrier layer or the two-electrode-hardened ITO strip electrode. The organic EL: 匕 TFT 4: Insulation-connected TFTs 46 are attached to the element and the 200903163 TFT4. Further, in order to planarize the unevenness due to the formation of the wiring 6, a planarization layer is formed on the insulating film 5 in a state in which the unevenness due to the wiring 6 is buried. 7. The planarization layer 7 is formed by coating the varnish obtained in the embodiment 11 on a substrate, pre-baking on a hot plate (1 20 ° C for 3 minutes), and then exposing through the mask of the desired pattern. The development was carried out by heat treatment at 23 ° C for 6 〇 minutes under air flow. The coating property at the time of applying the varnish was good, and the cured film obtained after exposure, development, and heat treatment did not show wrinkles or cracks. In addition, the average height difference of the wiring defects is 500 ι η η. In the flattening layer produced, a film thickness of 5 μm square contact holes is formed to be about 2 μηι 〇, and then on the obtained planarization layer 7 A top emission type organic EL element is formed. First, on the planarization layer 7, a first electrode 2 made of tantalum is formed, and the wiring 6 is connected via the contact hole 8. Then, the photoresist is coated, pre-baked, and exposed and developed by a mask of the desired pattern. The patterning of the first electrode 2 is performed by using this photoresist pattern as a mask 'wet etching using a 1 τ 〇 etchant'. Then, the photoresist pattern was peeled off using a photoresist stripping solution (a mixture of monoethanolamine and diethylene glycol monobutyl ether). The peeled substrate was washed with water and heated and dehydrated at 200 ° C for 30 minutes to obtain an electrode substrate with a planarization layer. The film thickness dimension change of the planarization layer was less than 1% after heating and dehydration with respect to the peeling liquid treatment. The first electrode thus obtained corresponds to the anode of the organic EL element. Next, an insulating layer 3 covering the shape of the end portion of the first electrode is formed. The varnish obtained in Example 11 was used in the same manner as the insulating layer. By providing this -52-200903163 edge layer, the first short circuit formed by the first electrode and the subsequent step can be prevented. Further, in the vacuum vapor deposition apparatus, the hole transport layer, the organic light-emitting layer, and the electricity are sequentially deposited by a desired pattern, and then Al/Mg is formed over the entire surface of the substrate. Further, a SiO 2 sealing film was formed by CVD film formation. The substrate was taken out from the vapor deposition machine, and a glass plate for sealing and a purple epoxy resin were used, and the film was bonded and sealed. As described above, an active matrix organic EL display device for driving each organic EL element was connected. Good light is emitted when a voltage is applied. Production and Industrial Applicability The heat-resistant resin pattern having a different low taper angle can be obtained from the positive photosensitive resin composition of the present invention. The positive electrode composition of the present invention can be preferably used for a surface protective film of a semiconductor element such as an LSI (Large Scale Integr integrated circuit), an insulating layer or a spacer layer of an interlayer EL element, or an organic transistor of a TFT substrate. Insulation layer, multilayer wiring film for high-density packaging, wiring protective film for circuit board, mirror for solid-state imaging device, various displays, flattening layer for solid-state imaging device, etc.: [Simplified description of the drawing] Fig. 1 shows the insulating layer Schematic diagram of the boundary portion.

Fig. 2 is a TFT diagram in which a planarization layer and an insulating layer are formed. - Shield between the electrodes, according to the transport layer. The second electrode obtained by the second electrode has a high resistance to chemical resistance, a large insulating film, and an interlayer insulating wafer having a flattening layer. Cross section of the substrate -53- 200903163 [Description of main components] 1 Substrate 2 First electrode 3 Insulation

4 TFT 5 Insulation film 6 Wiring 7 Flattening layer 8 Contact hole Θ Cone angle

-54

Claims (1)

200903163 X. Patent application scope: 1. A positive photosensitive resin composition comprising U) polyamic acid and/or polyphthalate having a structural unit represented by the general formula U), (b) bismuth stack Nitrogen compound, (c) polyfunctional acrylate compound; Γ (〇H)p (〇H)q (1) -CO-R1-CONH-R2-NH-L (COOR\ (COOR4)s" In the formula (i), R1 represents a 3 to 8-valent organic group having 2 or more carbon atoms, and r2 represents a 2 to 8-valent organic group having 2 or more carbon atoms; and R3 and R4 may be the same or different and represent a hydrogen atom or a carbon number of 1; a hydrocarbon group of -20; p and q represent an integer of 〇~4, where r represents 1 or 2's represents an integer of 〇~2; but 'p + q > 0). 2 as claimed in claim 1 The photosensitive resin composition is a component (an acrylate-based compound having a tri- or higher functionality). 3. A positive-type photosensitive resin composition as in the first or second aspect of the patent application. a compound of allyl and/or vinyl. 4. A positive photosensitive resin composition as claimed in claim 3 wherein the component (d) is bisallyl dinamidimide (Bis-al) A positive photosensitive resin composition according to any one of claims 1 to 4, which further contains (e) a hot parent having a base of the formula (2) (5) In the formula (2), R5 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 6. A method for producing a heat resistant resin pattern, at least In the order of U), the step of patterning the positive photosensitive resin composition of any one of claims 1 to 5, and (2) the temperature of 1 80 ° C or higher and 250 ° C or lower. The step of performing the heat treatment. 7. A heat-resistant resin pattern obtained by the method of claim 6 of the patent application, wherein the taper angle is 10° or more and 40° or less. 8. An organic electroluminescent device having a first electrode, a hole transporting layer, an organic light emitting layer, an electron transporting layer, and a second electrode in sequence, having the seventh aspect of the patent application scope of the first electrode surface An insulating layer formed of a heat resistant resin pattern. A display device is provided on a substrate on which a thin film transistor is formed, and has a planarization layer formed of a heat resistant resin pattern according to claim 7 of the patent application and a display element. The display device of claim 9, wherein the display element is an organic electroluminescence element.