JP2010210851A - Photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition, having high sensitivity and little film reduction upon development, regardless of the duration time of left-standing, from an exposure step to a post-exposure baking step. <P>SOLUTION: The photosensitive resin composition contains: (a) an alkali soluble resin; (b) a photopolymerizable compound; (c) a photopolymerization initiator; (d) a photoacid generator; and (e) a crosslinking agent that reacts by an acid. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition. More specifically, the present invention relates to a negative photosensitive resin composition that is easily dissolved in an alkaline aqueous solution before exposure and becomes insoluble in the alkaline aqueous solution upon exposure.

  As insulating materials used for semiconductor integrated circuits and printed circuit boards, photosensitive resin compositions such as photosensitive polyimide and photosensitive polybenzoxazole have been developed and put into practical use. In these photosensitive resin compositions, in recent years, in consideration of the environment, photosensitive resin compositions that can be developed with an aqueous alkaline solution from development with a conventional organic solvent have been developed. Such a photosensitive resin composition is required to have sensitivity and chemical resistance as important characteristics.

  As a negative photosensitive resin composition that can be developed with an alkaline aqueous solution, a photosensitive resin composition comprising a polyimide having an alkali-soluble group at the end of the main chain, a polymerizable compound, a polymerization initiator, and a thermally crosslinkable compound. A thing (for example, refer patent documents 1-2) is proposed. However, these photosensitive resin compositions cannot be said to have sufficient sensitivity, and further improvement is necessary.

  In addition, a negative photosensitive resin composition (for example, see Patent Document 3) containing an alkali-soluble resin, a polymerizable group-containing compound, a photoacid generator, and a crosslinking agent that reacts with an acid, a polyimide polymer, and a photoacid generator. And a resin composition containing a crosslinking agent (see, for example, Patent Document 4) have been proposed. However, these resin compositions need to be baked immediately after exposure, and there is a problem that the sensitivity greatly decreases as the standing time from exposure to post-exposure baking increases, and the film loss during development increases. .

International Publication No. 2004/109403 Pamphlet International Publication No. 2006/098291 Pamphlet JP 2008-76740 A JP 2008-231255 A

  An object of the present invention is to provide a photosensitive resin composition capable of forming a cured film with high sensitivity and reduced film loss during development regardless of the standing time from exposure to post-exposure baking.

  In order to solve the above problems, the photosensitive resin composition of the present invention has the following constitution. That is, it contains (a) an alkali-soluble resin, (b) a photopolymerizable compound, (c) a photopolymerization initiator, (d) a photoacid generator, and (e) a crosslinking agent that reacts with an acid. It is a photosensitive resin composition.

  According to the present invention, it is possible to obtain a photosensitive resin composition having high sensitivity and small film loss during development regardless of the standing time from exposure to baking after exposure. The photosensitive resin composition of the present invention can be suitably used for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, a wiring protective insulating film of a circuit board, and the like.

  Hereinafter, the present invention will be described in detail. The photosensitive resin composition of the present invention comprises (a) an alkali-soluble resin, (b) a photopolymerizable compound, (c) a photopolymerization initiator, (d) a photoacid generator, and (e) a crosslinking agent that reacts with an acid. It is characterized by containing. By containing all these components, it is possible to obtain a photosensitive resin composition having high sensitivity and small film loss during development, regardless of the standing time from exposure to post-exposure baking. For example, Patent Documents 1 and 2 disclose (a) to (c) and (d) as components constituting the photosensitive resin composition, but these photosensitive resin compositions have sufficient sensitivity. is not. On the other hand, for example, Patent Document 3 discloses a so-called chemically amplified negative photosensitive resin composition containing components (a) to (b) and (d) to (e). In such a photosensitive resin composition, the crosslinking reaction is insufficient only by exposure, and the crosslinking by the acid catalyst reaction is promoted by the subsequent baking treatment, and a cured film is obtained. However, in this method, it is necessary to perform a baking process immediately after the exposure, and as the standing time from the exposure to the post-exposure baking is extended, the sensitivity is greatly lowered, and the film loss during development is increased. This is because (d) the acid generated from the photoacid generator by light irradiation acts with the base component contained in the composition or in the atmosphere over time, and is deactivated before the post-exposure bake treatment. This is probably because of this. On the other hand, in the present invention, by combining (b) a photopolymerizable compound and (c) a photopolymerization initiator with (d) a photoacid generator and (e) a crosslinking agent that reacts with an acid, Radicals are generated and the exposed area is instantly crosslinked. Since the molecular motion of the exposed portion is limited by this cross-linking, the reaction between the acid generated from the photoacid generator (d) and the base component is suppressed, and the deactivation of the acid can be reduced. As a result, it is possible to obtain a cured film having a small film loss at the time of development irrespective of the standing time from exposure to post-exposure baking. Furthermore, when compared with a conventionally known negative photosensitive resin composition containing (b) a photopolymerizable compound and (c) a photopolymerization initiator, in the present invention, (b) a photopolymerizable compound and (c) light In addition to crosslinking by a polymerization initiator, (d) a crosslinking effect by a photoacid generator and (e) a crosslinking agent that reacts with an acid can be obtained, so that sensitivity can be improved. Therefore, according to the present invention, it is possible to obtain a photosensitive resin composition having high sensitivity and excellent chemical resistance irrespective of the standing time from exposure to post-exposure baking and having a small film loss during development.

  The photosensitive resin composition of the present invention contains (a) an alkali-soluble resin. In the present invention, alkali-soluble means that a solution in which a resin is dissolved in γ-butyrolactone is applied on a silicon wafer and prebaked at 120 ° C. for 4 minutes to form a prebaked film having a thickness of 10 μm ± 0.5 μm. The dissolution rate obtained from the decrease in film thickness when the membrane is immersed in a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ± 1 ° C. for 1 minute and then rinsed with pure water is 50 nm / min or more. Say.

  The (a) alkali-soluble resin used in the present invention preferably has an acidic group in the structural unit of the resin and / or at the end of the main chain in order to impart the alkali solubility. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. Moreover, it is preferable to have a fluorine atom, and when developing with an alkaline aqueous solution, water repellency can be imparted to the interface of the film and penetration of the interface can be suppressed. The fluorine atom content in the alkali-soluble resin is preferably 5% by weight or more from the viewpoint of preventing the penetration of the interface, and preferably 20% by weight or less from the viewpoint of solubility in an aqueous alkali solution.

  Examples of (a) alkali-soluble resins include polyimides, polyimide precursors, polyhydroxyamides that are polybenzoxazole precursors, acrylic resins having alkali-soluble groups, polyhydroxystyrene, novolac resins, and resole resins. Examples of the polyimide precursor include polyamic acid, polyamic acid ester, polyamic acid amide, polyisoimide, and the like. Two or more of these may be contained. Of these resins, polyimide, polyimide precursor, and polyhydroxyamide are preferable from the viewpoint of heat resistance and toughness of the cured film. Furthermore, polyimide is more preferable from the viewpoint of chemical resistance in low-temperature curing at 250 ° C. or lower.

  The polyimide described above has a structural unit represented by the following general formula (1), and the polyimide precursor and the polyhydroxyamide have a structural unit represented by the following general formula (2). Two or more of these may be contained, or a resin obtained by copolymerizing the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) may be used.

In general formula (1), R ¹ represents a 4 to 10 valent organic group, and R ² represents a ² to 8 valent organic group. R ³ and R ⁴ represent a phenolic hydroxyl group, a sulfonic acid group or a thiol group, and may be the same or different. p and q represent the integer of 0-6.

In general formula (2), R ⁵ represents a divalent to octavalent organic group, and R ⁶ represents a divalent to octavalent organic group. R ⁷ and R ⁸ represent a phenolic hydroxyl group, a sulfonic acid group, a thiol group, or COOR ⁹ and may be the same or different. R ⁹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. r and s represent the integer of 0-6. However, r + s> 0.

  The (a) alkali-soluble resin in the present invention preferably has 10 to 100,000 structural units represented by the general formula (1) or (2). Further, in addition to the structural unit represented by the general formula (1) or (2), another structural unit may be included. In this case, it is preferable that the structural unit represented by the general formula (1) or (2) has 50 mol% or more in all the structural units.

In the general formula (1), R ^1- (R ³ ) _p represents a residue of acid dianhydride. R ¹ is a tetravalent to 10-valent organic group, and among them, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable.

  Specific examples of the acid dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,3,3 ′, 4′-biphenyltetracarboxylic acid. Acid dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3 ′ -Benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1 -Bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, Bis (2,3-dicarboxy Phenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid Anhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorenic dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2- Bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, acid dianhydride having the structure shown below, etc. Examples include aliphatic tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, and the like. it can. Two or more of these may be used.

R ¹⁰ represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ . R ¹¹ and R ¹² represent a hydrogen atom, a hydroxyl group or a thiol group.

In the general formula (2), R ^5- (R ⁷ ) _r represents an acid residue. R ⁵ is a divalent to octavalent organic group, and among them, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable.

  Examples of the acid component include dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid. Examples of tetracarboxylic acids such as acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyl Tetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 2,2 ′, 3,3′-benzophenonetetracarboxylic acid, 2 , 2-bis (3,4-dical Xylphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,1-bis (3,4-dicarboxyphenyl) ethane, 1,1-bis (2,3- Dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxy) Phenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10 -Perylenetetracarboxylic acid and aromatic tetracarboxylic acid having the structure shown below, butanetetracarboxylic acid, 1,2,3,4-cyclopenta , And the like aliphatic tetracarboxylic acids such as tetracarboxylic acid. Two or more of these may be used.

R ¹⁰ represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ . R ¹¹ and R ¹² represent a hydrogen atom, a hydroxyl group or a thiol group.

Among these, in tricarboxylic acid and tetracarboxylic acid, one or two carboxyl groups correspond to the R ⁷ group in the general formula (2). Further, dicarboxylic acids exemplified above, tricarboxylic acid, a hydrogen atom of the tetracarboxylic acid of the general formula (2) in the R ⁷ groups, preferably those 1-4 substituted by a hydroxyl group or a sulfonic acid group, a thiol group More preferred. These acids can be used as they are, or as acid anhydrides and active esters.

R ² — (R ⁴ ) _q of the general formula (1) and R ⁶ — (R ⁸ ) _s of the general formula (2) represent a diamine residue. R ² and R ⁸ are divalent to octavalent organic groups, and among them, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable.

  Specific examples of diamines include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, p -Phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4 -(4-aminophenoxy) phenyl} -Ter, 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′-di (trifluoromethyl) -4,4′-diaminobiphenyl, 9,9-bis (4-aminophenyl) fluorene or Compounds in which at least a part of hydrogen atoms of these aromatic rings are substituted with alkyl groups or halogen atoms, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and Such as diamine of the structure, and the like. Two or more of these may be used.

R ¹⁰ represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ . R ^{11 to} R ¹⁴ represent a hydrogen atom, a hydroxyl group, or a thiol group.

  These diamines can be used as diamines or as corresponding diisocyanate compounds, trimethylsilylated diamines.

  The polyimide precursor preferably used in the present invention can be obtained by reacting tetracarboxylic acid, corresponding tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride and the like with diamine, corresponding diisocyanate compound, and trimethylsilylated diamine. Polyimide can be generally obtained by dehydrating and ring-closing polyamic acid, which is one of polyimide precursors obtained by reacting tetracarboxylic dianhydride and diamine, by heating or chemical treatment such as acid or base. .

  The polyhydroxyamide preferably used in the present invention can be obtained by reacting bisaminophenol with a dicarboxylic acid, a corresponding dicarboxylic acid chloride, a dicarboxylic acid active ester, or the like.

  Moreover, the resin which has an acidic group at the principal chain terminal can be obtained by sealing the terminal of these resins with the above-mentioned monoamine, acid anhydride, acid chloride, and monocarboxylic acid having an acidic group.

  Preferred examples of such monoamines include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy- 4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4- Aminobenzoic acid, 4-aminosalicylic acid, 5-aminosa Tyric acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like can be mentioned. Two or more of these may be used.

  Preferred examples of such acid anhydrides, acid chlorides, and monocarboxylic acids include acid anhydrides such as phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic acid anhydride, and 3-hydroxyphthalic acid anhydride. 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, Monocarboxylic acids such as 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid and their carbo Mono acid chloride compounds in which the sil group is converted to an acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2 , 6-dicarboxynaphthalene and other monocarboxylic acid compounds in which only one carboxyl group is converted to an acid chloride, monoacid chloride compounds and N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-di Examples include active ester compounds obtained by reaction with carboximide. Two or more of these may be used.

  The content of the end-capping agent such as monoamine, acid anhydride, acid chloride, monocarboxylic acid described above is preferably 2 to 25 mol% with respect to 100 mol% of the total acid and amine components constituting the resin.

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

  The photosensitive resin composition of the present invention contains (b) a photopolymerizable compound. (B) The photopolymerizable compound has an unsaturated bond in the molecule. Examples of the unsaturated bond include unsaturated double bonds such as vinyl group, allyl group, acryloyl group, and methacryloyl group, and unsaturated triple bonds such as propargyl group. Among these, a conjugated vinyl group, an acryloyl group, and a methacryloyl group are preferable in terms of polymerizability. Further, the number of unsaturated bonds in the photopolymerizable compound is preferably 1 to 6 from the viewpoint of stability. When two or more unsaturated bonds are present, each may not be the same group.

  (B) Preferred examples of the photopolymerizable compound include 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, isobornyl acrylate, isobornyl methacrylate, penta Erythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, 2,2 , 6,6-Tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acrylate N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, ethylene oxide modified bisphenol A diacrylate, ethylene oxide modified bisphenol A Examples include dimethacrylate, N-vinylpyrrolidone, and N-vinylcaprolactam. Two or more of these may be contained.

  The content of the (b) photopolymerizable compound is preferably 5 parts by weight or more with respect to 100 parts by weight of the resin of the component (a), and the film loss in the exposed part during development can be further reduced. Moreover, 150 weight part or less is preferable and compatibility with resin of (a) component can be improved.

  The photosensitive resin composition of the present invention contains (c) a photopolymerizable compound. (C) Examples of the photopolymerization initiator include benzophenones such as benzophenone, Michler's ketone, 4,4, -bis (diethylamino) benzophenone, 3,3,4,4, -tetra (t-butylperoxycarbonyl) benzophenone. Benzylidenes such as 3,5-bis (diethylaminobenzylidene) -N-methyl-4-piperidone and 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidone, 7-diethylamino-3-thenonylcoumarin 4,6-dimethyl-3-ethylaminocoumarin, 3,3-carbonylbis (7-diethylaminocoumarin), 7-diethylamino-3- (1-methylmethylbenzimidazolyl) coumarin, 3- (2-benzothiazolyl) -7 -Coumarins such as diethylaminocoumarin, 2 Anthraquinones such as t-butylanthraquinone, 2-ethylanthraquinone and 1,2-benzanthraquinone, benzoins such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, ethylene glycol di (3-mercaptopropionate), 2 -Mercaptos such as mercaptobenzthiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N- (p-chlorophenyl) glycine, N -Glycines such as-(4-cyanophenyl) glycine, 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-methoxy) Rubonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, bis (α-iso Nitrosopropiophenone oxime) isophthal, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime), OXE01 (trade name, manufactured by Ciba Specialty Chemicals), OXE02 Oximes such as (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-methyl-1 [4- (methylthio ) Phenyl] -2-morpholinopropan-1-one and other α-aminoalkylphenones, 2,2′-bi (O-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, and the like. Of these, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, bis (α-iso Nitrosopropiophenone oxime) isophthal, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime), OXE01 and OXE02 are preferred. Two or more of these may be contained.

  The content of the (c) photopolymerization initiator is preferably 0.5 parts by weight or more with respect to 100 parts by weight of the resin of the component (a), and the film loss of the exposed part during development can be further reduced. Moreover, 50 weight part or less is preferable and can improve the film | membrane characteristic of a cured film. Furthermore, you may contain a sensitizer as needed.

  The photosensitive resin composition of the present invention contains (d) a photoacid generator. (D) The photoacid generator is a substance that generates acids such as sulfonic acids and carboxylic acids by irradiation with light, and compounds having such properties include sulfonium salt compounds, iodonium salt compounds, sulfonimide compounds, and sulfonic acids. Examples include ester compounds, diazomethane compounds, and triazine compounds. Although the example of a photo-acid generator is shown below, it is not limited to these compounds. Moreover, you may contain 2 or more types of these.

  Specific examples of the sulfonium salt compound include the following structures.

  Specific examples of the iodonium salt compound include the following structures.

  Specific examples of the sulfonimide compound include the following structures.

  Specific examples of the sulfonate compound include the following structures.

  Specific examples of the diazomethane compound include the following structures.

  Specific examples of the triazine compound include the following structures.

  (D) The content of the photoacid generator is preferably 0.5 parts by weight or more with respect to 100 parts by weight of the resin of component (a), and the film loss of the exposed part during development can be further reduced. . Moreover, 50 weight part or less is preferable and can improve the film | membrane characteristic of a cured film.

  The photosensitive resin composition of the present invention contains (e) a crosslinking agent that reacts with an acid. (E) A crosslinking agent that reacts with an acid is a compound that undergoes a crosslinking reaction with the resin of the component (a), with the acid generated from the photoacid generator (d) upon photoirradiation as a catalyst. The structure is not particularly limited as long as it has a compound. The compound having such properties can be crosslinked with the resin of the component (a) by heat simultaneously with crosslinking with an acid. Thereby, compared with the bridge | crosslinking only by the heat of a prior art, the crosslinking density with resin can be raised and the cured film excellent in chemical resistance can be obtained as a result. In particular, when the curing temperature is 250 ° C. or lower, the effect of improving chemical resistance is more remarkable.

  (E) As a crosslinking agent which reacts with an acid, the compound which has a nitrogen atom couple | bonded with a methylol group and / or an alkoxymethyl group is mentioned, for example. As these compounds, for example, amino group-containing compounds such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine are reacted with formaldehyde or formaldehyde and an alcohol, and the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. Compounds. Moreover, the oligomer formed by self-condensing methylol groups of these compounds may be sufficient. Two or more of these may be contained.

  Among the above amino group-containing compounds, those using melamine are melamine-based crosslinking agents, those using glycoluril are glycoluril-based crosslinking agents, those using urea are urea-based crosslinking agents, and those using alkylene urea Is an alkylene urea type cross-linking agent, and one using benzoguanamine is called a benzoguanamine type cross-linking agent.

  Specific examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine and the like.

  Specific examples of the glycoluril-based crosslinking agent include, for example, mono, di, tri and / or tetrahydroxymethylated glycoluril, mono, di, tri and / or tetramethoxymethylated glycoluril, mono, di, tri and / or Examples include tetraethoxymethylated glycoluril, mono, di, tri and / or tetrapropoxymethylated glycoluril, mono, di, tri and / or tetrabutoxymethylated glycoluril.

  Specific examples of the urea crosslinking agent include bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, bisbutoxymethylurea and the like.

  Specific examples of alkylene urea-based crosslinking agents include mono and / or dihydroxymethylated ethylene urea, mono and / or dimethoxymethylated ethylene urea, mono and / or diethoxymethylated ethylene urea, mono and / or dipropoxymethylated Ethylene urea based crosslinkers such as ethylene urea, mono and / or dibutoxymethylated ethylene urea, mono and / or dihydroxymethylated propylene urea, mono and / or dimethoxymethylated propylene urea, mono and / or diethoxymethylated propylene Propylene urea-based crosslinking agents such as urea, mono and / or dipropoxymethylated propylene urea, mono and / or dibutoxymethylated propylene urea, 1,3-di (methoxymethyl) 4,5-dihydroxy-2- Midazorijinon, 1,3-di (methoxymethyl) -4,5-dimethoxy-2-imidazolidinone.

  Specific examples of the benzoguanamine-based crosslinking agent include, for example, mono, di, tri and / or tetrahydroxymethylated benzoguanamine, mono, di, tri and / or tetramethoxymethylated benzoguanamine, mono, di, tri and / or tetraethoxymethyl. Benzoguanamine, mono, di, tri and / or tetrapropoxymethylated benzoguanamine, mono, di, tri and / or tetrabutoxymethylated benzoguanamine and the like.

  Of these compounds, a melamine-based cross-linking agent is preferable in that the chemical resistance of the cured film can be further improved, and hexamethoxymethyl melamine is more preferable.

  (E) As for content of the crosslinking agent which reacts with an acid, 5 weight part or more is preferable with respect to 100 weight part of resin of (a) component, and can improve the film | membrane characteristic of a cured film. Moreover, 80 weight part or less is preferable and can improve the storage stability of the photosensitive resin composition.

  The photosensitive resin composition of the present invention may further contain a thermal crosslinking agent other than (e), and can further improve the heat resistance and chemical resistance of the cured film. Examples of the thermal crosslinking agent include ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, ML-TBC, DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, and 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-Bis25X-34XL, DML-Bis25X-PCHP, TriML-P, TriML-35XL, TriML-TrisCR-HAP, TML-BP, TML-HQ, TML-pp -BPF, TML- PA, TMOM-BP, HML-TPPHBA, HML-TPPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Ba type benzoxazine, Bm type benzoxazine ( As mentioned above, trade name, manufactured by Shikoku Chemicals Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc. Is mentioned.

  Furthermore, you may contain surfactant as needed and can improve the applicability | paintability of the photosensitive resin composition and a board | substrate. Moreover, inorganic particles, such as silicon dioxide and titanium dioxide, can also be contained. Further, it may contain a silane coupling agent such as methylmethacryloxydimethoxysilane and 3-aminopropyltrimethoxysilane, a titanium chelating agent, an aluminum chelating agent and the like, and the content is 0.5 to 0.5 in the photosensitive resin composition. 10% by weight is preferred. By containing these, adhesiveness with base substrates, such as a silicon wafer, can be improved.

  The photosensitive resin composition of the present invention generally contains an organic solvent, and the components (a) to (e) are preferably dissolved or dispersed in the organic solvent. As the organic solvent, those having a boiling point of 80 ° C. to 250 ° C. under atmospheric pressure are preferably used.

  Specific examples of the organic solvent having a boiling point of 80 ° C. to 250 ° C. preferably used in the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl- Acetates such as 3-methoxybutyl acetate, methyl lactate, ethyl lactate, butyl lactate, acetyl acetate , Ketones such as methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, 2-heptanone, butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2- Alcohols such as butanol, 3-methyl-3-methoxybutanol and diacetone alcohol, aromatic hydrocarbons such as toluene and xylene, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N- Examples include dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and γ-butyrolactone. Two or more of these may be used.

  Among these, those that dissolve the component (a) and have a boiling point under atmospheric pressure of 120 ° C. to 200 ° C. are more preferable. If the boiling point is within this range, volatilization during the application of the photosensitive resin composition can be suppressed and the heat treatment temperature for removing the solvent can be kept low, so that the material of the base substrate is not restricted. Further, by using a solvent that dissolves the component (a), a uniform coating film can be formed on the base substrate. Specific examples of preferable organic solvents having such boiling point include cyclopentanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, methyl lactate, ethyl lactate, diacetone alcohol, 3-methyl- 3-methoxybutanol is mentioned.

  In addition, the content of the organic solvent in the photosensitive resin composition of the present invention is preferably 20 to 800 parts by weight with respect to 100 parts by weight of the component (a) resin.

  Next, although the example is given and demonstrated about the manufacturing method of the photosensitive resin composition of this invention, it is not limited to the following methods.

  The resin solution obtained by stirring and dissolving the component (a) in an organic solvent or the polymerization reaction to obtain the component (a) is used as it is, and the components (b) to (e) are added to the resin solution at a predetermined ratio. To obtain a uniform solution. If necessary, other additives are mixed at an appropriate stage of the production process. When the additive is inorganic particles, a dispersion is obtained by using a stirring or dispersing machine. It is preferable to filter the photosensitive resin composition thus obtained with a filter having a pore size of about 0.2 to 5 μm.

  Next, a method for forming a heat resistant resin pattern using the photosensitive resin composition of the present invention will be described.

  A photosensitive resin composition is applied onto a substrate. A silicon wafer, ceramics, gallium arsenide, or the like is used as the substrate, but is not limited thereto. Alternatively, the substrate can be pretreated with a silane coupling agent such as methylmethacryloxydimethoxysilane or 3-aminopropyltrimethoxysilane, a titanium chelating agent, an aluminum chelating agent, or the like. For example, a solution obtained by dissolving 0.5 to 20% by weight of the coupling agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate Is subjected to surface treatment by spin coating, dipping, spray coating, steam treatment or the like. Depending on the case, reaction of a board | substrate and the said coupling agent can also be advanced by applying the temperature to 50 to 300 degreeC after that.

  Examples of the method for applying the photosensitive resin composition include spin coating using a spinner, spray coating, and roll coating. Further, the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying becomes 1 to 150 μm.

  Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin composition film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like in the range of 50 to 150 ° C. for 1 minute to several hours.

  Next, the photosensitive resin composition film is exposed to actinic radiation through a mask having a desired pattern. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. In the present invention, i rays (365 nm), h rays (405 nm), and g rays (436 nm) of a mercury lamp are preferable.

  Next, it is preferable to perform baking after exposure. The baking temperature is preferably in the range of 50 to 180 ° C, more preferably in the range of 60 to 150 ° C. The time is not particularly limited, but is preferably 10 seconds to several hours from the viewpoint of subsequent developability.

  In order to form the pattern of the photosensitive resin composition film, an unexposed portion is removed using a developer after exposure. As the developer, for example, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphortriamide or the like alone or methanol , Ethanol, isopropyl alcohol, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, 2 -Used in combination with organic solvents such as heptanone, ethyl acetate, tetramethylammonium aqueous solution, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate Potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, may be used an aqueous solution of a compound showing alkalinity, such as hexamethylenediamine. In particular, an aqueous solution of tetramethylammonium, an aqueous solution of an alkaline compound such as diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, or triethylamine is preferable. In some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added singly or in combination. Good. After development, it is preferable to rinse with water. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.

  After development, the film is heated at 120 to 400 ° C. to form a cured film. This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. As an example, a method of performing heat treatment at 130 ° C., 200 ° C., and 300 ° C. for 30 minutes each, or linearly raising the temperature from room temperature to 300 ° C. over 2 hours may be mentioned.

  The cured film formed by the photosensitive resin composition of the present invention is suitable for applications such as a semiconductor element passivation film, a semiconductor element protective film, an interlayer insulating film for multilayer wiring for high-density mounting, and a wiring protective insulating film for circuit boards. Can be used. Further, a display device including a first electrode formed on a substrate and a second electrode provided to face the first electrode, specifically, for example, a liquid crystal display, an organic EL display, an electrochromic display, It can be used for an insulating layer of a display device (organic electroluminescent device) using an organic electroluminescent element.

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

Measuring method of film thickness Using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., the refractive index was measured at 1.63.

Method for Measuring Resin Dissolution Rate Resin is dissolved in γ-butyrolactone to prepare a 40 wt% solution, and this resin solution is applied onto a 6-inch silicon wafer, followed by hot plate (Mark-7, manufactured by Tokyo Electron Limited). ) Was prebaked at 120 ° C. for 4 minutes to obtain a prebaked film having a thickness of 10 μm ± 0.5 μm. The prebaked film was immersed in a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ± 1 ° C. for 1 minute, and then rinsed with pure water to obtain a film after development. The film thickness of the film after development was measured, and the amount of film thickness reduction from the prebaked film was taken as the dissolution rate.

Preparation of photosensitive resin composition film A 6-inch silicon wafer was coated with a photosensitive resin composition (hereinafter referred to as varnish) so that the film thickness after pre-baking was 10 μm, and then hot plate (Tokyo Electron Limited). A photosensitive resin composition film was obtained by prebaking at 100 ° C. for 3 minutes using Mark-7).

Exposure A reticle with a pattern cut is set in an exposure machine (full wavelength stepper Spectrum 3e manufactured by Ultratech Co., Ltd.), and the exposure amount is 500 mJ / cm ² (i-line conversion) with respect to the photosensitive resin composition film. At all wavelengths.

Post-exposure baking The exposed photosensitive resin composition film was heat-treated at 100 ° C. for 1 minute using a hot plate (Mark-7, manufactured by Tokyo Electron Ltd.).

Development A photosensitive resin composition film baked after exposure was sprayed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide for 10 seconds at 50 revolutions using a Mark-7 developing device manufactured by Tokyo Electron Ltd. . Thereafter, the film was allowed to stand for 80 seconds at 0 rotation, then rinsed with water at 400 rotations, shaken and dried for 10 seconds at 3000 rotations, and a film after development was obtained.

Heat treatment (cure)
After the development, the coating film was heat-treated for 60 minutes at a temperature described in Examples and Comparative Examples using an inert oven INH-21CD (manufactured by Koyo Thermo System Co., Ltd.) under a nitrogen stream (oxygen concentration of 20 ppm or less). .

Measurement of remaining film ratio The remaining film ratio was calculated according to the following formula.
Residual film ratio (%) = film thickness after development / film thickness after pre-baking × 100.

Evaluation of film thickness reduction due to standing time between exposure and post-exposure baking For the varnishes described in each Example and Comparative Example, two samples of the photosensitive resin composition film were prepared by the above method, and the exposure amount was 500 mJ / cm ² . After the exposure, the film was allowed to stand for 0 minute and 120 minutes, respectively, post-exposure baking and development were performed, and the remaining film ratio was measured. A case where the difference between the remaining film rates of 0 minutes and 120 minutes was less than 5% was accepted, and a case where the difference was 5% or more was rejected.

The standing time from the evaluation exposure sensitivity to exposure bake as 0 minutes, exposure to an exposure amount in the range of 20-500mJ / cm ² at 20 mJ / cm ² increments to calculate the residual film rate after development, the residual film The minimum exposure when the rate was 80% or more was defined as sensitivity.

Evaluation of chemical resistance The exposure amount was 500 mJ / cm ² , the standing time from exposure to post-exposure bake was 0 minute, and other conditions were prepared by the above method so that the post-cure film thickness was 10 μm. An immersion treatment was performed at 40 ° C. for 10 minutes using a stripping solution 106 manufactured by Oka Kogyo Co., Ltd., and the film thickness before and after the treatment was measured to determine the amount of film thickness reduction.

Synthesis Example 1 Synthesis of Hydroxyl Group-Containing Diamine Compound (I) Bis (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., BAHF) 18.3 g (0.05 mol) in 100 mL acetone It was dissolved in 17.4 g (0.3 mol) of propylene oxide and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride in 100 mL of acetone was added dropwise thereto. After completion of dropping, the mixture was reacted at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white powder was filtered off and dried in vacuum at 50 ° C.

  30 g of the powder was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration and concentrated by a rotary evaporator to obtain a hydroxyl group-containing diamine compound (I) represented by the following formula.

Synthesis Example 2 Synthesis of Alkali-Soluble Resin BAHF 29.3 g (0.08 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 1.24 g (0.005 mol), end-capped under a dry nitrogen stream As a stopper, 3.27 g (0.03 mol) of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 150 g of N-methyl-2-pyrrolidone (NMP). 31.0 g (0.1 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride (manac Co., Ltd., ODPA) was added thereto together with 50 g of NMP, and the mixture was stirred at 20 ° C. for 1 hour, then 50 Stir at 4 ° C. for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150 ° C. for 5 hours while azeotropically distilling water with xylene. After stirring, the solution was poured into 3 L of water to collect a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried for 24 hours with a vacuum dryer at 80 ° C. to obtain a polyimide powder (hereinafter referred to as polymer (II)). The dissolution rate of this resin was 5530 nm / min.

Synthesis Example 3 Synthesis of alkali-soluble resin Under a dry nitrogen stream, 48.4 g (0.08 mol) of hydroxyl group-containing diamine compound (I) obtained in Synthesis Example 1 and 1,3-bis (3-aminopropyl) tetra 1.27 g (0.005 mol) of methyldisiloxane and 3.27 g (0.03 mol) of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) as an end-capping agent were dissolved in 150 g of NMP. ODPA 31.0g (0.1mol) was added here with NMP50g, and it stirred at 40 degreeC for 3 hours. Thereafter, a solution obtained by diluting 5.19 g (0.127 mol) of N, N-dimethylformamide dimethylacetal with 4 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 3 L of water to collect a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polyamic acid ester (hereinafter referred to as polymer (III)). The dissolution rate of this resin was 1980 nm / min.

Synthesis Example 4 Synthesis of alkali-soluble resin Under dry nitrogen flow, 18.3 g (0.05 mol) of BAHF was dissolved in 50 g of NMP and 26.4 g (0.3 mol) of glycidyl methyl ether, and the temperature of the solution was cooled to −15 ° C. did. A solution prepared by dissolving 14.7 g of diphenyl ether dicarboxylic acid dichloride (manufactured by Nippon Agricultural Chemicals Co., Ltd., 0.050 mol) in 25 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, stirring was continued for 6 hours at -15 ° C. After completion of the reaction, the solution was poured into 3 L of water containing 10% by weight of methanol to collect a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain polyhydroxyamide powder (hereinafter referred to as polymer (IV)). The dissolution rate of this resin was 870 nm / min.

  The structures of the compounds used in each example and comparative example are shown below.

Example 1
10 g of polymer (II) as an alkali-soluble resin, 4.0 g of PDBE-200 (trade name, manufactured by NOF Corporation) as a photopolymerizable compound, dipentaerythritol hexaacrylate (trade name: DPHA, Nippon Kayaku Co., Ltd.) ) 1.0 g, OXE02 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.2 g as a photopolymerization initiator, and WPAG-341 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) 0.3 g as a photoacid generator A varnish A of a photosensitive resin composition was obtained by dissolving 5.0 g of MW-100LM (trade name, manufactured by Nippon Carbide Corp.) as a crosslinking agent that reacts with an acid in 20 g of diacetone alcohol. Using the obtained varnish A, a photosensitive resin composition film was prepared on a silicon wafer as described above, and exposure, post-exposure bake, development, heat treatment at 200 ° C., and exposure time from exposure to post-exposure bake The film thickness reduction, sensitivity, and chemical resistance were evaluated.

Example 2
The varnish B of the photosensitive resin composition was prepared in the same manner as in Example 1 except that 10 g of the polymer (III) was used instead of the polymer (II) as the alkali-soluble resin, and 20 g of γ-butyrolactone was used as the solvent instead of diacetone alcohol. Obtained. Using the obtained varnish B, in the same manner as in Example 1, the film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking.

Example 3
Varnish C of the photosensitive resin composition was obtained in the same manner as in Example 2 except that 10 g of polymer (IV) was used instead of polymer (II) as the alkali-soluble resin. Using the obtained varnish C, in the same manner as in Example 1, film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking.

Example 4
Varnish D of the photosensitive resin composition was obtained in the same manner as in Example 1 except that 0.3 g of NAI-105 (trade name, manufactured by Midori Chemical Co., Ltd.) was used instead of WPAG-341 as the photoacid generator. It was. Using the obtained varnish D, the film thickness reduction, sensitivity, and chemical resistance were evaluated in the same manner as in Example 1 depending on the standing time from exposure to post-exposure baking.

Example 5
Varnish E of the photosensitive resin composition was obtained in the same manner as in Example 1 except that 0.3 g of DAM-101 (trade name, manufactured by Midori Chemical Co., Ltd.) was used instead of WPAG-341 as the photoacid generator. It was. Using the obtained varnish E, in the same manner as in Example 1, the film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking.

Example 6
Varnish F of the photosensitive resin composition in the same manner as in Example 1 except that 5.0 g of MX-270 (trade name, manufactured by Nippon Carbide Corporation) is used instead of MW-100LM as a crosslinking agent that reacts with an acid. Got. Using the obtained varnish F, in the same manner as in Example 1, the film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking.

Comparative Example 1
Varnish G of the photosensitive resin composition was obtained in the same manner as in Example 1 except that the photoacid generator was not added. Using the obtained varnish G, in the same manner as in Example 1, the film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking.

Comparative Example 2
Varnish H of the photosensitive resin composition was obtained in the same manner as Example 1 except that no photopolymerization initiator was added. Using the obtained varnish H, the film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking in the same manner as in Example 1.

Comparative Example 3
Varnish I of the photosensitive resin composition was obtained like Example 1 except not adding a photopolymerizable compound and a photoinitiator. Using the obtained varnish I, the film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking in the same manner as in Example 1.

Comparative Example 4
Varnish J of the photosensitive resin composition was obtained in the same manner as in Example 2 except that the photoacid generator was not added. Using the obtained varnish J, in the same manner as in Example 1, the film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking.

Comparative Example 5
Varnish K of the photosensitive resin composition was obtained in the same manner as in Example 3 except that no photoacid generator was added. Using the obtained varnish K, the film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking in the same manner as in Example 1.

Comparative Example 6
Varnish L of the photosensitive resin composition was obtained in the same manner as in Example 6 except that no photoacid generator was added. Using the obtained varnish L, in the same manner as in Example 1, the film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking.

Comparative Example 7
Photosensitive in the same manner as in Example 1 except that 5.0 g of thermal crosslinking agent DML-PC (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) is added instead of MW-100LM which is a crosslinking agent that reacts with an acid. A varnish M of the resin composition was obtained. Using the obtained varnish M, in the same manner as in Example 1, the film thickness reduction, sensitivity, and chemical resistance were evaluated according to the standing time from exposure to post-exposure baking.

  The compositions and evaluation results of Examples 1 to 6 and Comparative Examples 1 to 7 are shown in Tables 1 and 2 below.

Claims (6)

(A) An alkali-soluble resin, (b) a photopolymerizable compound, (c) a photopolymerization initiator, (d) a photoacid generator, and (e) a crosslinking agent that reacts with an acid. Resin composition. The photosensitive resin composition according to claim 1, wherein the crosslinking agent that reacts with the acid (e) is a compound having a nitrogen atom bonded to a methylol group and / or an alkoxymethyl group. The photosensitive resin composition according to claim 1, wherein the crosslinking agent that reacts with the acid (e) is a melamine-based crosslinking agent. The photosensitive resin composition according to claim 3, wherein the melamine-based crosslinking agent is hexamethoxymethylmelamine. The photosensitive resin composition according to claim 1, wherein the (a) alkali-soluble resin is polyimide, a polyimide precursor, or polyhydroxyamide. 6. The photosensitive resin composition according to claim 5, wherein the (a) alkali-soluble resin is polyimide.