Photosensitive resin composition, photosensitive resin film, photosensitive dry film, and pattern forming method

Abstract

To provide: a photosensitive resin composition good in storage stability as a varnish and a dry film, and capable of easily forming a thick and fine pattern, and capable of forming a resin film (resin layer) excellent in copper migration resistance, various film characteristics such as adhesiveness to a base material used particularly for a circuit board such as a substrate, an electronic component and a semiconductor element, and excellent in reliability as a film for protection of electric and electronic components and a film for circuit board adhesion; a photosensitive resin film; a photosensitive dry film; and a method of forming a pattern using them.SOLUTION: A photosensitive resin composition includes: (A) a silicone resin having an epoxy group and / or a phenolic hydroxy group; (B) an optical acid generator represented by the following formula (B); and (C) a benzotriazole-based compound.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photosensitive resin composition, a photosensitive resin film, a photosensitive dry film, and a pattern forming method. [Background technology]

[0002] Conventionally, photosensitive polyimide compositions, photosensitive epoxy resin compositions, photosensitive silicone compositions, and the like have been used as photosensitive semiconductor element protective films and insulating films for multilayer printed circuit boards. As a photosensitive material applied to the protection of such substrates and circuits, a photosensitive silicone composition, which is particularly excellent in flexibility, has been proposed (Patent Document 1). This photosensitive silicone composition can be cured at low temperatures and can form a film with excellent reliability such as moisture-resistant adhesion, but has a problem of poor chemical resistance to photoresist stripping solutions with strong dissolving power such as N-methyl-2-pyrrolidone.

[0003] In response to this, a photosensitive silicone composition has been proposed that contains a silicone polymer containing a silphenylene skeleton as a main component (Patent Document 2). The photosensitive silicone composition has improved chemical resistance to photoresist stripping solutions and the like, but further improvements are desired in terms of the level of fineness achieved by pattern formation and copper migration resistance. In addition, when the photosensitive silicone composition is made into a varnish, the viscosity of the varnish changes over time, which affects film thickness adjustment during spin coating on a wafer or dry film application, and therefore improvements are also desired in this respect. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2002-88158 A [Patent Document 2] JP 2008-184571 A Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive resin composition, a photosensitive resin film, and a photosensitive dry film which are capable of forming a resin film (resin layer) which has good storage stability in the form of a varnish or dry film, which can easily form a thick film and a fine pattern, and which is excellent in various film properties such as copper migration resistance and adhesion to substrates used for substrates such as boards, electronic components, and semiconductor elements, particularly circuit boards, and which is highly reliable as a film for protecting electric / electronic components or a film for bonding boards, and a pattern forming method using the same. [Means for solving the problem]

[0006] Means for Solving the Problems The present inventors conducted extensive research to achieve the above-mentioned object, and as a result, found that the above-mentioned object can be achieved by a photosensitive resin composition containing a silicone resin having an epoxy group and / or a phenolic hydroxy group, a photoacid generator having a specific structure, and a benzotriazole-based compound, and thus completed the present invention.

[0007] Accordingly, the present invention provides the following photosensitive resin composition, photosensitive resin film, photosensitive dry film, and pattern forming method. 1. (A) a silicone resin having an epoxy group and / or a phenolic hydroxy group, (B) a photoacid generator represented by the following formula (B): (C) Benzotriazole compounds A photosensitive resin composition comprising: [ka] (In the formula, R A represents a hydrocarbyl group having 1 to 12 carbon atoms, some or all of whose hydrogen atoms may be substituted with fluorine atoms. R B are each independently a monovalent organic group, and two or more R Bmay be directly bonded to each other or bonded via -O-, -S-, -SO-, -SO2-, -NH-, -CO-, -COO-, -CONH-, a saturated hydrocarbylene group having 1 to 20 carbon atoms or a phenylene group to form a ring structure containing element E. E is an element of valence n in Groups 15 to 17 of the periodic table. n is an integer from 1 to 3. ) 2. (A) A photosensitive resin composition in which the silicone resin is represented by the following formula (A).

Chemical formula

Chemical formula

[0008] The photosensitive resin composition of the present invention has good storage stability in varnishes and dry films, can form a film in a wide film thickness range, and can further form a thick film, fine, and highly vertical pattern by the pattern forming method described later. The film obtained by using the photosensitive resin composition and the photosensitive dry film of the present invention is excellent in adhesion, mechanical properties, electrical insulation properties, copper migration resistance, and chemical resistance to substrates, electronic components, semiconductor elements, etc., particularly to the base materials used for circuit boards. Further, the film has high reliability as an insulating protective film and can be suitably used as a film forming material for protecting various electrical and electronic components such as circuit boards, semiconductor elements, and display elements, and a film forming material for substrate adhesion.

Embodiments for Carrying Out the Invention

[0009] [Photosensitive Resin Composition] The photosensitive resin composition of the present invention contains (A) a silicone resin having an epoxy group and / or a phenolic hydroxyl group, (B) a photoacid generator having a specific structure, and (C) a benzotriazole-based compound.

[0010] [(A) Silicone Resin] The silicone resin of component (A) contains an epoxy group, a phenolic hydroxyl group, or both in the molecule. Such a silicone resin is not particularly limited, but those represented by the following formula (A) are preferred.

Chemical Formula

[0011] In formula (A), R 1 ~R 4 are each independently a hydrocarbyl group having 1 to 8 carbon atoms, preferably those having 1 to 6 carbon atoms. k is an integer of 1 to 600, preferably an integer of 1 to 400, and more preferably an integer of 1 to 200. a and b represent the composition ratio (molar ratio) of each repeating unit and are numbers satisfying 0 < a < 1, 0 < b < 1, and a + b = 1. X is a divalent organic group containing an epoxy group and / or a phenolic hydroxyl group.

[0012] The hydrocarbyl group may be linear, branched or cyclic, and specific examples thereof include alkyl groups such as methyl, ethyl, propyl, hexyl, and structural isomers thereof; cyclic saturated hydrocarbyl groups such as cyclohexyl; aryl groups such as phenyl, etc. Of these, methyl and phenyl groups are preferred because of the ease of availability of raw materials.

[0013] As the silicone resin represented by formula (A), those containing repeating units represented by the following formulas (a1) to (a4) and (b1) to (b4) (hereinafter also referred to as repeating units a1 to a4 and b1 to b4, respectively) are particularly preferred. [ka] (In the formula, R 1 ~R 4 and k are the same as above.)

[0014] In formulas (a1) and (b1), X 1 is a divalent group represented by the following formula (X1). [ka] (In the formula, the dashed lines represent bonds.)

[0015] In formula (X1), Y 1 R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 11 and R 12 R is each independently a hydrogen atom or a methyl group. 13 and R 14 are each independently a saturated hydrocarbyl group having 1 to 4 carbon atoms or a saturated hydrocarbyloxy group having 1 to 4 carbon atoms. 1 and p 2 are each independently an integer of 0 to 7. 1 and q 2 are each independently an integer of 0 to 2.

[0016] The saturated hydrocarbyl group may be linear, branched, or cyclic, and specific examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl, and structural isomers thereof; cyclic saturated hydrocarbyl groups such as cyclopropyl and cyclobutyl. The saturated hydrocarbyloxy group may be linear, branched, or cyclic, and specific examples thereof include alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, and structural isomers thereof; cyclic saturated hydrocarbyloxy groups such as cyclopropyloxy and cyclobutyloxy.

[0017] In formulas (a2) and (b2), X 2 is a divalent group represented by the following formula (X2). [ka] (In the formula, the dashed lines represent bonds.)

[0018] In formula (X2), Y 2 R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 21 and R 22 R is each independently a hydrogen atom or a methyl group. 23 and R 24 are each independently a saturated hydrocarbyl group having 1 to 4 carbon atoms or a saturated hydrocarbyloxy group having 1 to 4 carbon atoms. 1 and r 2 are each independently an integer of 0 to 7. 1 and s 2 are each independently an integer of 0 to 2. The saturated hydrocarbyl group and the saturated hydrocarbyloxy group include R 13 and R 14 Examples of the examples are similar to those given in the description of .

[0019] In formulas (a3) ​​and (b3), X 3is a divalent group represented by the following formula (X3). [ka] (In the formula, the dashed lines represent bonds.)

[0020] In formula (X3), R 31 and R 32 are each independently a hydrogen atom or a methyl group. 1 and t 2 are each independently an integer of 0 to 7.

[0021] In formulas (a4) and (b4), X 4 is a divalent group represented by the following formula (X4). [ka] (In the formula, the dashed lines represent bonds.)

[0022] In formula (X4), R 41 and R 42 R is each independently a hydrogen atom or a methyl group. 43 and R 44 are each independently a hydrocarbyl group having 1 to 8 carbon atoms. 1 and u 2 are each independently an integer of 0 to 7. v is an integer of 0 to 600, preferably an integer of 0 to 400, and more preferably an integer of 0 to 200. As the hydrocarbyl group, R 1 ~R 4 Examples of the examples are similar to those given in the description of .

[0023] The silicone resin of component (A) preferably has a weight average molecular weight (Mw) of 3,000 to 500,000, and more preferably 5,000 to 200,000. In the present invention, Mw is a value measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an elution solvent.

[0024] In the formulas (a1) to (a4) and (b1) to (b4), a 1 ~a 4 and b 1 ~b 4 represents the composition ratio (molar ratio) of each repeating unit, and 0≦a 1 < 1, 0 ≤ a 2 < 1, 0 ≤ a 3 < 1, 0 ≤ a 4 < 1, 0 ≤ b 1 < 1, 0 ≤ b 2 < 1, 0 ≤ b 3 < 1, 0 ≤ b 4 <1, 0 1 +a 2 +a 3 <1, 0 1 +b 2 +b 3 <1 and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 = 1, but 0≦a 1 ≦0.8, 0≦a 2 ≦0.8, 0≦a 3 ≦0.8, 0≦a 4 ≦0.8, 0≦b 1 ≦0.95, 0≦b 2 ≦0.95, 0≦b 3 ≦0.95, 0≦b 4 ≦0.95, 0.05≦a 1 +a 2 +a 3 ≦0.8, 0.2≦b 1 +b 2 +b 3 ≦0.95 and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 = 1 is more preferable, and 0≦a 1 ≦0.7, 0≦a 2 ≦0.7, 0≦a 3 ≦0.7, 0≦a 4 ≦0.7, 0≦b 1 ​​≦0.9, 0≦b 2 ≦0.9, 0≦b 3 ≦0.9, 0≦b 4 ≦0.9, 0.1≦a 1 +a 2 +a 3 ≦0.7, 0.3≦b 1 +b 2 +b 3 ≦0.9 and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 It is more preferable that the number satisfies:

[0025] The repeating units may be bonded randomly or as a block polymer. When there are two or more siloxane units in each repeating unit, the siloxane units may all be the same or may contain two or more different types of siloxane units. When there are two or more different types of siloxane units, the siloxane units may be bonded randomly or may contain a plurality of blocks of the same type of siloxane units. In the silicone resin, the silicone (siloxane unit) content is preferably 30 to 80% by mass.

[0026] The silicone resin of component (A) functions to provide film-forming ability, and the resulting resin film has good adhesion to laminates, substrates, etc., good pattern-forming ability, crack resistance, and heat resistance.

[0027] The silicone resin of the component (A) may use one type alone, or two or more types in combination.

[0028] [(A) Method for producing silicone resin] The silicone resin of component (A) can be produced by addition polymerization of a compound represented by the following formula (1), a compound represented by the following formula (2), at least one compound selected from a compound represented by the following formula (3), a compound represented by the following formula (4), and a compound represented by the following formula (5), and, if necessary, a compound represented by the following formula (6), in the presence of a metal catalyst. [ka] (In the formula, R 1 ~R 4 and k are the same as above.)

[0029] [ka] (In the formula, R 11 ~R 14 , R 21 ~R 24 , R 31 , R 32 , R 41 ~R 44 , Y 1 , Y 2 , p 1 , p 2 , q 1 , q 2 , r 1 , r 2 , s 1 , s 2 , t 1 , t 2 , u 1 , u 2 and v are the same as above.)

[0030] Examples of the metal catalyst include platinum group metals such as platinum (including platinum black), rhodium, and palladium; platinum chloride, chloroplatinic acid, and chloroplatinic acid salts such as H2PtCl4·xH2O, H2PtCl6·xH2O, NaHPtCl6·xH2O, KHPtCl6·xH2O, Na2PtCl6·xH2O, K2PtCl4·xH2O, PtCl4·xH2O, PtCl2, and Na2HPtCl4·xH2O (wherein x is preferably an integer of 0 to 6, and particularly preferably 0 or 6); alcohol-modified chloroplatinic acid (for example, those described in U.S. Pat. No. 3,220,972) ); complexes of chloroplatinic acid and olefins (for example, those described in U.S. Pat. Nos. 3,159,601, 3,159,662, and 3,775,452); platinum group metals such as platinum black and palladium supported on supports such as alumina, silica, and carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (the so-called Wilkinson's catalyst); complexes of platinum chloride, chloroplatinic acid or chloroplatinate with vinyl group-containing siloxanes (particularly vinyl group-containing cyclic siloxanes), and the like can be used.

[0031] The amount of the catalyst used is a catalytic amount, and is usually preferably 0.001 to 0.1 parts by mass, and more preferably 0.01 to 0.1 parts by mass, per 100 parts by mass of the total of the raw material compounds.

[0032] In the addition polymerization reaction, a solvent may be used as necessary. As the solvent, for example, a hydrocarbon solvent such as toluene or xylene is preferable.

[0033] The polymerization temperature is preferably 40 to 150°C, more preferably 60 to 120°C, from the viewpoint of not deactivating the catalyst and being able to complete the polymerization in a short time. The polymerization time varies depending on the type and amount of the resin to be obtained, but is preferably about 0.5 to 100 hours, more preferably 0.5 to 30 hours, in order to prevent the intrusion of moisture into the polymerization system. After the reaction is completed, if a solvent is used, it can be distilled off to obtain the silicone resin of component (A).

[0034] The reaction method is not particularly limited, but for example, in the case of reacting a compound represented by formula (1), a compound represented by formula (2), at least one selected from a compound represented by formula (3), a compound represented by formula (4), and a compound represented by formula (5), and optionally a compound represented by formula (6), a method can be mentioned in which first, at least one selected from a compound represented by formula (3), a compound represented by formula (4), and a compound represented by formula (5), and optionally a compound represented by formula (6) are mixed and heated, a metal catalyst is added to the mixture, and then the compound represented by formula (1) and the compound represented by formula (2) are dropwise added over 0.1 to 5 hours.

[0035] The compounds are preferably blended such that the molar ratio of the total of the hydrosilyl groups contained in the compound represented by formula (1) and the compound represented by formula (2) to the total of the alkenyl groups contained in at least one selected from the compound represented by formula (3), the compound represented by formula (4), and the compound represented by formula (5), and optionally the compound represented by formula (6), is preferably 0.67 to 1.67, more preferably 0.83 to 1.25.

[0036] The Mw of the resulting resin can be controlled by using a monoallyl compound such as o-allylphenol or a monohydrosilane or monohydrosiloxane such as triethylhydrosilane as a molecular weight regulator.

[0037] [(B) Photoacid generator] The photosensitive resin composition of the present invention contains a compound represented by the following formula (B) as a photoacid generator (B). [ka]

[0038] In formula (B), R A represents a hydrocarbyl group having 1 to 12 carbon atoms, some or all of whose hydrogen atoms may be substituted with fluorine atoms.

[0039] In formula (B), R BR is each independently a monovalent organic group. B Examples of the aromatic hydrocarbyl group having 6 to 14 carbon atoms include an aromatic hydrocarbyl group having 6 to 14 carbon atoms, a saturated hydrocarbyl group having 1 to 18 carbon atoms, and an unsaturated aliphatic hydrocarbyl group having 2 to 18 carbon atoms. The aromatic hydrocarbyl group having 6 to 14 carbon atoms includes a saturated hydrocarbyl group having 1 to 18 carbon atoms, a saturated hydrocarbyl group having 1 to 8 carbon atoms substituted with a halogen atom, an unsaturated aliphatic hydrocarbyl group having 2 to 18 carbon atoms, an aromatic hydrocarbyl group having 6 to 14 carbon atoms, a nitro group, a hydroxy group, a cyano group, an -OR group, a , -C(=O)-R b , -OC(=O)-R c , -SR d , -NR e R f or halogen atoms. a ~R d R is a saturated hydrocarbyl group having 1 to 8 carbon atoms or an aromatic hydrocarbyl group having 6 to 14 carbon atoms. e and R f are each independently a hydrogen atom, a saturated hydrocarbyl group having 1 to 8 carbon atoms, or an aromatic hydrocarbyl group having 6 to 14 carbon atoms.

[0040] Also, two or more R B may be bonded to each other directly or via -O-, -S-, -SO-, -SO2-, -NH-, -CO-, -COO-, -CONH-, a saturated hydrocarbylene group having 1 to 20 carbon atoms, or a phenylene group to form a ring structure containing the element E.

[0041] In formula (B), E is an element of group 15 to 17 of the periodic table with a valence of n, and R is an organic group. Band forms an onium ion. Preferred elements of Groups 15 to 17 include oxygen (O), nitrogen (N), phosphorus (P), sulfur (S) and iodine (I), and the corresponding onium ions are oxonium ion, ammonium ion, phosphonium ion, sulfonium ion and iodonium ion. Among them, ammonium ion, phosphonium ion, sulfonium ion and iodonium ion, which are stable and easy to handle, are preferred, and sulfonium ion, which has excellent cationic polymerization performance and crosslinking reaction performance, is more preferred. n represents the atomic valence of element E and is an integer of 1 to 3.

[0042] Specific examples of the oxonium ion include oxonium ions such as trimethyloxonium ion, diethylmethyloxonium ion, triethyloxonium ion, and tetramethylenemethyloxonium; pyryliums such as 4-methylpyrylium, 2,4,6-trimethylpyrylium, 2,6-di-tert-butylpyrylium, and 2,6-diphenylpyrylium; chromeniums such as 2,4-dimethylchromelinium; and isochromeliniums such as 1,3-dimethylisochromelinium.

[0043] Specific examples of the ammonium ion include tetraalkylammonium ions such as tetramethylammonium ion, ethyltrimethylammonium ion, diethyldimethylammonium ion, triethylmethylammonium ion, and tetraethylammonium ion; pyrrolidinium ions such as N,N-dimethylpyrrolidinium ion, N-ethyl-N-methylpyrrolidinium ion, and N,N-diethylpyrrolidinium ion; imidazolinium ions such as N,N'-dimethylimidazolinium ion, N,N'-diethylimidazolinium ion, N-ethyl-N'-methylimidazolinium ion, 1,3,4-trimethylimidazolinium ion, and 1,2,3,4-tetramethylimidazolinium ion; and tetramethylammonium ions such as N,N'-dimethyltetrahydropyrimidinium ion. quinolinium ions such as N-methylquinolinium ion, N-benzylquinolinium ion and N-phenacylquinolinium ion; isoquinolinium ions such as N-methylisoquinolinium ion; thiazonium ions such as benzylbenzothiazonium ion and phenacylbenzothiazonium ion; and acridinium ions such as benzylacridinium ion and phenacylacridinium ion.

[0044] Specific examples of the phosphonium ion include tetraarylphosphonium ions such as tetraphenylphosphonium ion, tetra-p-tolylphosphonium ion, tetrakis(2-methoxyphenyl)phosphonium ion, tetrakis(3-methoxyphenyl)phosphonium ion, and tetrakis(4-methoxyphenyl)phosphonium ion; triarylphosphonium ions such as triphenylbenzylphosphonium ion, triphenylphenacylphosphonium ion, triphenylmethylphosphonium ion, and triphenylbutylphosphonium ion; and tetraalkylphosphonium ions such as triethylbenzylphosphonium ion, tributylbenzylphosphonium ion, tetraethylphosphonium ion, tetrabutylphosphonium ion, tetrahexylphosphonium ion, triethylphenacylphosphonium ion, and tributylphenacylphosphonium ion.

[0045] Specific examples of the sulfonium ion include a triphenylsulfonium ion, a tri-p-tolylsulfonium ion, a tri-o-tolylsulfonium ion, a tris(4-methoxyphenyl)sulfonium ion, a 1-naphthyldiphenylsulfonium ion, a 2-naphthyldiphenylsulfonium ion, a tris(4-fluorophenyl)sulfonium ion, a tri-1-naphthylsulfonium ion, a tri-2-naphthylsulfonium ion, a tris(4-hydroxyphenyl)sulfonium ion, a 4-(phenylthio)phenyldiphenylsulfonium ion, a tri ... Phenylsulfonium ion, 4-(p-tolylthio)phenyldi-p-tolylsulfonium ion, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium ion, 4-(phenylthio)phenylbis(4-fluorophenyl)sulfonium ion, 4-(phenylthio)phenylbis(4-methoxyphenyl)sulfonium ion, 4-(phenylthio)phenyldi-p-tolylsulfonium ion, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium ion, [4-( 2-thioxanthonylthio)phenyl]diphenylsulfonium ion, bis[4-(diphenylsulfonio)phenyl]sulfide ion, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide ion, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide ion, bis{4-[bis(4-methylphenyl)sulfonio]phenyl}sulfide ion, bis{4-[bis(4-methoxyphenyl)sulfonio]phenyl}sulfide ion, 4-(4-benzoyl- 2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium ion, 4-(4-benzoyl-2-chlorophenylthio)phenyldiphenylsulfonium ion, 4-(4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium ion, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium ion, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium ion, 7-isopropyl-9-oxo-10-thia-9,10-Dihydroanthracen-2-yldiphenylsulfonium ion, 2-[(di-p-tolyl)sulfonio]thioxanthone ion, 2-[(diphenyl)sulfonio]thioxanthone ion, 4-(9-oxo-9H-thioxanthen-2-yl)thiophenyl-9-oxo-9H-thioxanthen-2-ylphenylsulfonium ion, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolyl sulfonium ion, 4-[4-(4-t ert-butylbenzoyl)phenylthio]phenyldiphenylsulfonium ion, 4-[4-(benzoylphenylthio)]phenyldi-p-tolylsulfonium ion, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium ion, 5-(4-methoxyphenyl)thiaanthrenenium ion, 5-phenylthiaanthrenenium ion, 5-tolylthianthrenenium ion, 5-(4-ethoxyphenyl)thiaanthrenenium ion, 5-(2,4,triarylsulfonium ions such as 6-trimethylphenyl)thiaanthrenenium ion; diarylsulfonium ions such as diphenylphenacylsulfonium ion, diphenyl-4-nitrophenacylsulfonium ion, diphenylbenzylsulfonium ion, and diphenylmethylsulfonium ion; phenylmethylbenzylsulfonium ion, 4-hydroxyphenylmethylbenzylsulfonium ion, 4-methoxyphenylmethylbenzylsulfonium ion, 4-acetocarbonyloxyphenylmethylbenzylsulfonium ion, 4-hydroxyphenyl(2-naphthylmethyl)methylsulfonium ion, 2-naphthylmethylbenzylsulfonium ion, and 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium Examples of the sulfonium ions include monoaryl sulfonium ions such as phenylmethylphenacylsulfonium ion, 4-hydroxyphenylmethylphenacylsulfonium ion, 4-methoxyphenylmethylphenacylsulfonium ion, 4-acetocarbonyloxyphenylmethylphenacylsulfonium ion, 2-naphthylmethylphenacylsulfonium ion, 2-naphthyloctadecylphenacylsulfonium ion, and 9-anthracenylmethylphenacylsulfonium ion; and trialkylsulfonium ions such as dimethylphenacylsulfonium ion, phenacylterahydrothiophenium ion, dimethylbenzylsulfonium ion, benzyltetrahydrothiophenium ion, and octadecylmethylphenacylsulfonium ion.

[0046] Specific examples of the iodonium ion include diphenyliodonium ion, di-p-tolyliodonium ion, bis(4-dodecylphenyl)iodonium ion, bis(4-methoxyphenyl)iodonium ion, (4-octyloxyphenyl)phenyliodonium ion, bis(4-decyloxy)phenyliodonium ion, 4-(2-hydroxytetradecyloxy)phenylphenyliodonium ion, 4-isopropylphenyl(p-tolyl)iodonium ion, and 4-isobutylphenyl(p-tolyl)iodonium ion.

[0047] From the viewpoint of photocurability, the content of the (B) component is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the (A) component. If the content of the (B) component is 0.05 parts by mass or more, sufficient acid is generated to sufficiently proceed with the crosslinking reaction, and if the content is 20 parts by mass or less, an increase in the absorbance of the photoacid generator itself can be suppressed, and there is no risk of problems such as a decrease in transparency, which is preferable. The (B) component may be used alone or in combination of two or more types.

[0048] [(C) Benzotriazole-based compounds] The photosensitive resin composition of the present invention contains a benzotriazole-based compound as component (C). The addition of a benzotriazole-based compound contributes to the following effects in the presence of the photoacid generator as component (B). First, it exerts a good quencher effect, and can suppress the diffusion speed when the acid generated by the photoacid generator diffuses in the photocurable resin layer, thereby improving the resolution, suppressing the change in sensitivity after exposure, reducing the substrate dependency or environmental dependency, and improving the exposure margin and pattern shape. Second, it exerts a good catalytic effect during post-curing, and can obtain a cured film with excellent reliability and migration resistance, and also has excellent storage stability because the varnish does not become more viscous due to the progress of reactions between functional groups at room temperature, and the varnish does not become less viscous due to scission of siloxane over time. In addition, the dry film also has excellent storage stability in terms of pattern forming ability because the reaction does not proceed at room temperature.

[0049] The benzotriazole-based compound is preferably one represented by the following formula (C1) or (C2). [ka]

[0050] In formulas (C1) and (C2), R 101 and R 103each independently represents a hydrogen atom, a hydroxy group, an aliphatic hydrocarbyl group having 1 to 8 carbon atoms, a saturated hydrocarbyloxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 24 carbon atoms.

[0051] R 101 and R 103 The aliphatic hydrocarbyl group having 1 to 8 carbon atoms represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and structural isomers thereof; cyclic saturated hydrocarbyl groups such as cyclopropyl and cyclobutyl; alkenyl groups such as vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, and structural isomers thereof.

[0052] R 101 and R 103 The saturated hydrocarbyloxy group having 1 to 8 carbon atoms represented by the following formula may be linear, branched, or cyclic, and specific examples thereof include a methoxy group, an ethoxy group, and a propoxy group.

[0053] R 101 and R 103 Examples of the aryl group having 6 to 24 carbon atoms represented by the formula (I) include a phenyl group, a naphthyl group, and groups in which some or all of the hydrogen atoms of these groups have been substituted with an aliphatic hydrocarbyl group having 1 to 8 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. Examples of the aliphatic hydrocarbyl group having 1 to 8 carbon atoms include R 101 and R 103 Examples of the aralkyl group having 7 to 15 carbon atoms include a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 3-phenyl-1-propyl group, and a 2-phenyl-2-propyl group.

[0054] In addition, some or all of the hydrogen atoms of the aliphatic hydrocarbyl group and the aryl group may be substituted with a hydroxy group, and some of the -CH2- of the aliphatic hydrocarbyl group may be substituted with an ether bond or an ester bond. Examples of the groups in which some or all of the hydrogen atoms of the aliphatic hydrocarbyl group and the aryl group are substituted with a hydroxy group include a hydroxymethyl group, a 2-hydroxyethyl group, and a hydroxyphenyl group. Examples of the groups in which some of the -CH2- of the aliphatic hydrocarbyl group are substituted with an ether bond or an ester bond include a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, a (meth)acryloylethyl group, and a (meth)acryloylpropyl group.

[0055] In formulas (C1) and (C2), R 102 and R 104 are each independently a halogen atom or a hydrocarbyl group having 1 to 6 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with fluorine atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbyl group having 1 to 6 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and structural isomers thereof; cyclic saturated hydrocarbyl groups such as a cyclopropyl group and a cyclobutyl group; alkenyl groups such as a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, and structural isomers thereof; and a phenyl group. Examples of the hydrocarbyl group substituted with a fluorine atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, and a 1,1,1,3,3,3-hexafluoro-2-propyl group.

[0056] In the formulae (C1) and (C2), x and y each independently represent an integer of 0 to 4.

[0057] Examples of the benzotriazole-based compounds include benzotriazole, 1-(methoxymethyl-1H-benzotriazole, 2-n-octylbenzotriazole, methyl-1H-benzotriazole, 1-methyl-1H-benzotriazole, 1H-benzotriazole-1-methanol, 1-hydroxy-6-(trifluoromethyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, 5,6-dimethyl-1,2,3-benzotriazole, 5-chlorobenzotriazole, 4,5,6,7-tetrabromobenzotriazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, and 2-(2H-benzotriazole-2-yl)-4-methyl-6-(2-propenyl)phenol.

[0058] The content of the (C) component is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the (A) component, from the viewpoints of compatibility, quencher effect, and curing acceleration during post-curing. If the content of the (C) component is 0.01 part by mass or more, sufficient quencher effect and curability are obtained, and if the content is 10 parts by mass or less, compatibility with the (A) component is good and there is no risk of problems such as reduced transparency, which is preferable. The (C) component may be used alone or in combination of two or more types.

[0059] [(D) Crosslinking agent] The photosensitive resin composition of the present invention preferably further comprises a crosslinking agent as component (D). The crosslinking agent is a crosslinking agent that converts the phenolic hydroxyl group or R 13 , R 14 , R 23 or R 24 This component undergoes a condensation reaction with the saturated hydrocarbyloxy group represented by the formula (I) and facilitates pattern formation, while also increasing the strength of the cured product.

[0060] Preferred examples of the crosslinking agent include melamine compounds, guanamine compounds, glycoluril compounds, and urea compounds containing, on average, two or more methylol groups and / or alkoxymethyl groups per molecule; amino condensates modified with formaldehyde or formaldehyde-alcohol; phenol compounds having, on average, two or more methylol groups or alkoxymethyl groups per molecule; and epoxy compounds having, on average, two or more epoxy groups per molecule.

[0061] The melamine compound may be one represented by the following formula (D1). [ka]

[0062] In formula (D1), R 201 ~R 206 are each independently a methylol group, a saturated hydrocarbyloxymethyl group having 2 to 5 carbon atoms, or a hydrogen atom, and at least one of them is a methylol group or a saturated hydrocarbyloxymethyl group. Examples of the saturated hydrocarbyloxymethyl group include alkoxymethyl groups such as a methoxymethyl group and an ethoxymethyl group.

[0063] Examples of the melamine compound represented by the formula (D1) include trimethoxymethyl monomethylol melamine, dimethoxymethyl monomethylol melamine, trimethylol melamine, hexamethylol melamine, hexamethoxymethyl melamine, and hexaethoxymethyl melamine.

[0064] The melamine compound represented by formula (D1) can be obtained, for example, by first modifying a melamine monomer with formaldehyde by methylolation according to a known method, or by further modifying the melamine monomer by alkoxylation with an alcohol, preferably a lower alcohol, for example an alcohol having 1 to 4 carbon atoms.

[0065] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, and tetramethoxyethylguanamine.

[0066] Examples of the glycoluril compound include tetramethylol glycoluril and tetrakis(methoxymethyl) glycoluril.

[0067] Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, tetramethoxyethyl urea, tetraethoxymethyl urea, and tetrapropoxymethyl urea.

[0068] Examples of the amino condensate modified with formaldehyde or formaldehyde-alcohol include a melamine condensate modified with formaldehyde or formaldehyde-alcohol, and a urea condensate modified with formaldehyde or formaldehyde-alcohol.

[0069] The modified melamine condensate may be obtained by addition condensation polymerization of a compound represented by formula (D1) or a multimer thereof (e.g., an oligomer such as a dimer or trimer) with formaldehyde until a desired molecular weight is reached. As the addition condensation polymerization method, a conventionally known method may be adopted. The modified melamine represented by formula (D1) may be used alone or in combination of two or more.

[0070] Examples of urea condensates modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensates, ethoxymethylated urea condensates, and propoxymethylated urea condensates.

[0071] The modified urea condensate can be obtained, for example, by modifying a urea condensate having a desired molecular weight with formaldehyde by methylolation according to a known method, or by further modifying the urea condensate by alkoxylation with an alcohol.

[0072] Examples of the phenol compound having two or more methylol groups or alkoxymethyl groups on average per molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2',6,6'-tetramethoxymethylbisphenol A, and the like.

[0073] Examples of the epoxy compound having two or more epoxy groups on average per molecule include bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins, novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins, triphenol alkane type epoxy resins, biphenyl type epoxy resins, dicyclopentadiene-modified phenol novolac type epoxy resins, phenol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, naphthalene ring-containing epoxy resins, glycidyl ester type epoxy resins, alicyclic epoxy resins, and heterocyclic type epoxy resins.

[0074] When the (D) component is contained, its content is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, relative to 100 parts by mass of the (A) component. If it is 0.5 parts by mass or more, sufficient curability can be obtained upon light irradiation, and if it is 50 parts by mass or less, the proportion of the (A) component in the photosensitive resin composition does not decrease, so that a sufficient effect can be exerted in the cured product. The (D) component may be used alone or in combination of two or more types.

[0075] [(E) Solvent] The photosensitive resin composition of the present invention may further contain a solvent as component (E). The solvent is not particularly limited as long as it is capable of dissolving components (A) to (D) and various additives described below, but organic solvents are preferred because they have excellent solubility in these components.

[0076] Examples of the organic solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, and γ-butyrolactone. In particular, ethyl lactate, cyclohexanone, cyclopentanone, PGMEA, γ-butyrolactone, and mixed solvents thereof, which have the best solubility for the photoacid generator, are preferred. These organic solvents can be used alone or in combination of two or more.

[0077] From the viewpoints of compatibility and viscosity of the photosensitive resin composition, the content of the component (E) is preferably 50 to 2,000 parts by mass, more preferably 50 to 1,000 parts by mass, and particularly preferably 50 to 100 parts by mass, per 100 parts by mass of the component (A). The component (E) may be used alone or in combination of two or more kinds.

[0078] [Other additives] The photosensitive resin composition of the present invention may contain other additives in addition to the above-mentioned components. Examples of the other additives include surfactants commonly used to improve coatability.

[0079] The surfactant is preferably a nonionic one, and examples thereof include fluorine-based surfactants, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkylamine oxides, fluorine-containing organosiloxane compounds, etc. Commercially available surfactants can be used, and examples thereof include Fluorad (registered trademark) FC-430 (manufactured by 3M), Surflon (registered trademark) S-141, S-145 (manufactured by AGC Seimi Chemical Co., Ltd.), Unidyne (registered trademark) DS-401, DS-4031, DS-451 (manufactured by Daikin Industries, Ltd.), Megafac (registered trademark) F-8151 (manufactured by DIC Corporation), and X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.). Among these, Fluorad FC-430 and X-70-093 are preferred. The content of the surfactant is preferably 0.05 to 1 part by mass relative to 100 parts by mass of component (A).

[0080] The photosensitive resin composition of the present invention may contain a silane coupling agent as another additive. By containing a silane coupling agent, the adhesion of the coating obtained from the composition to the adherend can be further improved. Examples of the silane coupling agent include an epoxy group-containing silane coupling agent and an aromatic group-containing aminosilane coupling agent. These can be used alone or in combination of two or more. The content of the silane coupling agent is not particularly limited, but when contained, it is preferably 0.01 to 5 mass% in the photosensitive resin composition of the present invention.

[0081] The photosensitive resin composition of the present invention can be prepared by a conventional method, for example, by stirring and mixing the above-mentioned components, and then filtering the solid content with a filter or the like as necessary.

[0082] The photosensitive resin composition of the present invention thus prepared is suitably used, for example, as a protective film for semiconductor elements, a protective film for wiring, a coverlay film, a solder mask, a material for an insulating film for a through-hole electrode (for TSV), and further as an adhesive between laminated substrates in three-dimensional lamination.

[0083] [Pattern formation method using photosensitive resin composition] The pattern forming method using the photosensitive resin composition of the present invention comprises the steps of: (i) forming a photosensitive resin film on a substrate using the photosensitive resin composition of the present invention; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to form a pattern. It includes.

[0084] Step (i) is a step of forming a photosensitive resin film on a substrate using the photosensitive resin composition. Examples of the substrate include silicon wafers, silicon wafers for through-hole electrodes, silicon wafers thinned by backside polishing, plastic or ceramic substrates, and substrates having metals such as Ni and Au on the entire surface or part of the substrate by ion sputtering or plating. Substrates having irregularities may also be used.

[0085] The photosensitive resin film may be formed, for example, by applying the photosensitive resin composition onto a substrate and pre-heating (pre-baking) as necessary. The application method may be a known method, such as a dip method, a spin coating method, or a roll coating method. The amount of the photosensitive resin composition applied may be appropriately selected depending on the purpose, but it is preferable to apply the composition so that the thickness of the resulting photosensitive resin film is preferably 0.1 to 200 μm, more preferably 1 to 150 μm.

[0086] In order to improve the film thickness uniformity on the substrate surface, a solvent may be dropped onto the substrate before applying the photosensitive resin composition (pre-wetting method). The solvent and the amount of the dropped solvent can be appropriately selected depending on the purpose. As the solvent, for example, alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, glycols such as PGME, etc. are preferable, but it is also possible to use a solvent used in the photosensitive resin composition.

[0087] Here, in order to efficiently carry out the photocuring reaction, pre-baking may be carried out as necessary to evaporate the solvent etc. Pre-baking can be carried out, for example, at 40 to 140° C. for about 1 minute to 1 hour.

[0088] Next, (ii) the photosensitive resin film is exposed to light. In this case, the exposure is preferably performed with light having a wavelength of 10 to 600 nm, and more preferably with light having a wavelength of 190 to 500 nm. Examples of light having such wavelengths include light of various wavelengths generated by a radiation generator, such as ultraviolet rays such as g-rays, h-rays, and i-rays, and far ultraviolet rays (248 nm, 193 nm). Of these, light having a wavelength of 248 to 436 nm is particularly preferred. The exposure dose is 10 to 10,000 mJ / cm. 2 is preferred.

[0089] The exposure may be performed through a photomask. The photomask may be, for example, a photomask having a desired pattern cut out. The material of the photomask is not particularly limited, but is preferably one that blocks light of the wavelengths. For example, a photomask having a light-shielding film made of chromium or the like is preferably used.

[0090] Furthermore, in order to enhance the development sensitivity, a post-exposure bake (PEB) may be performed. The PEB is preferably performed at 40 to 150° C. for 0.5 to 10 minutes. The exposed portion is crosslinked by the PEB to form an insolubilized pattern that is insoluble in an organic solvent, which is a developer.

[0091] After exposure or PEB, (iii) the photosensitive resin film is developed with a developer to form a pattern. As the developer, for example, organic solvents such as alcohols such as IPA, ketones such as cyclohexanone, and glycols such as PGME are preferred, but it is also possible to use a solvent used in the photosensitive resin composition. As a development method, a normal method, for example, a method of immersing a substrate on which a pattern has been formed in the developer, can be mentioned. The non-exposed portion is dissolved and removed by organic solvent development to form a pattern. Thereafter, washing, rinsing, drying, etc. are performed as necessary to obtain a resin film having a desired pattern.

[0092] Furthermore, (iv) the film on which the pattern is formed may be post-cured using an oven or a hot plate, preferably at 100 to 250°C, more preferably at 150 to 220°C. If the post-curing temperature is 100 to 250°C, the crosslink density of the photosensitive resin composition can be increased and the remaining volatile components can be removed, which is preferable from the viewpoints of adhesion to the substrate, heat resistance and strength, electrical properties, and adhesive strength. The post-curing time is preferably 10 minutes to 10 hours, more preferably 10 minutes to 3 hours. If the photosensitive resin composition of the present invention is used, a film having excellent various film properties can be obtained even if the post-curing is performed at a relatively low temperature of about 200°C. The film thickness of the film (cured film) after post-curing is usually 1 to 200 μm, preferably 5 to 50 μm.

[0093] When it is not necessary to form a pattern, for example when it is desired to simply form a uniform film, in step (ii) of the pattern formation method, the film can be formed by exposing the film to light of an appropriate wavelength without using the photomask.

[0094] [Board bonding method] The photosensitive resin composition of the present invention can also be used as an adhesive for bonding two substrates. An example of a method for bonding substrates is a method in which a substrate on which a film is formed using the photosensitive resin composition of the present invention is bonded to a second substrate under suitable conditions of heat and pressure so that an adhesive bond is formed between the two substrates. Either or both of the substrate on which the film is formed and the second substrate may be chipped by dicing or the like. As bonding conditions, a heating temperature of 50 to 200°C and a time of 1 to 60 minutes are preferred. A wafer bonder device may be used as a bonding device to bond wafers together under reduced pressure while applying a load, or chip-wafer or chip-chip bonding may be performed using a flip chip bonder device. The adhesive layer formed between the substrates has a higher bonding strength by a post-curing treatment described later, resulting in permanent adhesion.

[0095] The substrates that have been attached (bonded) are post-cured under the same conditions as in step (iv) described above, thereby increasing the crosslink density of the coating and increasing the substrate adhesive strength. A crosslinking reaction occurs due to heating during bonding, but the crosslinking reaction does not cause a side reaction accompanied by degassing, so that bonding defects (voids) are not induced, particularly when used as a substrate adhesive.

[0096] [Photosensitive dry film] The photosensitive dry film of the present invention comprises a support film and a photosensitive resin coating obtained from the photosensitive resin composition on the support film.

[0097] The photosensitive dry film (support film and photosensitive resin film) is solid, and since the photosensitive resin film does not contain a solvent, there is no risk of air bubbles caused by the evaporation of the solvent remaining inside the photosensitive resin film or between the photosensitive resin film and the uneven substrate.

[0098] The thickness of the photosensitive resin film is preferably 5 to 200 μm, more preferably 10 to 100 μm, from the viewpoints of flatness on an uneven substrate, step coverage, and substrate lamination spacing.

[0099] In addition, the viscosity and fluidity of the photosensitive resin film are closely related, and the photosensitive resin film can exhibit appropriate fluidity in an appropriate viscosity range, and can penetrate deep into narrow gaps and strengthen adhesion to the substrate by softening the resin. Therefore, from the viewpoint of fluidity, the viscosity of the photosensitive resin film is preferably 10 to 5,000 Pa·s, more preferably 30 to 2,000 Pa·s, and even more preferably 50 to 300 Pa·s at 80 to 120°C. In the present invention, the viscosity is a value measured using a rotational viscometer.

[0100] When the photosensitive dry film of the present invention is adhered to a substrate having irregularities, the photosensitive resin film conforms to the irregularities and covers the substrate, achieving high flatness. In particular, the photosensitive resin film is characterized by low viscoelasticity, so that a higher flatness can be achieved. Furthermore, when the photosensitive resin film is adhered to the substrate in a vacuum environment, the occurrence of gaps can be more effectively prevented.

[0101] The photosensitive dry film of the present invention can be produced by applying the photosensitive resin composition onto a support film and drying it to form a photosensitive resin film. As a production device for the photosensitive dry film, a film coater for producing a pressure-sensitive adhesive product can be used. Examples of the film coater include a comma coater, a comma reverse coater, a multi-coater, a die coater, a lip coater, a lip reverse coater, a direct gravure coater, an offset gravure coater, a three-bottom reverse coater, and a four-bottom reverse coater.

[0102] When the support film is unwound from the unwinding shaft of the film coater and passed through the coater head of the film coater, the photosensitive resin composition is applied to the support film in a predetermined thickness, and then the film is passed through a hot air circulating oven at a predetermined temperature and time, and dried on the support film to form a photosensitive resin film, thereby producing a photosensitive dry film. In addition, if necessary, the photosensitive dry film is passed through a laminating roll at a predetermined pressure together with a protective film unwound from another unwinding shaft of the film coater to bond the photosensitive resin film on the support film to the protective film, and then the film is wound up on the winding shaft of the film coater to produce a photosensitive dry film with a protective film. In this case, the temperature is preferably 25 to 150°C, the time is preferably 1 to 100 minutes, and the pressure is preferably 0.01 to 5 MPa.

[0103] The support film may be a single-layer film made of a single film, or a multi-layer film made of a plurality of laminated films. Examples of the material of the film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Among these, polyethylene terephthalate is preferred because it has appropriate flexibility, mechanical strength, and heat resistance. These films may be subjected to various treatments such as corona treatment and release agent coating. Commercially available products may be used, such as Therapeel WZ (RX), Therapeel BX8 (R) (all manufactured by Toray Film Processing Co., Ltd.), E7302, E7304 (all manufactured by Toyobo Co., Ltd.), Purex G31, Purex G71T1 (all manufactured by Teijin DuPont Films Co., Ltd.), PET38×1-A3, PET38×1-V8, and PET38×1-X08 (all manufactured by Nippa Corporation).

[0104] The protective film may be the same as the support film described above, but polyethylene terephthalate and polyethylene are preferred because they have appropriate flexibility. Commercially available products may be used, and examples of polyethylene terephthalate include those already exemplified, and examples of polyethylene include GF-8 (manufactured by Tamapoly Co., Ltd.) and PE film type 0 (manufactured by Nippa Co., Ltd.).

[0105] The thickness of each of the support film and the protective film is preferably 10 to 100 μm, more preferably 25 to 50 μm, from the viewpoints of stability in the production of the photosensitive dry film and prevention of curling, ie, winding tendency around the core.

[0106] [Patterning method using photosensitive dry film] The pattern forming method using the photosensitive dry film of the present invention includes the steps of: (i') forming a photosensitive resin film on a substrate using the photosensitive dry film of the present invention; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to form a pattern. It includes.

[0107] First, in step (i'), a photosensitive resin film is formed on a substrate using a photosensitive dry film. Specifically, the photosensitive resin film of the photosensitive dry film is attached to the substrate to form the photosensitive resin film on the substrate. In addition, when the photosensitive dry film has a protective film, the protective film is peeled off from the photosensitive dry film, and then the photosensitive resin film of the photosensitive dry film is attached to the substrate. The attachment can be performed, for example, using a film attachment device.

[0108] The substrate may be the same as that described in the pattern forming method using a photosensitive resin composition. The film laminating device is preferably a vacuum laminator. For example, the protective film of the photosensitive dry film is peeled off, and the exposed photosensitive resin film is adhered to the substrate on a table at a predetermined temperature in a vacuum chamber at a predetermined vacuum degree using a laminating roll at a predetermined pressure. The temperature is preferably 60 to 120°C, the pressure is preferably 0 to 5.0 MPa, and the vacuum degree is preferably 50 to 500 Pa.

[0109] In order to obtain a photosensitive resin film of the required thickness, the film may be applied multiple times as necessary. The number of times of application is, for example, about 1 to 10 times, and a photosensitive resin film having a thickness of 10 to 1,000 μm, particularly about 100 to 500 μm, can be obtained.

[0110] In order to efficiently carry out the photocuring reaction of the photosensitive resin film and to improve the adhesion between the photosensitive resin film and the substrate, pre-baking may be performed as necessary. Pre-baking can be performed, for example, at 40 to 140° C. for about 1 minute to 1 hour.

[0111] As in the case of the pattern forming method using the photosensitive resin composition, the photosensitive resin film attached to the substrate can be patterned by (ii) exposing the photosensitive resin film to light, (iii) developing the exposed photosensitive resin film with a developer to form a pattern, and (iv) performing a post-curing treatment as necessary. Note that the support film of the photosensitive dry film is peeled off before pre-baking or PEB, or removed by other methods depending on the process.

[0112] The films obtained from the photosensitive resin composition and the photosensitive dry film have excellent heat resistance, flexibility, electrical insulation, mechanical properties, and adhesion to substrates, etc., and are suitably used as protective films for electrical and electronic components such as semiconductor elements and as films for bonding substrates. EXAMPLES

[0113] The present invention will be described in more detail below with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples. Note that Mw was measured by GPC using a TSKgel Super HZM-H (manufactured by Tosoh Corporation) column under analysis conditions of a flow rate of 0.6 mL / min, an elution solvent of THF, and a column temperature of 40° C., with monodisperse polystyrene as the standard.

[0114] The compounds (S-1) to (S-6) used in the synthesis examples are shown below. [ka]

[0115] [1] Synthesis of silicone resin [Synthesis Example 1] Into a 3 L flask equipped with a stirrer, a thermometer, a nitrogen purge device, and a reflux condenser, 215.0 g (0.5 mol) of compound (S-6) was added, followed by 2,000 g of toluene, and the mixture was heated to 70° C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 67.9 g (0.35 mol) of compound (S-4) and compound (S-5) (y 1453.0 g (0.15 mol) of dimethylformamide (H2O4, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups=1 / 1 (molar ratio)). After completion of the addition, the mixture was heated to 100° C. and aged for 6 hours, after which toluene was removed from the reaction solution by distillation under reduced pressure to obtain Silicone Resin A-1. Silicone Resin A-1 is 1 It was confirmed by H-NMR (manufactured by Bruker) that the silicone resin contained repeating units a1, a2, b1, and b2. The Mw of the silicone resin A-1 was 62,000, and the silicone content was 61.6% by mass.

[0116] [Synthesis Example 2] Into a 3 L flask equipped with a stirrer, a thermometer, a nitrogen purge device, and a reflux condenser, 53.00 g (0.20 mol) of compound (S-2) and 117.6 g (0.30 mol) of compound (S-1) were added, followed by the addition of 2,000 g of toluene and heating to 70° C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 48.5 g (0.25 mol) of compound (S-4) and 48.5 g (0.25 mol) of compound (S-5) (y 1 755.0 g (0.25 mol) of dimethylformamide (H2O3=40, Shin-Etsu Chemical Co., Ltd.) was added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups=1 / 1 (molar ratio)). After completion of the addition, the mixture was heated to 100° C. and aged for 6 hours, after which toluene was removed from the reaction solution by vacuum distillation to obtain Silicone Resin A-2. Silicone Resin A-2 was prepared by the following procedure: 1 It was confirmed by H-NMR (manufactured by Bruker) that it contained repeating units a1, a3, a4, b1, b3 and b4. Silicone resin A-2 had Mw of 83,000 and a silicone content of 77.5% by mass.

[0117] [Synthesis Example 3] In a 3 L flask equipped with a stirrer, a thermometer, a nitrogen purge device, and a reflux condenser, 27.9 g (0.15 mol) of compound (S-3), 19.6 g (0.05 mol) of compound (S-1), and 129.0 g (0.30 mol) of compound (S-6) were added, followed by adding 2,000 g of toluene and heating to 70° C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 87.3 g (0.45 mol) of compound (S-4) and compound (S-5) (y 1 79.3 g (0.05 mol) of dimethylformamide (H2O20, Shin-Etsu Chemical Co., Ltd.) was added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups=1 / 1 (molar ratio)). After completion of the addition, the mixture was heated to 100°C and aged for 6 hours, after which toluene was removed from the reaction solution by vacuum distillation to obtain Silicone Resin A-3. Silicone Resin A-3 was prepared by the following procedure: 1 It was confirmed by H-NMR (manufactured by Bruker) that it contained repeating units a1, a2, a4, b1, b2, and b4. Silicone resin A-3 had Mw of 24,000 and a silicone content of 31.2% by mass.

[0118] [2] Preparation of photosensitive resin composition [Examples 1 to 12 and Comparative Examples 1 to 19] The components were mixed according to the amounts shown in Tables 1 to 3, and then the mixture was stirred at room temperature to dissolve. The mixture was then microfiltered through a 1.0 μm Teflon (registered trademark) filter to prepare the photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 19.

[0119] [Table 1]

[0120] [Table 2]

[0121] [Table 3]

[0122] In Tables 1 to 3, B-1 to B-4 and B'-1 to B'-5 are as follows. [ka]

[0123] [ka]

[0124] In Tables 1 to 3, C-1 to C-2 and C'-1 to C'-6 are as follows. [ka]

[0125] [ka]

[0126] In Tables 1 to 3, CL-1 and CL-2 are as follows. [ka]

[0127] In Tables 2 and 3, A'-1 is as follows. [ka]

[0128] [3] Storage stability of varnish The viscosity of the varnish of the photosensitive resin composition shown in Tables 1 to 3 was measured using a viscometer RB-85R manufactured by Toki Sangyo Co., Ltd., and then the varnish was stored at room temperature (25°C) under light-shielded conditions for 360 days, after which the viscosity was measured again. A viscosity change rate of less than ±10% after 360 days compared to the initial day was marked as O, and a viscosity change rate of ±10% or more was marked as ×. The results are shown in Tables 4 to 6.

[0129] [4] Preparation of photosensitive dry film Using a die coater as a film coater and a polyethylene terephthalate film (75 μm thick) as a support film, the varnish of the photosensitive resin composition described in Tables 1 to 3 was applied onto the support film. Next, the film was dried by passing through a hot air circulating oven (length 4 m) set at 100° C. for 5 minutes to form a photosensitive resin film on the support film, thereby obtaining a photosensitive dry film. A polyethylene film (thickness 50 μm) was laminated as a protective film on the photosensitive resin film with a laminating roll at a pressure of 1 MPa to produce a photosensitive dry film with a protective film. The film thickness of each photosensitive resin film was 150 μm. The film thickness of the photosensitive resin film was measured using an optical interference film thickness measuring instrument (F50-EXR manufactured by Filmetrics Inc.).

[0130] [5] Evaluation of resin coating (1) Pattern formation and evaluation, and storage stability evaluation The pattern was formed one day after the production of the photosensitive dry film with the protective film. The photosensitive dry film with the protective film was peeled off, and the degree of vacuum in the vacuum chamber was set to 80 Pa using a vacuum laminator TEAM-100RF (manufactured by Takatori Co., Ltd.), and the photosensitive resin film on the support film was adhered to a migration test substrate (a comb-shaped electrode substrate with copper conductive material, conductive part interval and conductive part width of 20 μm, and conductive part thickness of 4 μm). The temperature condition was 100° C. After returning to normal pressure, the substrate was removed from the vacuum laminator and the support film was peeled off. Next, in order to increase the adhesion to the substrate, preheating was performed at 120° C. for 5 minutes using a hot plate. In order to form a line and space pattern and a contact hole pattern on the obtained photosensitive resin film, exposure was performed using a contact aligner type exposure device under exposure conditions of a wavelength of 405 nm through a mask. After exposure, PEB was performed using a hot plate at 140° C. for 5 minutes, followed by cooling and spray development with PGMEA for 300 seconds to form a pattern.

[0131] The photosensitive resin film on the substrate on which the pattern was formed by the above method was post-cured in an oven at 150°C for 4 hours while purging with nitrogen. Then, the cross sections of the contact hole patterns formed at 300μm, 150μm, 100μm, 70μm, and 50μm were observed by a scanning electron microscope (SEM), and the smallest hole pattern in which the holes penetrated to the bottom of the film was determined as the limiting resolution. Furthermore, the perpendicularity of the 300μm contact hole pattern was evaluated from the obtained cross-sectional photograph, and a perpendicular pattern was marked with ◎, a pattern with a slight inverse taper shape or footing was marked with ○, a pattern with a strong inverse taper shape or footing was marked with △, and an opening failure was marked with ×. The results are shown in Tables 4 to 6.

[0132] In addition, the photosensitive dry film was stored for 360 days under light-shielded conditions at room temperature (25°C), and then the same pattern was formed by the above method. The photosensitive resin film on the substrate on which the pattern was formed was post-cured using an oven at 170°C for 2 hours while purging with nitrogen. Thereafter, the cross sections of the formed contact hole patterns of 300μm, 150μm, 100μm, 70μm, and 50μm were observed by SEM, and the smallest hole pattern in which the holes penetrated to the bottom of the film was determined as the limiting resolution. Furthermore, the perpendicularity of the 300μm contact hole pattern was evaluated from the obtained cross-sectional photograph, and a perpendicular pattern was marked with ◎, a pattern with a slight inverse taper shape or footing was marked with ○, a pattern with a strong inverse taper shape or footing was marked with △, and an opening failure was marked with ×. The results are shown in Tables 4 to 6.

[0133] (2) Evaluation of electrical properties (copper migration) The substrate on which the pattern was formed by the method (1) was used as the substrate for copper migration evaluation, and a test was conducted. The copper migration test was conducted under the conditions of a temperature of 130°C, a humidity of 85%, and an applied voltage of 10V, and the time until a short circuit occurred was confirmed up to an upper limit of 1,000 hours. The results are shown in Tables 4 to 6.

[0134] (3) Evaluation of electrical properties (dielectric breakdown strength) In order to evaluate the dielectric breakdown strength of the photosensitive resin film made of the photosensitive resin composition, each photosensitive resin composition listed in Tables 1 to 3 was applied to a 13 cm x 15 cm, 0.7 mm thick iron plate using a bar coater, exposed to light using a contact aligner type exposure device without a mask under exposure conditions of a wavelength of 405 nm, and then heated at 170°C for 2 hours using an oven to obtain a photosensitive resin film. The photosensitive resin composition was applied so that the film thickness obtained was 0.2 μm. Using this photosensitive resin film, a voltage was applied at a voltage rise rate of 5 V / sec using a dielectric breakdown tester TM-5031AM (manufactured by Tama Densoku Co., Ltd.), and the voltage at which the test specimen broke was measured and taken as the dielectric breakdown strength of the film. The results are shown in Tables 4 to 6.

[0135] (4) Evaluation of reliability (adhesion, crack resistance) The photosensitive dry film with the protective film described above was peeled off, and the degree of vacuum in the vacuum chamber was set to 80 Pa using a vacuum laminator TEAM-100RF (manufactured by Takatori Co., Ltd.), and the photosensitive resin film on the support film was adhered to a CCL substrate on which 10 mm x 10 mm square silicon chips were laminated. The temperature condition was 100°C. After returning to normal pressure, the substrate was removed from the vacuum laminator, and the support film was peeled off. Next, in order to improve adhesion to the substrate, preheating was performed at 120°C for 5 minutes using a hot plate. The obtained photosensitive resin film was exposed to light using a contact aligner type exposure device without a mask under exposure conditions of a wavelength of 405 nm. After light irradiation, PEB was performed on a hot plate at 140°C for 5 minutes, followed by cooling, and post-curing using an oven at 170°C for 2 hours while purging with nitrogen. Then, the substrate was cut into 20 mm x 20 mm square test pieces using a dicing saw (DAD685, manufactured by DISCO, spindle rotation speed 40,000 rpm, cutting speed 20 mm / sec) equipped with a dicing blade, so that the outer circumference of the silicon chip was 5 mm. The obtained test pieces (10 pieces each) were subjected to a heat cycle test (1,000 cycles of holding at -30°C for 10 minutes and at 130°C for 10 minutes). The peeling state of the resin film from the wafer after the heat cycle test and the presence or absence of cracks were confirmed. Those that did not peel or crack at all were marked with ○, those that peeled at least one were marked with ×, and those that cracked at least one were marked with ×. The presence or absence of peeling and cracks was confirmed by top-down observation using an optical microscope and cross-sectional SEM observation. The results are shown in Tables 4 to 6.

[0136] (5) Evaluation of adhesion performance between substrates In order to evaluate the inter-substrate adhesion performance, the photosensitive dry film with the protective film described above was peeled off, and the degree of vacuum in the vacuum chamber was set to 80 Pa using a vacuum laminator TEAM-100RF (manufactured by Takatori Co., Ltd.), and the photosensitive resin film on the support film was adhered to an 8-inch silicon wafer. The temperature condition was 100°C. After returning to normal pressure, the substrate was removed from the vacuum laminator and the support film was peeled off. Next, in order to enhance adhesion to the substrate, preheating was performed at 120°C for 5 minutes using a hot plate. In order to form a 300 μm line and space pattern on the obtained photosensitive resin film, exposure was performed using a contact aligner type exposure device through a mask under exposure conditions of a wavelength of 405 nm. After light irradiation, PEB was performed using a hot plate at 140°C for 5 minutes, followed by cooling, and spray development with PGMEA for 300 seconds to form a pattern. The substrate was then bonded to untreated 8-inch quartz glass or Tempax glass, and heated on a hot plate at 150°C for 5 minutes for temporary bonding. This was followed by post-curing in an oven at 170°C for 2 hours to form an inter-substrate adhesive layer. The bonded wafer was exposed to a temperature of 130°C and a humidity of 85% for 1,000 hours, and the presence or absence of induced bonding defects was confirmed. The results are shown in Tables 4 to 6.

[0137] (6) Evaluation of solvent resistance In order to evaluate the solvent resistance to N-methyl-2-pyrrolidone (NMP), which is often used when forming semiconductor elements, etc., a 15 mm x 15 mm pattern was formed on a silicon wafer using the photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 19 in the same manner as in the wafer preparation for the copper migration test in (1). After immersing the wafer in NMP at 40°C for 1 hour, the change in film thickness and appearance were investigated to evaluate the solvent resistance. Those that showed no change in appearance or film thickness were marked with an ◯, and those that showed swelling, etc. were marked with an ×. The results are shown in Tables 4 to 6.

[0138] (7) Evaluation of relative dielectric constant and dielectric tangent The photosensitive dry film with the protective film described above was peeled off, and exposed to light without a mask using a contact aligner type exposure device under exposure conditions of a wavelength of 405 nm. Then, the film was post-cured in an oven at 170°C for 2 hours while purging with nitrogen. After removing from the oven and peeling off the support film, the relative dielectric constant (10 GHz, 25°C) and dielectric loss tangent (10 GHz, 25°C) were measured. The relative dielectric constant and dielectric loss tangent were measured by a cavity resonator method using an AET device. The results are shown in Tables 4 to 6.

[0139] [Table 4]

[0140] [Table 5]

[0141] [Table 6]

[0142] From the above results, the photosensitive resin composition and photosensitive dry film of the present invention have good storage stability, can easily form a fine pattern in a thick film, and exhibit sufficient properties as a photosensitive material. In addition, the photosensitive resin film obtained from them has high chemical resistance to photoresist stripping solution and the like, and is excellent in adhesion, electrical insulation, and copper migration resistance, and is highly reliable as an insulating protective film, and can be suitably used as a material for forming a film for protecting various electric and electronic parts such as circuit boards, semiconductor elements, and display elements. According to the present invention, it is possible to provide a more reliable photosensitive resin composition and photosensitive dry film.

Claims

1. (A) a silicone resin having an epoxy group and / or a phenolic hydroxy group, represented by the following formula (A): (B) a photoacid generator represented by the following formula (B): (C) benzotriazole-based compounds, and (D) Crosslinking Agent A photosensitive resin composition comprising: 【Chemistry 1】 (In the formula, R 1 to R 4 are each independently a hydrocarbyl group having 1 to 8 carbon atoms. k is an integer from 1 to 600. a and b represent the composition ratio (molar ratio) of each repeating unit and are numbers that satisfy 0<a<1, 0<b<1, and a+b=1. X is a divalent organic group containing an epoxy group and / or a phenolic hydroxy group.) 【Chemistry 2】 (In the formula, R A is a hydrocarbyl group having 1 to 12 carbon atoms, some or all of whose hydrogen atoms may be substituted with fluorine atoms. R B are each independently a monovalent organic group, and two or more R B are directly bonded to each other, or —O—, —S—, —SO—, —SO 2 They may form a ring structure containing the element E by bonding via -, -NH-, -CO-, -COO-, -CONH-, a saturated hydrocarbylene group having 1 to 20 carbon atoms, or a phenylene group. E is an element of valence n from groups 15 to 17 of the periodic table. n is an integer from 1 to 3.

2. 2. The photosensitive resin composition according to claim 1, wherein the silicone resin (A) contains repeating units represented by the following formulas (a1) to (a4) and (b1) to (b4): 【Chemistry 3】 [In the formula, R 1 ~R 4 are each independently a hydrocarbyl group having 1 to 8 carbon atoms. k is an integer of 1 to 600. 1 ~a 4 and b 1 ~b 4 represents the composition ratio (molar ratio) of each repeating unit, and 0≦a 1 <1, 0≦a 2 <1, 0≦a 3 <1, 0≦a 4 <1, 0≦b 1 <1, 0≦b 2 <1, 0≦b 3 <1, 0≦b 4 <1, 0<a 1 +a 2 +a 3 <1, 0<b 1 +b 2 +b 3 <1, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 = 1. 1 is a divalent group represented by the following formula (X1): 2 is a divalent group represented by the following formula (X2). 3 is a divalent group represented by the following formula (X3). 4 is a divalent group represented by the following formula (X4). 【Chemistry 4】 (In the formula, Y 1 R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 11 and R 12 R is each independently a hydrogen atom or a methyl group. 13 and R 14 are each independently a saturated hydrocarbyl group having 1 to 4 carbon atoms or a saturated hydrocarbyloxy group having 1 to 4 carbon atoms. 1 and p 2 are each independently an integer from 0 to 7. 1 and q 2 are each independently an integer of 0 to 2. The dashed lines represent bonds. 【Chemistry 5】 (In the formula, Y 2 R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 21 and R 22 R is each independently a hydrogen atom or a methyl group. 23 and R 24 are each independently a saturated hydrocarbyl group having 1 to 4 carbon atoms or a saturated hydrocarbyloxy group having 1 to 4 carbon atoms. 1 and r 2 are each independently an integer from 0 to 7. 1 and s 2 are each independently an integer of 0 to 2. The dashed lines represent bonds. 【Chemistry 6】 (In the formula, R 31 and R 32 are each independently a hydrogen atom or a methyl group. 1 and t 2 are each independently an integer from 0 to 7. The dashed lines represent bonds. 【Chemistry 7】 (In the formula, R 41 and R 42 R is each independently a hydrogen atom or a methyl group. 43 and R 44 are each independently a hydrocarbyl group having 1 to 8 carbon atoms. 1 and u 2 are each independently an integer of 0 to 7. v is an integer of 0 to 600. The dashed lines represent bonds.

3. 3. The photosensitive resin composition according to claim 1, wherein E is a sulfur atom and n is 2.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the crosslinking agent (D) is at least one selected from the group consisting of nitrogen-containing compounds selected from melamine compounds, guanamine compounds, glycoluril compounds and urea compounds containing, on average, two or more methylol groups and / or alkoxymethyl groups in one molecule; amino condensates modified with formaldehyde or formaldehyde-alcohol; phenol compounds having, on average, two or more methylol groups or alkoxymethyl groups in one molecule; and epoxy compounds having, on average, two or more epoxy groups in one molecule.

5. The photosensitive resin composition according to any one of claims 1 to 4, further comprising (E) a solvent.

6. A photosensitive resin film obtained from the photosensitive resin composition according to any one of claims 1 to 5.

7. A photosensitive dry film comprising a support film and the photosensitive resin film according to claim 6 on the support film.

8. (i) forming a photosensitive resin film on a substrate using the photosensitive resin composition according to any one of claims 1 to 5; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to form a pattern. A pattern forming method comprising the steps of:

9. (i') forming a photosensitive resin film on a substrate using the photosensitive dry film according to claim 6; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to form a pattern. A pattern forming method comprising the steps of:

10. 10. The method for forming a pattern according to claim 8, further comprising the step of (iv) post-curing the photosensitive resin film patterned by development at a temperature of 100 to 250°C.

11. The photosensitive resin composition according to any one of claims 1 to 5, which is a material for a protective film for electric / electronic parts.

12. The photosensitive resin composition according to any one of claims 1 to 5, which is a material for a substrate bonding film for bonding two substrates together.

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