TWI329786B - Photosensitive resin composition - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition, and more particularly to a semiconductor device, a flat panel display (FPD), etc., particularly a semiconductor device and A photosensitive resin composition formed of an interlayer insulating film or a planarizing film such as FPD; an FPD and a semiconductor device formed using the photosensitive resin composition; and a method of forming a heat-resistant film using the photosensitive resin composition. 2. In the broad field, such as the manufacture of semiconductor integrated circuits such as LSIs or the manufacture of FPD display panels, such as the manufacture of circuit boards such as thermal heads, lithography has been used so far in order to form or finely process fine components. Imaging technology. In the lithography imaging technique, a positive or negative photosensitive resin composition is used in order to form a photoresist pattern. In recent years, in the new application of the photosensitive resin composition, the formation technique of the interlayer insulating film or the planarizing film which is performed by the insulation between the semiconductor integrated circuit or the wiring circuit such as FPD has been attracting attention. In particular, the market has a strong demand for high definition of the FPD display surface, and in order to achieve such high definition, a flattening film having high transparency and excellent insulating properties is an essential material. There are many studies on the photosensitive resin composition used for this purpose, and the invention is applied and disclosed (for example, refer to Patent Documents 1 and 2, etc.). However, the photosensitive resin composition which has been proposed for use in applications such as interlayer insulating films has been required to have a crosslinking (hardening) agent in order to improve heat resistance, so that it has poor stability over time and is compared with a positive photoresist used for general microfabrication. In particular, special attention must be paid to the preservation environment of the composition. In addition, in the lithography imaging of the FPD display surface, the weight 1329786 is used in combination with the developing solution, and a circulating developing solution can be used. In the liquid of the cycle, when a positive photoresist for TFT (film transistor) is mixed with a photosensitive resin composition containing the above-mentioned crosslinking agent, 'because of the positive photoresist and the above-mentioned crosslinking agent Since the crosslinking agent in the composition reacts, there is a problem that a large amount of insoluble precipitates are generated in the developing solution. On the other hand, it is known that I, 2-naphthoquinonediazidesulfonate which is a polyhydroxy compound represented by the following general formula (I) can be used as a sensitizer, and high development and high aspect ratio can be formed. A photosensitive resin composition having a heat-resistance and a resist pattern having a good cross-sectional shape (for example, refer to Patent Document 3), but there is no acrylic resin as an alkali-soluble resin, and there is no time-dependent stability of the photosensitive resin composition. Improve the record. Further, it is also known that a technique in which an epoxy group monomer is incorporated in a polymer main chain to prevent the planarization film after heat treatment from becoming cloudy (for example, refer to Patent Documents 1 and 2), but polymerization of the method The stability of the object is poor, and the storage stability of the photosensitive resin composition becomes very short. Further, in the case where the polymer and the epoxy resin are not used in combination with the copolymer, the storage stability system is extremely excellent, but the surface of the flattened film after the heat treatment has a problem of clouding. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. DISCLOSURE OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION In view of the above circumstances, an object of the present invention is to provide a photosensitive resin group 1329786 which comprises an alkali-soluble resin, a bismuth-containing sensitizer, and a hardening agent. The agent can also obtain a film which maintains the flatness of the surface of the film, has a good light transmittance, and has a low dielectric constant after baking at a high temperature, and has good stability over time. Further, the present invention provides an FPD or a semiconductor device having a planarizing film or an interlayer insulating film formed of the above-mentioned photosensitive resin composition. Furthermore, the present invention provides a method for forming a heat-resistant film which is patterned by using the above-mentioned photosensitive resin composition, and then subjected to overall exposure and post-baking. Means for Solving the Problem The inventors of the present invention have conducted intensive research and review, and found that in the photosensitive resin composition having an alkali-soluble resin, a sensitizer containing quinonediazide group, and a hardener, by using a base The above-mentioned object can be attained by using a soluble resin and a specific substance as a curing agent, and a carboxylic acid in the photosensitive resin composition, and it is found that a photosensitive resin composition can be obtained, for example, at 220 ° C for 1 hour. After the high-temperature heat treatment, a film which maintains the flatness of the surface of the film, has a good light transmittance, a low dielectric constant, and excellent stability over a long period of time can be obtained, and the present invention has been completed. That is, the present invention provides the photosensitive resin composition of the following (1) to (1 2). (1) A photosensitive resin composition comprising an alkali-soluble resin, a sensitizer having a quinonediazide group, and a hardener, wherein the alkali-soluble resin is an acrylic resin, the hardener contains an epoxy group, and the above-mentioned photosensitive The resin composition contains a carboxylic acid. (2) The photosensitive resin composition according to the above (1), wherein the sensitizing agent having a quinonediazide group is a phenolic compound represented by the following formula (I) or (II) and a naphthoquinone A reaction product of a nitrogen compound. -7- 1329786

r" R3 (I)

(wherein R1, R2, R3 and R4 each independently represent H or C!-C2 alkyl group, and R5 and R6 each independently represent C^C2 alkyl group).

(In the formula, ..., ., ^, ... ^, : ^ ^ ruler and ruler ^ are each independently expressed!!, C1-C4 yard base or table

1329786 'm and η are each an integer representing 〇~2, a' b, c, d, e, f' g and M are satisfied with a + b$5, c + d$5' e + f$5, g + h$5 is an integer from 0 to 5, 1 i is an integer from 0 to 2). (3) The photosensitive resin composition according to the above (1) or (2), wherein the photosensitive resin composition further contains a phenolic compound represented by the above formula (1) or (11). (4) The photosensitive resin composition according to any one of the above items (1) to (3), wherein the carboxylic acid is represented by the formula CnH2n + 1CO〇H (n represents an integer of 11 to 17) (a) The photosensitive resin composition according to any one of the above-mentioned items (1) to (3), wherein the carboxylic acid has i~ in the molecule. (2) The photosensitive resin composition according to any one of the above items (1) to (5), wherein the two-acidic resin is contained in the photosensitive resin composition according to any one of the above items (1) to (5). The constituent unit derived from the (meth)acrylic acid alkyl ester and the constituent unit derived from (meth)acrylic acid. (7) The photosensitive resin composition according to any one of the above items (1) to (6) In the photosensitive resin composition according to any one of the above-mentioned items (1) to (7), the acrylic resin is contained in the photosensitive resin composition according to any one of the above items (1) to (7). 'The weight average molecular weight of the acrylic resin in terms of polystyrene is 5,000^30,000 〇(9). It is described in the above items (1) to (8). In the photosensitive resin composition, the 'alkali-soluble resin is synthesized using an azo polymerization initiator having no cyano group. -9- 1329786 Ο 〇) is described in any one of the above items (1) to (8). In the photosensitive resin composition, the soluble resin was synthesized using an azo polymerization initiator having a cyano group. (11) The photosensitive resin composition according to any one of the above-mentioned items (1) to (8), wherein the soluble resin is an azo polymerization initiator having no cyano group and an ocyan group having a cyano group. A nitrogen-based polymerization initiator is used as a synthesizer. The molar ratio of the azo polymerization initiator having no aromatic group to the azo polymerization initiator having a cyano group is 20:80 to 80:20. Further, the present invention provides the flat display device or the semiconductor device described in the following (12) or (13). (12) A flattening film or an interlayer insulating film formed of the photosensitive resin composition according to any one of the above items (1) to (u). (13) A semiconductor device comprising a planarizing film or an interlayer insulating film formed of the photosensitive resin composition according to any one of the above items (1) to (11). The following film formation method is mentioned. (14) A method of forming a heat-resistant film, which is characterized in that the photosensitive resin composition according to any one of the above items (1) to (11) is patterned, and then subjected to overall exposure, followed by post-baking. . Advantageous Effects of Invention The photosensitive resin composition of the present invention is excellent in stability over time and coating properties, and the photosensitive resin composition of the present invention can form high heat resistance, for example, heat treatment at a high temperature of 20 ° C for 1 hour. After that, it does not cause the 132996 of the film surface to deteriorate 'and maintain flatness'. The film has good light transmittance, low dielectric constant, and solvent resistance. Therefore, the photosensitive resin composition of the present invention can be applied to a flattening film or an interlayer insulating film of a semiconductor element or the like, and an FPD and a semiconductor device having excellent characteristics can be obtained by using the photosensitive resin composition of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. In the photosensitive resin composition of the present invention, an acrylic resin is used as the alkali-soluble resin. However, the alkali-soluble acrylic resin used in the present invention may be any of the acrylic acid-based resins conventionally used as the alkali-soluble resin of the photosensitive resin. The resin is preferably an alkali-soluble acrylic resin synthesized by using an azo polymerization initiator having a cyano group as a polymerization initiator, and an alkali-soluble acrylic resin synthesized using an azo polymerization initiator having no cyano group. Any one of the alkali-soluble acrylic resin synthesized by using an azo polymerization initiator having a cyano group and an azo polymerization initiator having a cyano group. An azo polymerization initiator having no cyano group used in the synthesis of the above alkali-soluble acrylic resin, for example, 1,1'-azobis(1-ethenyloxy-1-phenylethane) 1,1'-azobis(1_propionoxy-1-phenylethane), 1,1,-azobis(1-butoxyl-1-phenylethane), U' -azobis(1·trimethylethoxy-1-phenylethane)' 1,1,-azobis(1-ethenyloxy-1-phenylpropane), U'-azo Bis[1-ethenyloxy]1·(p-methylphenyl)ethane], 1,1,-azobisethoxycarbonyl-1-(p-chlorophenyl)ethane], 1, plant - azobis(1-acetoxy-1-phenylbutane), dimethyl-2,2,-azobis(2-methylpropionate), 1,1,- 1329786 azo Bis(1-chloro-p-phenylethane), 1,1'-azobis(1-chloro-1-propane), 1,1,-azobis[]-espan-1-(p-methyl) Phenyl) 乙院]' 1,1'-azobis[1-involved-1-(p-chlorophenyl)ethane], 1,1'-azobis(1-chloro-1-phenylbutyrate Alkane), 2,2'-azobis U-ethyloxy-3,3-dimethylbutane, 2,2'-azobis(2-acetoxy-4-methylpentyl) Alkane), 2, 2'- Nitrogen bis(2-propoxy-3,3-dimethylbutane), 2,2,_ azobis(2-propenyloxy_4.methylpentane), 2,2'-even Nitrogen bis(2-isobutoxy-3,3-dimethylbutane) 2,2'-azobis(2-isobutoxy-4-methylpentane), 2,2'- Azobis(2-trimethylethoxy-3,3-dimethylbutane), 2,2'-azobis(2-trimethylethoxy-4-methylpentane), 2,2,-azobis(2-benzylideneoxy-3,3-dimethylbutane), 2,2'-azobis(2-benzylideneoxy-4-methylbutyl) Alkane), 2,2'-azobis(2-ethoxypropanepropane), 2,2'-azobis(2-ethoxyoxybutane), 2,2'-azobis (2) -Ethyloxy-3-methylbutane), 2,2'-azobis(2-propoxypropane), 2,2'-azobis(2-propenyloxybutane), 2,2'-azobis(2-propoxycarbonyl-3-methylpropane), 2,2'-azobis(2-isobutyloxypropane), 2,2'-azo double (2. Isobutyloxybutane), 2,2'-azobis(2-isobutyloxy-3-methylbutane), 2,2,-azobis(trimethylethyl) Oxypropane), 2,2 azobis(2·trimethylethoxylate) -3-methylbutane), 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), 1,1 ,-azobis(1-methoxycyclohexane), 2,2'-azobis(2-methyl-N-propionyl) dihydrochloride, 2,2'-azo double [N-(4-Hydroxyphenyl)-2-methylpropionamidine] dihydrochloride, 2,2'-azobis[2-methyl-N-(2-propenyl)propene] Dihydrochloride, 2,2'-azobis[N-(2-hydroxyethyl)-2-methylpropionamidine] dihydrochloride, 2,2,-azobis[2-(5 -Methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2,-azobis[2-(4,5,6,7-tetrahydro-111-1,3-di Azepine-2-yl)propane]dihydrogen 1329786 salt, 2,2'-azobis[2-(5-trans-yl-3,4,5,6-tetrahydropyran-2-yl)-丙院] ~HCl, 2,2 '-azobis[N - (2-propyl)-2-methylpropanosamine], 2,2,-azobis[2-(2-imidazole啉-2-yl)propane], 2,2'-azobis{2-methyl-N-[bis(hydroxymethyl)-2-hydroxyethyl]propanamine}, 2,2,_ Nitrogen double {2_methyl-N-[l,l'.bis(hydroxymethyl)ethyl]propanamide}, 2 2,-azobis[2·methyl-N-(2-hydroxyl) Base) propionamide], 2 , 2'-azobis{2-methylpropanamide} dihydrate, and the like. Preferred azo polymerization initiators having no cyano group are, for example, U1, azobis(1-ethenyloxy-1-phenylethane), 1,1,-azobis(1_-propyl)醯oxy-h phenylethane), 1,1'-azobis(bautinoxy-;!-phenylethane), ^, azobis(1-trimethylethoxy- 1-phenylethane), i,l,-azobis(1-ethyloxy-1-phenylpropane), 1,1'-azobis[1-ethyloxy (p-methyl) Phenyl) ethane], 1,],-azobis[1-ethenyloxy-1-(p-chlorophenyl)ethane], 1, plant-even gas bis(1-chloro-1-benzene Keding Institute) 'Dimethyl-2,2'-azobis(2-methylpropionate) and the like. Further, the above azo-based polymerization initiator having a cyano group is, for example, 1,1,-azobis(cyclohexane·1-cyclohexane-1-carbonitrile) 2,2,-azobis(2- Methylbutyronitrile), 2,2,-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis (2,4 A preferred azo-based polymerization initiator having a cyano group is 2,2'-azobisisobutyronitrile, such as dimethyl-4-methoxyvaleronitrile or the like. In the synthesis of the acrylic resin, an acrylic resin is synthesized using an azo polymerization initiator having no cyano group as a polymerization initiator, and when the resin is used as the acrylic resin of the photosensitive resin composition of the present invention, A film excellent in light transmittance and excellent in heat resistance and solvent resistance can be formed. When the acrylic resin is synthesized by using an azo polymerization initiator having a cyano group as a polymerization initiator, a photosensitive resin composition excellent in heat resistance and solvent resistance can be obtained. In addition, when an acrylic resin is synthesized by using an azo polymerization initiator having no cyano group and an azo polymerization initiator having a cyano group as a polymerization initiator, light transmittance, solvent resistance, and heat resistance can be obtained. A photosensitive resin composition excellent in balance of various properties such as properties. Further, in the case of using either one, the photosensitive resin composition of the present invention is extremely excellent in stability over time. When an acrylic resin is synthesized by using an azo polymerization initiator having no cyano group and an azo polymerization initiator having a cyano group, generally, the molar ratio thereof is in the range of 20:80 to 80:20. Preferably, it is in the range of from 3:70 to 70:30. The alkali-soluble acrylic resin usable in the photosensitive resin composition of the present invention is, for example, (a) an alkali-soluble polyacrylate, (b) an alkali-soluble polymethacrylate, and (c) an acrylate having at least one of At least one methacrylate is used as a constituent unit of alkali-soluble poly(acrylate-methacrylate). These acrylic resins may be used singly or in combination of two or more. Further, in order to form an alkali-soluble resin, these acrylic resins preferably contain an organic acid monomer as a copolymerization component, but the copolymerization single system which imparts alkali solubility to the resin is not limited to the above organic acid monomer. Examples of the monomer component constituting the alkali-soluble polyacrylic resin include acrylate 'methacrylate, organic acid monomer and other copolymerizable monomers. The monomer component constituting these polymers is preferably an acrylate, a methyl decanoate or an organic acid monomer exemplified below. Acrylate: -14- 1329786 methyl acrylate, ethyl acrylate 'n-propyl acrylate, n-butyl acrylate, n-hexyl acrylate, isopropyl acrylate, isobutyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, Benzyl acrylate, acrylate 2-chloroethyl ester, methyl-α-acrylate, benzyl-α-acrylate, and the like. Methacrylate: methyl methacrylate, ethyl methacrylate 'n-propyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, isobutyl methacrylate 'T-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, 1-phenylethyl methacrylate, 2-phenylethyl methacrylate, methyl Ethyl acrylate, diphenyl methyl methacrylate, pentachlorophenyl methacrylate: naphthyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and the like. Organic acid monomer: a monocarboxylic acid such as acrylic acid methacrylic acid or crotonic acid, a dicarboxylic acid such as itaconic acid, maleic acid, fumaric acid, citraconic acid or mesaconic acid, and the like. Anhydride, 2-propenylhydrazine hydride, 2-propylene propylene hydroxy hydride, and the like. Further, as other copolymerizable monomers, for example, maleic acid diester, fumaric acid diester, styrene and styrene derivatives 'acrylonitrile, (meth) acrylamide 'vinyl acetate' chlorine Ethylene, vinylidene chloride, etc. These other copolymers can be used as needed. The amount and the acrylic resin are in an amount which is within the range of the purpose of the invention. The acrylic resin in the present invention preferably contains a constituent unit derived from (meth) propyl 1329886 alkylate and is derived from The copolymer of the constituent unit of (methyl)propionic acid is more preferably 5 to 30 mol% of (meth)acrylic acid. Further, the weight average molecular weight of the alkali-soluble acrylic resin used in the present invention, which is calculated by polystyrene, is preferably 5,000 to 30,000. When the molecular weight of the acrylic resin is less than 5,000, the solvent resistance and heat resistance are inferior. If it exceeds 30,000, the development residue may occur. The sensitizer having a quinonediazide group used in the photosensitive resin composition of the present invention is preferably a reaction of a phenolic compound represented by the above formula (I) or (II) with a naphthoquinonediazide compound. Product. The phenolic compound represented by the formula (I) is, for example, the following compound. The synthesis of these compounds can be suitably carried out by a conventional method, for example, the method described in Patent Document 3.

-16- 1329786

Further, the phenolic compound represented by the formula (Π) is, for example, o-cresol, m-cresol 'p-cresol, 2,4-xylenol, 2,5-xylenol, 2,6-dimethyl Phenol, bisphenol A, B, C, E, F and G, 4,4',4"-methinetriol, 2,6-bis[(2-hydroxy-5-methylphenyl)methyl ]-4-methylindole, 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol, 4,4 '-[1-[4-[2-(4-Hydroxyphenyl)-2-propyl]phenyl]ethylidene] biguanide, 4,4',4"·ethylidene triol, 4- [Bis(4-hydroxyphenyl)methyl)-2-ethoxyphenol, 4,4'-[(2-hydroxyphenyl)methylene]bis[2,3-dimethylphenol], 4 , 4, [(3-hydroxyphenyl)methylene] bis[2,6-dimethyl-17- 1329786 phenol], 4,4'-[(4-hydroxyphenyl)methylene] bis[ 26·dimethylphenol], 2,2′-[(2-hydroxyphenyl)methylene]bis[2,6·dimethylphenol], 2,2′-[(2-hydroxyphenyl) Methylene] bis[3,5-dimethylphenol]' 2,2'-[(4-hydroxyphenyl)methylene]bis[3,5-dimethylphenol], 4,4'- [(3,4-Dihydroxyphenyl)methylene]bis[2,3,6-trimethylphenol], 4-bis(3-cyclohexyl-6-methylphenyl)methyl]-L2 -benzenediol, 4,6-double [(3,5-two Methyl 4-hydroxyphenyl)methyl]-1,2,3-benzenetriol, 4,4'-[(2-hydroxyphenyl)methylene]bis[3-methylphenol], 4 , 4:, 4"-(3-methyl-propylene-3-yl)triol, 4,4',4",4"(1,4-phenylene secondary methyl)tetraphenol, 2 ,4,6_Tri[(3,5-Dimethyl-4-hydroxyphenyl)methyl]-1,3-benzenediol, 2,4,6-tris[(3,5-dimethyl) · 2-Hydroxyphenyl)methyl]-1,3-benzenediol, 4,4'-[1-[4-[1-[4-hydroxy-3,5-bis[(hydroxy_3·A) Phenylphenyl)methyl]phenyl]-1-methylethyl]phenyl]ethylidene]bis[2,6-bis(hydroxymethylphenyl)methyl]phenol, etc. Preferred compounds such as Is 4,4',4"-methinetriol, 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methyl, 4,4'-[1 -[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol ' 4,4'-[1-[4-[2-(4-hydroxyl) Phenyl)-2-propyl]phenyl]ethylidene]bisphenol, 4,4',4''-ethylidenetriol, and the like. Among the phenolic compounds represented by the above formula (II), a compound represented by the following formula (111) or the following formula (IV) is particularly preferred. 1329786

On the other hand, the naphthoquinonediazide compound which is reacted with the phenolic compound represented by the formula (I) or (II) may be formed by reacting with a phenolic compound represented by the formula (I) or (π). Any of the esterified compounds containing a quinonediazide group. The quinonediazide compound is, for example, naphthoquinonediazidesulfonium chloride or benzoquinone represented by 1,2-naphthoquinonediazide-5-sulfonyl chloride or 12-naphthoquinonediazidesulfonium chloride. The β-azidosulfonium halide β esterification reaction of azide sulfonium chloride or the like is, for example, a phenolic compound represented by the above formula (I) or (II) and a quinonediazide sulfonium halide. The catalyst is usually reacted at a temperature of about -20 to 60 ° C in the presence of a sodium hydroxide, sodium carbonate, sodium hydrogencarbonate or triethylamine. The esterification system may be a part or all of the hydroxyl groups of the hydroxyl group of the phenolic compound represented by the formula (1) or (II). The esterification ratio can be suitably adjusted by adjusting the amount of the phenolic compound represented by the formula (I) or (II) and the amount of the compound having quinonediazide. In the esterification reaction, various mixtures having different esterification numbers and esterification positions can be obtained from 19 to 1329786. Thus, the esterification rate is expressed as the average enthalpy of the mixtures. Further, these reaction products may be used singly or in combination of two or more. In the present invention, by using the reaction product of the phenolic compound represented by the above formula (I) or (II) and the naphthoquinonediazide compound, it is excellent in long-term storage stability, light transmittance, solvent resistance, In the present invention, the reaction product is usually used in an amount of from 1 to 30 parts by weight based on 100 parts by weight of the alkali-soluble resin component in the photosensitive resin composition. Further, as the light-sensitive agent, together with the above reaction product, other photosensitizers may be used within the range not inhibiting the object of the present invention. Further, the photosensitive resin composition of the present invention contains a curing agent having an epoxy group as a curing agent. The epoxy group-containing curing agent is, for example, a bisphenol epoxy resin cresol/novolac epoxy resin, a cyclic aliphatic epoxy resin, a glycidyl ether epoxy resin, or a glycidylamine epoxy resin. Resin, heterocyclic epoxy resin, etc. However, the curing agent which can be used in the present invention is not limited to these polymer epoxy resins, and may be a low molecular weight epoxy compound such as bisphenol A or a glycidyl ether of bisphenol F. The amount of the epoxy group-containing hardener is preferably from 2 to 60 parts by weight, more preferably from 10 to 40 parts by weight, per 100 parts by weight of the alkali-soluble resin. Further, the photosensitive resin composition of the present invention A carboxylic acid can be used. The carboxylic acid which can be used in the present invention may be an unsaturated carboxylic acid or an unsaturated carboxylic acid. A preferred saturated carboxylic acid is, for example, a C12-C18 fatty acid represented by the formula: CnH2n+1COOH (n represents an integer of 11 to 17). The aliphatic group of the saturated fatty acid represented by the above formula may be linear or branched, but is preferably a linear aliphatic -20-1329786 aliphatic group. These saturated fatty acids are, for example, lauric acid, endomyric acid, palmitic acid, stearic acid and the like, of which stearic acid and lauric acid are preferred. Further, a preferred unsaturated carboxylic acid is a C12 to C24 unsaturated fatty acid having 1 to 3 unsaturated double bonds in the molecule. As the unsaturated fatty acid having one double bond, for example, tetradecanoic acid [CH3(CH2)7CH=CH(CH2)COOH], sinapic acid [CHHCH^hCIKmCHOHCOOH], cis-U-eicosenoic acid [CH3 ( CH2)7CH = CH(CH2)9COOH], oleic acid [CH3(CH2)CH7 = CH(CH2)7COOH], palmitic acid [CH(CH)CH, CH(CH)COOH], myristoleic acid [CH3 (CH2)CH=CH(CH2)7COOH]' cis-5-dodecenoic acid [CH3(CH2)5CH=CH(CH2)3COOH), etc.; as an unsaturated fatty acid having two double bonds, for example, 11 , 14 - eicosadienoic acid [CH3(CH2)4CH = CHCH2)2(CH2)8COOH], linoleic acid [CH3(CH2)4(CH=CHCH2)2(CH2)6COOH], etc.; 3 double-bonded unsaturated fatty acids, such as cis-8, 1 1,1 4 -eicosatrienoic acid [CH3(CH2)3(CH=CHCH2)2(CH2)6COOH], linolenic acid [CH3 (CH = CHCH2) 3(CH2)7COOH] and the like. In the unsaturated fatty acid, when the length of the alkyl chain is shortened, the white turbidity preventing effect tends to be small. On the other hand, when the alkyl chain is elongated, the white turbidity preventing effect is good, but the development residue occurs. Case. Further, when the alkyl chain is elongated, the melting point is at room temperature or higher, and since boiling occurs during drying under reduced pressure, it is preferred to select an unsaturated fatty acid which does not have such a problem. One of the most preferred unsaturated fatty acids is oleic acid. The photosensitive resin composition of the present invention preferably contains a reaction product of the above-mentioned alkali-soluble 1329786 acrylic resin, a phenolic compound represented by the above formula (I) or (II), and a naphthoquinonediazide compound, and The epoxy group-containing curing agent preferably further contains a phenolic compound represented by the above formula (1) or (II). The phenolic compound represented by the above formula (1) or (II) is usually used as a dissolution inhibitor in the photosensitive resin composition of the present invention to adjust the dissolution rate, or to increase the residual film ratio or adjustment of the photosensitive resin composition. Sensitivity. The phenolic compound represented by the formula (II) is preferably a phenolic compound represented by the above formula (III) or (IV). These phenolic compounds are used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the alkali-soluble resin. In the photosensitive resin composition of the present invention, a solvent for dissolving an alkali-soluble resin, a photosensitizer, a curing agent, a carboxylic acid, a phenolic compound or the like to form a solution of the photosensitive resin composition, for example, ethylene glycol monomethyl Ethylene glycol monoalkyl ethers such as ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoalkyl ether acetate, diethylene glycol a propylene glycol monoalkyl ether such as diethylene glycol dialkyl ether such as dimethyl ether or diethylene glycol diethyl ether diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether, propylene glycol Propylene glycol monoalkyl ether acetate such as monomethyl ether acetate propylene glycol monoethyl ether acetate, lactic acid ester such as methyl lactate 'ethyl lactate, aromatic hydrocarbon such as toluene or xylene, methyl ethyl ketone a ketone such as 2-heptanone or cyclohexanone; a guanamine such as N,N-dimethylacetamide or N-methylpyrrolidone; or a lactone such as γ-butyrolactone. These solvents may be used singly or in combination of two or more. In the photosensitive resin composition of the present invention, an adhesion aid, a surfactant, or the like may be blended as needed. Examples of the adhesion promoter are alkyl imidazoline, butyric acid, alkane-22-1329786 acid, polyhydroxystyrene, polyvinyl methyl ether 'tert-butyl novolac, epoxy decane, epoxy polymer, decane, and the like. The surfactant is, for example, a nonionic surfactant such as a polyglycol and a derivative thereof, that is, polypropylene glycol or a polyoxyethylene lauryl ether, a fluorine-containing surfactant, such as Fluoride (trade name, Sumitomo 3M ( Co., Ltd.), Meika Fluor (trade name, Dainippon Ink Chemical Industry Co., Ltd.), Seflon (trade name, Asahi Glass Co., Ltd.), or organic oxane surfactant, such as KP 341 (trade name, Shin-Etsu Chemical Industry Co., Ltd.). The photosensitive resin composition of the present invention can be prepared by dissolving each component in a predetermined amount of a solvent. In this case, each component may be separately dissolved in a solvent in advance, and the components may be prepared by mixing the components in a predetermined ratio immediately before use. Usually, the solution of the photosensitive resin composition is used after being filtered by using a 2 μm filter or the like. The photosensitive resin composition of the present invention can be used as a film having a high insulating property, high transparency, high heat resistance, solvent resistance, a flat film or an interlayer insulating film, etc. by the following method. First, the present invention is A solution of the photosensitive resin composition is applied onto a substrate and prebaked to form a coating film (photoresist film) of the photosensitive resin composition. In this case, the substrate to which the photosensitive resin composition is applied may be any known substrate such as a conventional FPD or a substrate for forming a semiconductor device such as glass or tantalum. The substrate may be a bare substrate, or an oxide film, a nitride film, a metal film or the like may be formed, or a substrate on which a circuit pattern or a semiconductor element or the like is formed may be used. Next, the photoresist film is exposed through a predetermined mask, and then the image is processed by using an alkali developing solution, and if necessary, a rinsing treatment can be performed to form a positive film pattern of the photosensitive resin composition. After the full exposure, post-baking is applied, thus forming a film having a high heat-resistant temperature. 1329786 The exposure at full exposure can usually be 600mJ/cm2 or more. Further, the post-baking temperature is usually from 150 to 250 ° C, preferably from 180 to 23 ° C. The post-baking time is usually 30 to 90 minutes. Although the reason why the method of the present invention can form a film having a high heat-resistant temperature is not determined, it is presumed that the photosensitive agent is decomposed by the overall exposure to form an acid to promote crosslinking and hardening of the hardener having an epoxy group, thereby forming high heat resistance. Sex film. The formed high-heat-resistance film positive pattern can be used as a flattening film or an interlayer insulating film of a FPD such as a semiconductor element, a liquid crystal display device, a plasma display panel, or the like. Further, in the case of forming a film having heat resistance and solvent resistance in total, pattern exposure, development, or the like may not be performed. In the formation of the above-mentioned film, as a method of applying the photosensitive resin composition solution, any of a spin coating method, a roll coating method, a flange coating method, a spray coating method, a cast coating method, a dip coating method, or the like can be used. method. Further, the radiation used for the exposure may be, for example, ultraviolet rays such as g-line, far ultraviolet rays such as KrF excimer laser or ArF quasi-molecular laser light, X-rays, electron lines, or the like. Further, as the development method, a method used in conventional photoresist development such as a stirring development method, an immersion development method, or a immersion immersion development method may be employed. Further, the developer may be, for example, an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate or sodium hydride, ammonia, ethylamine, propylamine, diethylamine, diethylamine ethanol or triethylamine. An organic amine, a quaternary amine such as tetramethylammonium hydroxide or the like. EXAMPLES Hereinafter, the present invention will be more specifically illustrated by the examples, but the aspects of the invention are not limited by the examples. Synthesis Example 1 (Synthesis of Acrylic Copolymer 1) • 24- 1329786 In a 200 ml four-necked flask equipped with a stirrer, a cooling tube, and a thermometer 'nitrogen introduction tube, put and stir 7 g of propylene glycol monomethyl ether acetate Ester, m g methyl methacrylate, 90 g 2-hydroxypropyl methacrylate, 39 g methacrylic acid, 12.6 g dimethyl 2,2'-azobis(2-methylpropionate) The temperature was raised while blowing nitrogen gas, and polymerization was carried out at 85 ° C for 8 hours to obtain an acrylic copolymer 1 having a weight average molecular weight of 11. Synthesis Example 2 (Synthesis of Acrylic Copolymer 2)

Into a 200-neck four-necked flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen inlet tube, put and stir 700 g of propylene glycol monomethyl ether acetate '171 g of methyl methacrylate, 90 g of 2-hydroxy methacrylate Propyl ester, 39 g methacrylic acid, 6.3 g dimethyl 2,2'-azobis(2-methylpropionate) [molecular weight: 230.26]' 4.5 g azobisisobutyronitrile [molecular weight: 164.21] The temperature was raised while blowing nitrogen gas, and polymerization was carried out at 85 ° C for 8 hours to obtain an acrylic copolymer 2 having a weight average molecular weight of 1,1 Å. Synthesis Example 3 (Synthesis of Acrylic Copolymer 3)

In a 2 mL four-necked flask equipped with a stirrer 'cooling tube, thermometer' and nitrogen inlet tube, 700 g of propylene glycol monomethyl ether acetate, 171 g of methyl methacrylate, and 90 g of methacrylic acid were added and stirred. Hydroxypropyl ester, 39 g of methacrylic acid, and 9 g of azobisisobutyronitrile were heated while blowing nitrogen gas, and polymerized at 85 ° C for 8 hours to obtain an acrylic copolymer 3 having a weight average molecular weight of 11, fluorene. Example 1 1 part by weight of the acrylic copolymer obtained in Synthesis Example 1 and 25 parts by weight of an esterified product represented by the following formula (V) (esterification ratio: 50) and 5 parts by weight of the above formula (III). a phenolic compound, 17 parts by weight of an epoxy group-containing hardener, Dekumoa-25- 1329786 VG3 1 OIL (manufactured by Mitsui Chemicals Co., Ltd.), and 1.0 part by weight of stearic acid dissolved in propylene glycol monomethyl ether acetate /Ethyl lactate (75/25), in order to prevent possible radial wrinkles on the photoresist film during spin coating, so-called streaks, and add 300 ppm of fluorine-based surfactant, ie, meflurazine R-08 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), after stirring, was filtered with a filter of 〇.2 μm to prepare the photosensitive resin composition 1 of the present invention.

<Formation of Thin Film Pattern> The photosensitive resin composition 1 obtained above was spin-coated on a 4-inch wafer, and baked on a hot plate at 100 ° C for 9 sec seconds to obtain a thickness of 3.0 μm. Photoresist film. For the photoresist film, the test pattern of various line widths and contact holes which are most suitable for the line and gap width of 1:1 is most suitable for the g + h + i line mask aligner (PLA-501F) manufactured by Canon. The exposure was exposed to 23 in a 0.4 wt% aqueous solution of tetramethylammonium hydroxide 26- 1329786 in ammonium. (: 60 seconds of development, and a pattern and contact hole having a line and gap width of 1:1 were formed. <Evaluation of film surface characteristics>

The patterned substrate obtained as described above was subjected to full exposure (600 mJ/cm 2 ) by a g + h + i line mask aligner (PLA-501F) manufactured by Canon, and then at 120 ° on a hot plate. After heat treatment for 15 minutes, the mixture was heat-treated at 220 ° C for 60 minutes by a circulating cleaning oven. Then, the surface state of the film was observed with an optical microscope. If no white turbidity was observed, it was evaluated as 〇, when it was observed to be slightly cloudy, it was evaluated as Δ, and when white turbidity was observed, it was evaluated as X. The results are shown in Table 1. <Evaluation of stability over time>

The photosensitive resin composition 1 obtained above was allowed to stand at 5 ° C for 20 days as sample A, and was allowed to stand at 23 ° C for 20 days as sample B. Sample A and Sample B were each spin-coated on a 4 Å wafer, and baked on a 10 TC hot plate for 90 seconds to obtain a 3.0 thick photoresist film. The photoresist film was obtained by Canon ( The g + h + i-line mask aligner (PLA-501F) is exposed to the exposure of the test pattern of various line widths and contact holes that are most suitable for line and gap widths of 1:1, at 0.4% by weight. The image was developed at 23 ° C for 60 seconds in an aqueous solution of tetramethylammonium hydroxide to form a pattern and contact hole having a line and gap width of 1:1. The thickness of the photoresist film after development was divided by the thickness of the photoresist film after coating. The obtained enthalpy is expressed as a percentage, and is defined as the residual film ratio. If the difference between the residual film ratios of the sample A and the sample B is less than 3%, it is evaluated as 〇, and if the residual film rate difference is 3% or more, it is evaluated as X. The results are shown in Table 1. Example 2 A photosensitive resin composition 2 was prepared in the same manner as in Example 1 except that the acrylic copolymer 2 obtained in Synthesis Example 2 was used instead of the acrylic -27-1329786 copolymer 1. Using the photosensitive resin composition 2, a film pattern was formed in the same manner as in Example 1, and the surface properties of the film were evaluated and stabilized over time. The evaluation results are not shown in Table 1. Example 3 A photosensitive resin was prepared in the same manner as in Example 1 except that the acrylic copolymer 3 obtained in Synthesis Example 3 was used instead of the acrylic copolymer 1. Composition 3. Using the photosensitive resin composition 3, a film pattern was formed in the same manner as in Example 1, and evaluation of film surface properties and evaluation of stability over time were carried out. The evaluation results are shown in Table 1. Example 4 An esterified product (esterification ratio: 5 Å) of a phenolic compound represented by the above formula (ΙΠ) and 1,2-naphthoquinone di-azidosulfonyl chloride is used in place of the sensitizer of the formula (V). In the same manner as in Example 1, the photosensitive resin composition 4 was prepared. The film pattern was formed in the same manner as in Example 1 using the photosensitive resin composition 4', and the evaluation of the surface properties of the film and the evaluation of the stability over time were performed. The results are shown in Table 1. In the same manner as in Example 4 except that the acrylic copolymer 2 obtained in Synthesis Example 2 was used instead of the acrylic copolymer 1, the photosensitive resin composition 5 was prepared. Sensitivity The resin composition 5' was formed into a film pattern in the same manner as in Example 4, and evaluation of film surface characteristics and evaluation of stability over time were performed. The evaluation results are shown in Table 1. Example 6 -28 - 1329786 Except that the synthesis example 2 was used In the same manner as in Example 4 except that the obtained acrylic copolymer 3 was used in place of the acrylic copolymer 1, the photosensitive resin composition was prepared at 6°, and the photosensitive resin composition 6 was used, and a film was formed in the same manner as in Example 4. The pattern was evaluated for the evaluation of the surface properties of the film and the evaluation of the stability over time. The evaluation results are shown in Table 1. Example 7 The same procedure as in Example 1 was carried out except that lauric acid was used instead of stearic acid to prepare photosensitivity. Resin composition 7. Using this photosensitive resin composition 7, a film pattern was formed in the same manner as in Example 1, and evaluation of film surface characteristics was evaluated. The evaluation results are shown in Table 1. (Example 8) A photosensitive resin composition 8 was prepared in the same manner as in Example 2 except that lauric acid was used instead of stearic acid. Using this photosensitive resin composition 8, a film pattern was formed in the same manner as in Example 2, and evaluation of film surface characteristics and evaluation of stability over time were performed. The evaluation results are shown in Table 1. (Example 9) A photosensitive resin composition 9 was prepared in the same manner as in Example 3 except that lauric acid was used instead of stearic acid. Using this photosensitive resin composition 9, a film pattern was formed in the same manner as in Example 3, and evaluation of film surface characteristics and evaluation of stability over time were performed. The evaluation results are shown in Table 1. Example 1 0 A photosensitive resin composition was prepared in the same manner as in Example 4 except that lauric acid was used instead of stearic acid. Using this photosensitive resin composition 10, a film pattern was formed in the same manner as in Example 4, and evaluation of the surface stability of the film was carried out in -29 to 1329786. The evaluation results are shown in Table 1. (Example 1) The photosensitive resin composition 11 was prepared in the same manner as in Example 5 except that lauric acid was used instead of stearic acid. Using the photosensitive resin composition 11, a film pattern was formed in the same manner as in Example 5, and evaluation of the film surface characteristics was evaluated. The evaluation results are shown in Table 1. Example 1 2

The photosensitive resin composition 12 was prepared in the same manner as in Example 6 except that lauric acid was used instead of stearic acid. Using this photosensitive resin composition 12, a film pattern was formed in the same manner as in Example 6, and evaluation of film surface properties and evaluation of stability over time were performed. The evaluation results are shown in Table 1. Example 1 3 100 parts by weight of the acrylic copolymer obtained in Synthesis Example 1, 25 parts by weight of the esterified product represented by the above formula (V) (esterification ratio: 5 Å), and 5 parts by weight of the above formula (III) Phenolic compound '14 parts by weight of an epoxy group-containing hardener, Dekumoa VG 31 OIL (manufactured by Mitsui Chemicals Co., Ltd.) and 5.0 parts by weight of oleic acid dissolved in propylene glycol monomethyl ether acetate / ethyl lactate (7 In 5/25), in order to prevent possible radial ridges on the photoresist film during spin coating, so-called streaks, 300 ppm of a fluorine-based surfactant is added, that is, mecarfluoric acid R-〇8 (Daily Ink Chemical Industry Co., Ltd.), after stirring, it was filtered with a 0.2 μm filter to prepare the photosensitive resin composition 13 of the present invention. Comparative Example 1 A photosensitive resin composition I4 was prepared in the same manner as in Example 1 except that stearic acid was not used. The photosensitive resin composition 14 was formed in the same manner as in Example -30-1329786 〇〇〇〇〇〇〇〇〇〇〇〇〇x〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇x Example 1. The film pattern was evaluated for the evaluation of the surface properties of the film and the evaluation of the stability over time. The evaluation results are shown in Table 1. Comparative Example 2 In the same manner as in Example 1, except that 1.0 part by weight of U-CATSA 106 (manufactured by SAN-APRO Co., Ltd.) was used as the curing accelerator, the photosensitive resin composition 15 was used to prepare the photosensitive resin. In the composition 14, a film pattern was formed in the same manner as in Example 1, and evaluation of the surface properties of the film and evaluation of the stability over time were performed. The evaluation results are shown in Table 1. Table 1 Evaluation of film surface properties Evaluation of stability over time Examples: Examples, examples, examples, examples, application, implementation, implementation, implementation, implementation, implementation, implementation Authentic ratio

<Evaluation of the low-temperature storage property> Each of the photosensitive resin compositions 13 and 15 was placed in 180 cc of a 200 cc transparent glass bottle, and allowed to stand at 5 ° C for 10 hours. Photosensitive tree in the present invention

-31-^29786 I-time replacement page Corrected precipitation of crystals was not observed in the male fat composition 1 3, but precipitation of crystals occurred in the comparative photosensitive resin composition 15 . <With or without bump evaluation>

The photosensitive resin composition was spin-coated on a 4 Å wafer, respectively, and baked on a 9 〇t t hot plate for 90 seconds to obtain a 3.0 μm thick photoresist film. The photoresist film was placed in a decompression device and decompressed to 10 Torr. No bubbles were formed on the surface of the photoresist film coated with the photosensitive resin composition 13 of the present invention, but bubbles were formed on the surface of the photoresist film coated with the comparative photosensitive resin composition 15, and it was found that a bubble was generated. As a result of the above, it was found that the photosensitive resin composition of the present invention has an excellent balance between film surface properties and stability over time. Further, the photosensitive resin compositions of the examples were all excellent in terms of the insulating properties of the photoresist film after the heat treatment. Further, the films formed in Examples 1 to 13 were also excellent in heat resistance, solvent resistance, flatness, and electrical properties, and no swelling was observed even after application and drying under reduced pressure.

On the other hand, the photosensitive resin composition of Comparative Example 1 containing no carboxylic acid became cloudy due to heating after exposure, and the photosensitive resin composition of Comparative Example 2 containing a curing accelerator to prevent white turbidity The stability of time is poor. -32-

Claims (1)

I32m6- •pi"Daily Amendment No. 9 3 1 1 8 7 1 8 "Photosensitive Resin Composition" Patent (amended on May 11, 2010) X. Patent application scope: 1. Composition of photosensitive resin And comprising a soluble resin, a sensitizer having a quinonediazide group, and a hardener, wherein the soluble resin is an acrylic resin, the hardener contains an epoxy group, and the photosensitive resin composition further contains a carboxylic acid, the carboxyl group The acid is selected from the group consisting of CI2 to CI8 saturated fatty acids represented by the formula cnH2n + lc00H (n represents an integer of n to 17) and Ci2 to C24 unsaturated fatty acids having 1 to 3 unsaturated double bonds in the molecule. At least one of the group φ, wherein the sensitizing agent having a quinonediazide group is 1 to 30 parts by weight and the hardener is 2 to 60 parts by weight with respect to 100 parts by weight of the soluble resin. 2. The photosensitive resin composition according to claim 1, wherein the bismuth-containing sensitizer is a phenolic compound represented by the following formula (I) or (Π) and naphthoquinone Reaction product of azide compound: nw OH Wherein R1, ^2, 1^3, and R4 each independently represent Η or C1-C2 院基 R5 and R6 each independently represent a Ci-Ca alkyl group; 1329786 (wherein R7, R8, R9, R1, R1, and 2, and R 3 each independently represent H, C丨-C4 alkyl or , m and η are each independently representing an integer of 〇~2, and a, b, c, d, e, f, g, and h are satisfying a + bS5, c + d$5, e + fS5, g + hS5 An integer from 0 to 5, i is an integer from 0 to 2.) 3. The photosensitive resin composition according to claim 1 or 2, further comprising φ a phenolic compound represented by the above formula (I) or (Π). 4. The photosensitive resin composition of claim 1, wherein the acrylic resin contains a constituent unit derived from an alkyl (meth)acrylate and a constituent unit derived from (meth)acrylic acid. 5. The photosensitive resin composition of claim 1 wherein the acrylic resin contains 5 to 30 mol% of a constituent unit derived from (meth)acrylic acid. A photosensitive resin composition according to any one of claims 1 to 4, wherein the acrylic resin has a weight average molecular weight of 5,000 to 30,000 in terms of polystyrene. 7. The photosensitive resin composition of claim 1, wherein the alkali-soluble resin is synthesized using an azo polymerization initiator having no cyano group. 8. The photosensitive resin composition of claim 1, wherein the alkali-soluble resin is synthesized using an azo polymerization initiator having a cyano group. 9. The photosensitive resin composition of claim 1, wherein the alkali-soluble resin is synthesized by using an azo polymerization initiator having no cyano group and an azo polymerization initiator having a cyano group; The molar ratio of the azo polymerization initiator having no cyano group to the azo polymerization initiator having a cyano group is 20:80 to 80:20. 10. A flat panel display characterized by having a flattening film or an interlayer insulating film formed of the photosensitive resin composition as set forth in any one of claims 1 to 9. A semiconductor device characterized by having a planarizing film or a interlayer insulating film formed of a photosensitive resin composition as set forth in any one of claims 1 to 9. A method of forming a heat-resistant film, which is characterized in that a photosensitive resin composition according to any one of claims 1 to 9 is used for patterning, followed by full exposure, followed by post-baking.