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

Abstract

To provide: a photosensitive resin composition capable of easily forming a thickly filmed and fine vertical pattern, and capable of forming a resin film (a resin layer) excellent in solder resistance, heat resistance, crack resistance, and various film characteristics such as adhesion and reduced warpage of substrate particularly to a base material used for a circuit board such as a substrate, an electronic component, and a semiconductor element, and excellent in fidelity as a protective film for electric and electronic components, and a film for substrate 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) an acid-crosslinkable group-containing silicone resin; (B) an epoxy compound expressed by the following formula (B1); and (C) an optical acid generator. In the formula, R1 is a hydrogen atom, a 1-4C saturated hydrocarbyl group, a phenyl group, a hydroxyphenyl group, or a halogenated phenyl group.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Conventionally, photosensitive polyimide compositions, photosensitive epoxy resin compositions, and photosensitive silicone compositions have been used as photosensitive protective films for semiconductor devices and insulating films for multilayer printed circuit boards. As a photosensitive material applicable to the protection of such substrates and circuits, a photosensitive silicone composition with particularly excellent 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 resistance and adhesion, but it has the 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 mainly composed of a silphenylene skeleton-containing silicone polymer has been proposed (Patent Document 2). While this photosensitive silicone composition improves chemical resistance to photoresist stripping solutions, it has problems such as the cured material peeling off the substrate after heat resistance testing, reduced adhesion to the substrate, and solder resistance, and further improvements were desired. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2002-88158 [Patent Document 2] Japanese Patent Publication No. 2008-184571 [Overview of the project] [Problems that the invention aims to solve]

[0005] The present invention has been made in view of the above circumstances, and aims to provide a photosensitive resin composition, a photosensitive resin film, a photosensitive dry film, and a pattern forming method using the same, which can easily form thick, fine vertical patterns, and which have excellent various film properties such as solder resistance, heat resistance, crack resistance, adhesion to substrates used in circuit boards, electronic components, semiconductor elements, etc., and low warping of the substrate, and which can form a resin film (resin layer) that is highly reliable as a protective film for electrical and electronic components or a bonding film for substrates. [Means for solving the problem]

[0006] The inventors conducted diligent studies to achieve the above objective and found that the above objective can be achieved by a photosensitive resin composition comprising (A) an acid-crosslinkable group-containing silicone resin, (B) an epoxy compound having a specific structure, and (C) a photoacid generator, thereby completing the present invention.

[0007] In other words, the present invention provides the following photosensitive resin composition, photosensitive resin coating, photosensitive dry film, and pattern forming method. 1. (A) Silicone resin containing acid crosslinkable groups, (B) Epoxy compounds represented by the following formula (B1), and (C) Photoacid Generator A photosensitive resin composition containing [a specific substance]. [ka] (In the formula, R 1 (This refers to a hydrogen atom, a saturated hydrocarbyl group having 1 to 4 carbon atoms, a phenyl group, a hydroxyphenyl group, or a halogen-substituted phenyl group.) 2. (A) A photosensitive resin composition of type 1, wherein the silicone resin is represented by the following formula (A1). [ka] (In the formula, R 1 ~R 4Each is independently a hydrocarbyl group having 1 to 8 carbon atoms. k is an integer of 1 to 600. 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. ) 3. (A) The photosensitive resin composition according to 2, wherein the silicone resin contains repeating units represented by the following formulas (a1) to (a4) and (b1) to (b4). [Chemical formula] [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. a 1 ~a 4 and b 1 ~b 4 represent 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. X 1 is a divalent group represented by the following formula (X1). X 2 is a divalent group represented by the following formula (X2). X 3 is a divalent group represented by the following formula (X3). X 4 is a divalent group represented by the following formula (X4). ] [Chemical formula] (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 Each of these is independently either a hydrogen atom or a methyl group. 13 and R 14 These are, independently, saturated hydrocarbyl groups having 1 to 4 carbon atoms or saturated hydrocarbyloxy groups having 1 to 4 carbon atoms. 1 and p 2 Each of these is an integer between 0 and 7, independently of the others. 1 and q 2 Each of these is an integer between 0 and 2, independently of the others. The dashed lines represent combinations. [ka] (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 Each of these is independently either a hydrogen atom or a methyl group. 23 and R 24 These are, independently, saturated hydrocarbyl groups having 1 to 4 carbon atoms or saturated hydrocarbyl oxy groups having 1 to 4 carbon atoms. 1 and r 2 Each of these is an integer between 0 and 7, independently of the others. 1 and s 2 Each of these is an integer between 0 and 2, independently of the others. The dashed lines represent combinations. [ka] (In the formula, R 31 and R 32 These are, independently, a hydrogen atom or a methyl group. 1 and t 2 Each of these is an integer between 0 and 7, independently of the others. The dashed lines represent combinations. [ka] (In the formula, R 41 and R 42 Each of these is independently either a hydrogen atom or a methyl group. 43 and R 44 These are, independently, hydrocarbyl groups having 1 to 8 carbon atoms. 1 and u 2 Each of the integers is independently between 0 and 7. v is an integer between 0 and 600. The dashed line represents a combination. 4. A photosensitive resin composition of any one of 1 to 3, wherein the content of the epoxy compound of component (B) is 3 to 100 parts by mass per 100 parts by mass of component (A). 5. Furthermore, (D) a photosensitive resin composition according to any of 1 to 4, comprising a crosslinking agent. 6. (D) A photosensitive resin composition of 5 in which the crosslinking agent is at least one selected from melamine compounds, guanamine compounds, glycoluryl compounds and urea compounds, amino condensates modified with formaldehyde or formaldehyde-alcohol, phenol compounds having an average of two or more methylol groups or alkoxymethyl groups per molecule, and epoxy compounds having an average of two or more epoxy groups per molecule. 7. Furthermore, (E) a photosensitive resin composition according to any of 1 to 6, comprising a solvent. A photosensitive resin film obtained from any of the photosensitive resin compositions described in 8.1 to 7. 9. A photosensitive dry film comprising a support film and a photosensitive resin coating of 8 on the support film. 10. (i) A step of forming a photosensitive resin film on a substrate using any of the photosensitive resin compositions 1 to 7. (ii) A step of exposing the photosensitive resin film, and (iii) A step of developing the exposed photosensitive resin film using a developer to form a pattern. A pattern formation method including the following. 11.(i') A step of forming a photosensitive resin film on a substrate using the photosensitive dry film of 9, (ii) A step of exposing the photosensitive resin film, and (iii) A step of developing the exposed photosensitive resin film using a developer to form a pattern. A pattern formation method including the following. 12. A pattern forming method according to 10 or 11, further comprising the step of (iv) post-curing the photosensitive resin film, which has been patterned by development, at a temperature of 100 to 250°C. 13. A photosensitive resin composition according to any of 1 to 7, which is a material for a protective coating for electrical and electronic components. 14. A photosensitive resin composition, one of 1 to 7, which is a material for a substrate bonding film for bonding two substrates together. [Effects of the Invention]

[0008] The photosensitive resin composition of the present invention can form films over a wide range of film thicknesses, and furthermore, it is possible to easily form thick, fine, and highly perpendicular patterns using the pattern formation method described later. Films obtained using the photosensitive resin composition and photosensitive dry film of the present invention have excellent solder resistance, heat resistance, and low substrate warping, and also have excellent mechanical properties such as adhesion to substrates used in circuit boards, electronic components, semiconductor elements, etc., crack resistance, and copper migration resistance. In addition, 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, as well as a film-forming material for substrate adhesion. [Modes for carrying out the invention]

[0009] [Photosensitive resin composition] The photosensitive resin composition of the present invention comprises (A) an acid-crosslinkable group-containing silicone resin, (B) an epoxy compound having a specific structure, and (C) a photoacid generator.

[0010] [(A) Acid-crosslinked silicone resin] (A) The silicone resin contains an acid-crosslinkable group in the molecule. Here, the acid-crosslinkable group means a group in which functional groups can be chemically bonded directly or via a crosslinking agent by the action of an acid. As the acid-crosslinkable group, an epoxy group and a phenolic hydroxy group are preferable. The epoxy group and the phenolic hydroxy group may be contained only one of them, or both of them may be contained.

[0011] As the acid-crosslinkable group-containing silicone resin, those represented by the following formula (A) are preferable.

Chemical formula

[0012] 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 hydroxy group.

[0013] The hydrocarbyl group may be linear, branched, or cyclic. Specific examples thereof include alkyl groups such as methyl group, ethyl group, propyl group, hexyl group, and structural isomers thereof; cyclic saturated hydrocarbyl groups such as cyclohexyl group; aryl groups such as phenyl group, etc. Among these, the methyl group and the phenyl group are preferable due to the ease of obtaining raw materials.

[0014] 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 preferable.

Chemical formula

[0015] In equations (a1) and (b1), X 1 This is a divalent group represented by the following formula (X1). [ka] (In the equation, dashed lines represent connections.)

[0016] 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 Each of these is independently either a hydrogen atom or a methyl group. 13 and R 14 These are, independently, saturated hydrocarbyl groups having 1 to 4 carbon atoms or saturated hydrocarbyloxy groups having 1 to 4 carbon atoms. 1 and p 2 Each of these is an integer between 0 and 7, independently of the others. 1 and q 2 Each of these is an integer between 0 and 2, independently of the others.

[0017] The saturated hydrocarbyl group may be linear, branched, or cyclic. Specific examples include alkyl groups such as methyl, ethyl, propyl, and butyl groups, and their structural isomers; and cyclic saturated hydrocarbyl groups such as cyclopropyl and cyclobutyl groups. The saturated hydrocarbyloxy group may be linear, branched, or cyclic. Specific examples include alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups, and their structural isomers; and cyclic saturated hydrocarbyloxy groups such as cyclopropyl and cyclobutyl groups.

[0018] In equations (a2) and (b2), X 2 This is a divalent group represented by the following formula (X2). [ka] (In the formula, the dashed line represents a bond.)

[0019] In formula (X2), Y 2 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. R 21 and R 22 are each independently a hydrogen atom or a methyl group. R 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. r 1 and r 2 are each independently an integer from 0 to 7. s 1 and s 2 are each independently an integer from 0 to 2. Examples of the saturated hydrocarbyl group and the saturated hydrocarbyloxy group include those similar to those exemplified in the description of R 13 and R 14 .

[0020] In formulas (a3) and (b3), X 3 is a divalent group represented by the following formula (X3). [Chemical formula] (In the formula, the dashed line represents a bond.)

[0021] In formula (X3), R 31 and R 32 are each independently a hydrogen atom or a methyl group. t 1 and t 2 are each independently an integer from 0 to 7.

[0022] In formulas (a4) and (b4), X 4 is a divalent group represented by the following formula (X4). [Chemical formula] (In the formula, the broken line represents a bond.)

[0023] In formula (X4), R 41 and R 42 are each independently a hydrogen atom or a methyl group. R 43 and R 44 are each independently a hydrocarbyl group having 1 to 8 carbon atoms. u 1 and u 2 are each independently an integer from 0 to 7. v is an integer from 0 to 600, preferably an integer from 0 to 400, more preferably an integer from 0 to 200. Examples of the hydrocarbyl group include those similar to those exemplified in the description of R 1 ~R 4 .

[0024] The silicone resin of component (A) preferably has a weight average molecular weight (Mw) of 3,000 to 500,000, more preferably 5,000 to 200,000. In the present invention, Mw is a polystyrene equivalent measurement value by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an elution solvent.

[0025] In formulas (a1) to (a4) and (b1) to (b4), a 1 ~a 4 and b 1 ~b 4 represent the composition ratio (molar ratio) of each repeating unit, where 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 + b1 +b 2 +b 3 +b 4 A number that satisfies = 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 Numbers that satisfy =1 are 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 A number that satisfies =1 is even more preferable. Furthermore, from the point of reaction, 0 2 Preferably, <1, and 0.2 ≤ b 2 It is more preferable that ≤0.95, and 0.3 ≤ b 2 ​It is even more preferable that the value be ≤0.9.

[0026] The repeating units described above may be bonded randomly or bonded as a block polymer. Furthermore, if there are two or more siloxane units in each repeating unit, each siloxane unit may be identical, or it may contain two or more different types of siloxane units. If it contains two or more different types of siloxane units, the siloxane units may be bonded randomly, or it may contain multiple blocks of the same type of siloxane unit. In addition, the silicone (siloxane unit) content in the silicone resin is preferably 30 to 80% by mass.

[0027] The silicone resin component (A) functions to provide film-forming ability. The resulting resin film has good adhesion to laminates, substrates, etc., good pattern-forming ability, crack resistance, and heat resistance.

[0028] The silicone resin of component (A) may be used alone or in combination of two or more types.

[0029] [(A) Method for manufacturing silicone resin] The silicone resin of component (A) can be produced by addition polymerization in the presence of a metal catalyst, using a compound represented by formula (1), a compound represented by formula (2), at least one compound selected from the compounds represented by formula (3), formula (4), and formula (5), and optionally a compound represented by formula (6). [ka] (In the formula, R 1 ~R 4 (and k are the same as above.)

[0030] [ka] (In the formula, R 11 ~R 14 , R21 ~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.)

[0031] The aforementioned metal catalysts include elemental platinum group metals such as platinum (including platinum black), rhodium, and palladium; platinum chloride, chloroplatinic acid, and chloroplatinate salts such as H2PtCl4·xH2O, H2PtCl6·xH2O, NaHPtCl6·xH2O, KHPtCl6·xH2O, Na2PtCl6·xH2O, K2PtCl4·xH2O, PtCl4·xH2O, PtCl2, and Na2HPtCl4·xH2O (where x is preferably an integer from 0 to 6, and particularly preferably 0 or 6); and alcohol-modified chloroplatinic acid (for example, as described in U.S. Patent No. 3,220,972). ); complexes of chloroplatinic acid and olefins (for example, those described in U.S. Patent No. 3,159,601, U.S. Patent No. 3,159,662 and U.S. Patent No. 3,775,452); platinum group metals such as platinum black and palladium supported on a carrier such as alumina, silica, or carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (so-called Wilkinson catalyst); complexes of platinum chloride, chloroplatinic acid or chloroplatinate salts with vinyl group-containing siloxanes (especially vinyl group-containing cyclic siloxanes), etc. can be used.

[0032] The amount of 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 raw material compounds.

[0033] In the addition polymerization reaction described above, a solvent may be used as needed. Hydrocarbon solvents such as toluene and xylene are preferred as solvents.

[0034] The polymerization temperature is preferably 40 to 150°C, and more preferably 60 to 120°C, from the viewpoint of preventing catalyst deactivation and enabling polymerization to be completed in a short time. The polymerization time depends on the type and amount of resin obtained, but to prevent moisture from interfering with the polymerization system, it is preferably about 0.5 to 100 hours, and more preferably 0.5 to 30 hours. After the reaction is complete, if a solvent was used, it can be removed by distillation to obtain the silicone resin of component (A).

[0035] The reaction method is not particularly limited, but for example, when reacting a compound represented by formula (1), a compound represented by formula (2), at least one selected from the compounds represented by formula (3), formula (4), and formula (5), and optionally a compound represented by formula (6), one method is to first mix at least one selected from the compounds represented by formula (3), formula (4), and formula (5), and optionally a compound represented by formula (6), heat the mixture, add a metal catalyst to the mixture, and then dropwise add the compounds represented by formula (1) and formula (2) over 0.1 to 5 hours.

[0036] Each compound is preferably formulated such that the total number of hydrosilyl groups from the compound represented by formula (1) and the compound represented by formula (2) is, in molar ratio, 0.67 to 1.67, more preferably 0.83 to 1.25, relative to the total number of alkenyl groups 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).

[0037] The Mw of the resulting resin can be controlled by using monoallyl compounds such as o-allylphenol, or monohydrosilanes such as triethylhydrosilane, or monohydrosiloxanes as molecular weight modifiers.

[0038] [(B) Epoxy compounds] The epoxy compound of component (B) is represented by the following formula (B1). [ka]

[0039] In formula (B1), R 1 This is a hydrogen atom, a saturated hydrocarbyl group having 1 to 4 carbon atoms, a phenyl group, a hydroxyphenyl group, or a halogen-substituted phenyl group.

[0040] The saturated hydrocarbyl group may be linear, branched, or cyclic, and specific examples include methyl, ethyl, propyl, and butyl groups.

[0041] R 1 Preferably, the element is a hydrogen atom, a methyl group, or an ethyl group, with a hydrogen atom or a methyl group being more preferred.

[0042] As the alicyclic epoxy compound, commercially available products can be used, such as HP-4700 and HP-4710 manufactured by DIC Corporation.

[0043] The content of component (B) is preferably 3 to 100 parts by mass, more preferably 3 to 75 parts by mass, and even more preferably 5 to 50 parts by mass, per 100 parts by mass of component (A). A content of component (B) within the above range is preferable because it results in a better coating when made into a dry film. Component (B) may be used alone or in combination of two or more types.

[0044] [(C) Photoacid Generator] The photoacid generator of component (C) is not particularly limited as long as it decomposes upon light irradiation and generates acid, but it is preferable that it decomposes upon light with a wavelength of 190 to 500 nm and generates acid. The photoacid generator serves as a curing catalyst. The photosensitive resin composition of the present invention has excellent compatibility with photoacid generators, so a wide range of photoacid generators can be used.

[0045] Examples of the photoacid generators include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzylsulfonate derivatives, sulfonic acid ester derivatives, imido-yl-sulfonate derivatives, oxime sulfonate derivatives, and iminosulfonate derivatives.

[0046] Examples of the onium salts include sulfonium salts represented by the following formula (C1) and iodonium salts represented by the following formula (C2). [ka]

[0047] In formulas (C1) and (C2), R 101 ~R 105 Each of these is independently a saturated hydrocarbyl group having 1 to 12 carbon atoms, which may have substituents, an aryl group having 6 to 12 carbon atoms, which may have substituents, or an aralkyl group having 7 to 12 carbon atoms, which may have substituents. - It is a non-nucleophilic counterion.

[0048] The saturated hydrocarbyl group may be linear, branched, or cyclic. Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and their structural isomers; and cyclic saturated hydrocarbyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl. Examples of the aryl group include phenyl, naphthyl, and biphenylyl groups. Examples of the aralkyl group include benzyl and phenethyl groups.

[0049] Examples of the substituents include oxo groups, saturated hydrocarbyl groups having 1 to 12 carbon atoms, saturated hydrocarbyloxy groups having 1 to 12 carbon atoms, aryl groups having 6 to 24 carbon atoms, aralkyl groups having 7 to 25 carbon atoms, aryloxy groups having 6 to 24 carbon atoms, and arylthio groups having 6 to 24 carbon atoms. The hydrocarbyl portion of the saturated hydrocarbyl group and saturated hydrocarbyloxy group may be linear, branched, or cyclic, and specific examples include R 101 ~R 105 Examples of saturated hydrocarbyl groups represented by the formula shown are similar to those exemplified above.

[0050] R 101 ~R 105 Preferred substituents include saturated hydrocarbyl groups which may have substituents such as methyl, ethyl, propyl, butyl, cyclohexyl, norbornyl, adamantyl, and 2-oxocyclohexyl; aryl groups which may have substituents such as phenyl, naphthyl, biphenylyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 3- or 4-tert-butoxyphenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl, terphenylyl, biphenylyloxyphenyl, and biphenylylthiophenyl; and aralkyl groups which may have substituents such as benzyl and phenethyl. Of these, aryl groups which may have substituents and aralkyl groups which may have substituents are more preferred.

[0051] Examples of the aforementioned non-nucleophilic counterions include halide ions such as chloride ions and bromide ions; fluoroalkanesulfonate ions such as triflate ions, 1,1,1-trifluoroethanesulfonate ions, and nonafluorobutanesulfonate ions; arylsulfonate ions such as tosylate ions, benzenesulfonate ions, 4-fluorobenzenesulfonate ions, and 1,2,3,4,5-pentafluorobenzenesulfonate ions; alkanesulfonate ions such as mesylate ions and butanesulfonate ions; fluoroalkanesulfonimide ions such as trifluoromethanesulfonimide ions; fluoroalkanesulfonylmethide ions such as tris(trifluoromethanesulfonyl)methide ions; borate ions such as tetrakisphenylborate ions and tetrakis(pentafluorophenyl)borate ions; and phosphate ions such as hexafluorophosphate ions and tris(pentafluoroethyl)trifluorophosphate ions.

[0052] Examples of the aforementioned diazomethane derivatives include compounds represented by the following formula (C3). [ka]

[0053] In formula (C3), R 111 and R 112 These are, independently, a saturated hydrocarbyl group having 1 to 12 carbon atoms, a halogenated saturated hydrocarbyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have substituents, or an aralkyl group having 7 to 12 carbon atoms.

[0054] The saturated hydrocarbyl group may be linear, branched, or cyclic, and a specific example of this is R 101 ~R 105 Examples of saturated hydrocarbyl groups represented by the formula are similar to those exemplified above. Examples of the halogenated saturated hydrocarbyl group include trifluoromethyl group, 1,1,1-trifluoroethyl group, 1,1,1-trichloroethyl group, nonafluorobutyl group, etc.

[0055] Examples of aryl groups that may have the substituent include phenyl groups; alkoxyphenyl groups such as 2-,3- or 4-methoxyphenyl groups, 2-,3- or 4-ethoxyphenyl groups, and 3- or 4-tert-butoxyphenyl groups; alkylphenyl groups such as 2-,3- or 4-methylphenyl groups, 2-,3- or 4-ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, and dimethylphenyl groups; and aryl halogen groups such as fluorophenyl groups, chlorophenyl groups, and 1,2,3,4,5-pentafluorophenyl groups. Examples of aralkyl groups include benzyl groups and phenethyl groups.

[0056] Specifically, the onium salts mentioned above include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyliodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, and bis(p-tert-butoxyphenyl) trifluoromethanesulfonate. Phenyl(xyphenyl)phenylsulfonium, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate Sulfonium, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, p-toluenesulfonate Cyclohexylphenylsulfonium, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, 4-(phenylthio)phenyldiphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tris(trifluoromethanesulfonyl)methide, tetrakis(fluorophenyl)borate triphenylsulfonium,Examples include tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(fluorophenyl)borate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, and tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(pentafluorophenyl)borate.

[0057] Specifically, the aforementioned diazomethane derivatives include bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis( Examples include tert-butylsulfonyl)diazomethane, bis(n-pentylsulfonyl)diazomethane, bis(isopentylsulfonyl)diazomethane, bis(sec-pentylsulfonyl)diazomethane, bis(tert-pentylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-pentylsulfonyl)diazomethane, and 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane.

[0058] Specifically, the aforementioned glyoxime derivatives include bis-o-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-o-(p-toluenesulfonyl)-α-diphenylglyoxime, bis-o-(p-toluenesulfonyl)-α-dicyclohexylglyoxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedioneglyoxime, bis-(p-toluenesulfonyl)-2-methyl-3,4-pentanedioneglyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis-o-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedioneglyoxime, bis- Examples include o-(methanesulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-o-(tert-butanesulfonyl)-α-dimethylglyoxime, bis-o-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-o-(cyclohexanesulfonyl)-α-dimethylglyoxime, bis-o-(benzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime, and bis-o-(camphorsulfonyl)-α-dimethylglyoxime.

[0059] Specific examples of the β-ketosulfone derivatives include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane.

[0060] Examples of the aforementioned disulfone derivatives include diphenyldisulfone and dicyclohexyldisulfone.

[0061] Specific examples of the nitrobenzyl sulfonate derivatives include 2,6-dinitrobenzyl p-toluenesulfonic acid and 2,4-dinitrobenzyl p-toluenesulfonic acid.

[0062] Specific examples of the sulfonic acid ester derivatives include 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene.

[0063] Specific examples of the aforementioned imido-yl-sulfonate derivatives include phthalimido-yl-triflate, phthalimido-yl-tosylate, 5-norbornene-2,3-dicarboximido-yl-triflate, 5-norbornene-2,3-dicarboximido-yl-tosylate, 5-norbornene-2,3-dicarboximido-yl-n-butylsulfonate, and n-trifluoromethylsulfonyloxynaphthylimide.

[0064] Specific examples of the oxime sulfonate derivatives include α-(benzenesulfonium oxyimino)-4-methylphenylacetonitrile and α-(p-tolylsulfonium oxyimino)-p-methoxyphenylacetonitrile.

[0065] Specific examples of the iminosulfonate derivatives include (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile and (5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile.

[0066] In addition, 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane and the like can also be suitably used.

[0067] (C) The content of component (C) is preferably 0.05 to 20 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of component (A), from the viewpoint of photocurability. If the content of component (C) is 0.05 parts by mass or more, sufficient acid is generated and the crosslinking reaction proceeds sufficiently, and if it is 20 parts by mass or less, it is preferable because it can suppress the increase in absorbance of the photoacid generator itself, and there is no risk of problems such as a decrease in transparency. Component (C) may be used alone or in combination of two or more types.

[0068] [(D) Crosslinking agent] The photosensitive resin composition of the present invention preferably further contains a crosslinking agent as component (D). The crosslinking agent is a phenolic hydroxyl group in component (A) described above, or R 13 , R 14 , R 23 or R 24 This component undergoes a condensation reaction with saturated hydrocarbyloxy groups, as represented by [formula], facilitating pattern formation and further increasing the strength of the cured product.

[0069] Preferred crosslinking agents include melamine compounds, guanamine compounds, glycoluryl compounds, or urea compounds containing an average of two or more methylol groups and / or alkoxymethyl groups per molecule; amino condensates modified with formaldehyde or formaldehyde-alcohol; phenol compounds having an average of two or more methylol groups or alkoxymethyl groups per molecule; and epoxy compounds having an average of two or more epoxy groups per molecule.

[0070] Examples of the melamine compound mentioned above include those represented by the following formula (D1). [ka]

[0071] In formula (D1), R 201 ~R 206Each of these is independently a methylol group, a saturated hydrocarbyloxymethyl group having 2 to 5 carbon atoms, or a hydrogen atom, but at least one is a methylol group or a saturated hydrocarbyloxymethyl group. Examples of the saturated hydrocarbyloxymethyl group include alkoxymethyl groups such as methoxymethyl group and ethoxymethyl group.

[0072] Examples of melamine compounds represented by formula (D1) include trimethoxymethylmonomethylolmelamine, dimethoxymethylmonomethylolmelamine, trimethylolmelamine, hexamethylolmelamine, hexamethoxymethylmelamine, and hexaethoxymethylmelamine.

[0073] The melamine compound represented by formula (D1) can be obtained, for example, by first methylolating and modifying a melamine monomer with formaldehyde according to a known method, or by further modifying it by alkoxylation with an alcohol. A lower alcohol, such as an alcohol having 1 to 4 carbon atoms, is preferred as the alcohol.

[0074] Examples of the guanamine compounds include tetramethylolguanamine, tetramethoxymethylguanamine, and tetramethoxyethylguanamine.

[0075] Examples of the glycoluryl compounds mentioned above include tetramethylol glycoluryl and tetrakis(methoxymethyl) glycoluryl.

[0076] Examples of the aforementioned urea compounds include tetramethylolurea, tetramethoxymethylurea, tetramethoxyethylurea, tetraethoxymethylurea, and tetrapropoxymethylurea.

[0077] Examples of amino condensates modified with formaldehyde or formaldehyde-alcohol include melamine condensates modified with formaldehyde or formaldehyde-alcohol, and urea condensates modified with formaldehyde or formaldehyde-alcohol.

[0078] Examples of the modified melamine condensate include those obtained by addition-condensation polymerization of a compound represented by formula (D1) or a polymer thereof (e.g., an oligomer such as a dimer or trimer) with formaldehyde until a desired molecular weight is reached. Conventional known methods can be used as the addition-condensation polymerization method. Furthermore, the modified melamine represented by formula (D1) can be used alone or in combination of two or more types.

[0079] Examples of urea condensates modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensates, ethoxymethylated urea condensates, and propoxymethylated urea condensates.

[0080] The modified urea condensate can be obtained, for example, by methylolating a urea condensate of a desired molecular weight with formaldehyde according to a known method, or by further modifying it by alkoxylation with an alcohol.

[0081] Examples of phenol compounds having an average of two or more methylol groups or alkoxymethyl groups in one molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol and 2,2',6,6'-tetramethoxymethylbisphenol A.

[0082] Examples of epoxy compounds having an average of two or more epoxy groups in one molecule include bisphenol-type epoxy resins such as bisphenol A-type epoxy resin and bisphenol F-type epoxy resin, novolac-type epoxy resins such as phenol novolac-type epoxy resin and cresol novolac-type epoxy resin, triphenol alkane-type epoxy resin, biphenyl-type epoxy resin, dicyclopentadiene-modified phenol novolac-type epoxy resin, phenol aralkyl-type epoxy resin, biphenyl aralkyl-type epoxy resin, naphthalene ring-containing epoxy resin, glycidyl ester-type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, and the like.

[0083] If component (D) is included, its content is preferably 0.5 to 50 parts by mass, and more preferably 1 to 30 parts by mass, per 100 parts by mass of component (A). 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 component (A) in the photosensitive resin composition does not decrease, so that sufficient effect can be expressed in the cured product. Component (D) may be used alone or as a mixture of two or more types.

[0084] [(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 can dissolve components (A) to (D) and the various additives described later, but an organic solvent is preferred because it has excellent solubility for these components.

[0085] Examples of the aforementioned organic solvents 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; 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 are preferred as they exhibit the best solubility of the photoacid generator.

[0086] The amount of component (E) used is preferably 50 to 2000 parts by mass, more preferably 50 to 1000 parts by mass, and particularly preferably 50 to 100 parts by mass, per 100 parts by mass of component (A), from the viewpoint of compatibility and viscosity of the photosensitive resin composition. Component (E) may be used alone or as a mixture of two or more.

[0087] [Other additives] The photosensitive resin composition of the present invention may contain other additives in addition to the components described above. Examples of other additives include surfactants that are commonly used to improve coatability.

[0088] The surfactant is preferably nonionic, and examples include fluorinated surfactants, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkylamine oxides, and fluorinated organosiloxane compounds. These can be commercially available, such as Fluorad® FC-430 (manufactured by 3M), Surflon® S-141, S-145 (manufactured by AGC Seimi Chemical Co., Ltd.), Unidyne® DS-401, DS-4031, DS-451 (manufactured by Daikin Industries, Ltd.), Megafac® 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 per 100 parts by mass of component (A).

[0089] The photosensitive resin composition of the present invention may also contain a silane coupling agent as another additive. By including a silane coupling agent, the adhesion of the film obtained from the composition to the substrate can be further enhanced. Examples of silane coupling agents include epoxy group-containing silane coupling agents and aromatic group-containing aminosilane coupling agents. These can be used individually or in combination of two or more. The content of the silane coupling agent is not particularly limited, but if included, it is preferably 0.01 to 5% by mass in the photosensitive resin composition of the present invention.

[0090] The photosensitive resin composition of the present invention can be prepared by conventional methods. For example, the photosensitive resin composition of the present invention can be prepared by stirring and mixing the components, and then filtering the mixture using a filter or the like as needed to remove any solid matter.

[0091] The photosensitive resin composition of the present invention prepared in this manner is suitably used, for example, as a protective film for semiconductor devices, a protective film for wiring, a coverlay film, a solder mask, a through-electrode insulating film (for TSVs), and as an adhesive between laminated substrates in three-dimensional stacking.

[0092] [Pattern formation method using photosensitive resin composition] The pattern forming method using the photosensitive resin composition of the present invention is: (i) A step of forming a photosensitive resin film on a substrate using the photosensitive resin composition of the present invention, (ii) A step of exposing the photosensitive resin film, and (iii) A step of developing the exposed photosensitive resin film using a developer to form a pattern. It includes.

[0093] 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 electrodes, silicon wafers thinned by backside polishing, plastic or ceramic substrates, and substrates having metals such as Ni or Au on the entire surface or in part by ion sputtering or plating. In addition, substrates with uneven surfaces may also be used.

[0094] One method for forming a photosensitive resin film is to apply the photosensitive resin composition onto a substrate and preheat (pre-bake) it as needed. The application method can be any known method, such as the dip method, spin coating method, or roll coating method. The amount of the photosensitive resin composition applied can be appropriately selected depending on the purpose, but it is preferable to apply it so that the resulting photosensitive resin film thickness is preferably 0.1 to 200 μm, more preferably 1 to 150 μm.

[0095] To improve 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 to be dropped and its amount can be appropriately selected depending on the purpose. Preferred solvents include alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, and glycols such as PGME, but solvents used in photosensitive resin compositions can also be used.

[0096] To ensure efficient photocuring, pre-baking may be performed to evaporate solvents and other substances beforehand, if necessary. Pre-baking can be carried out, for example, at 40-140°C for 1 minute to 1 hour.

[0097] Next, (ii) the photosensitive resin film is exposed to light. At this time, exposure is preferably carried out with light of a wavelength of 10 to 600 nm, and more preferably with light of 190 to 500 nm. Examples of such wavelengths of light include various wavelengths of light generated by a radiation generator, such as ultraviolet rays (g-rays, h-rays, i-rays, etc.) and far-ultraviolet rays (248 nm, 193 nm). Of these, light of a wavelength of 248 to 436 nm is particularly preferred. The exposure amount is 10 to 10000 mJ / cm². 2 It is preferable.

[0098] Exposure may be performed via a photomask. The photomask may, for example, have a desired pattern cut out of it. The material of the photomask is not particularly limited, but it is preferably one that blocks light of the aforementioned wavelength, and for example, one that has chromium or the like as a light-shielding film is preferably used.

[0099] Furthermore, post-exposure heating (PEB) may be performed to increase the development sensitivity. PEB is preferably performed at 40-150°C for 0.5-10 minutes. PEB causes the exposed areas to crosslink, forming an insolubilized pattern that is insoluble in the organic solvent used as the developer.

[0100] After exposure or PEB, (iii) the photosensitive resin film is developed using a developer to form a pattern. As the developer, organic solvents such as alcohols like IPA, ketones like cyclohexanone, and glycols like PGME are preferred, but solvents used in the photosensitive resin composition can also be used. The development method can be a conventional method, such as immersing the patterned substrate in the developer. The unexposed areas are dissolved and removed by organic solvent development, thereby forming the pattern. Afterward, washing, rinsing, drying, etc., are performed as necessary to obtain a resin film with the desired pattern.

[0101] Furthermore, (iv) the patterned film may be post-cured using an oven or hot plate, preferably at 100-250°C, more preferably at 130-220°C. A post-curing temperature of 100-250°C is preferable from the viewpoint of adhesion to the substrate, heat resistance, strength, electrical properties, and adhesive strength, as it increases the crosslinking density of the photosensitive resin composition and removes remaining volatile components. The post-curing time is preferably 10 minutes to 10 hours, and more preferably 10 minutes to 3 hours. Using the photosensitive resin composition of the present invention, a film with excellent various film properties can be obtained even with post-curing at a relatively low temperature of 200°C or less. The film thickness of the post-cured film (cured film) is usually 1-200 μm, preferably 5-50 μm.

[0102] If it is not necessary to form a pattern, for example, if it is simply desired to form a uniform film, the film can be formed in step (ii) of the pattern formation method by exposing the material to light of an appropriate wavelength without using the photomask.

[0103] [Method of bonding circuit boards] The photosensitive resin composition of the present invention can also be used as an adhesive for bonding two substrates. One method of bonding the substrates is to bond a substrate coated with the photosensitive resin composition of the present invention to a second substrate under suitable heat and pressure conditions, so that an adhesive bond is formed between the two substrates. Either the coated substrate or the second substrate, or both, may be chipped by dicing or the like. Preferably, the heating temperature is 50 to 200°C for 1 to 60 minutes. As a bonding apparatus, a wafer bonder can be used to bond wafers together under reduced pressure while applying a load, or a flip-chip bonder can be used to perform chip-wafer or chip-chip bonding. The adhesive layer formed between the substrates becomes permanently bonded after a post-curing treatment described later, which increases the bonding strength.

[0104] By post-curing the bonded substrate under the same conditions as in step (iv) described above, the crosslinking density of the film can be increased, thereby improving the substrate adhesion strength. Although a crosslinking reaction occurs due to heating during bonding, this crosslinking reaction does not produce side reactions involving degassing, and therefore does not induce bonding defects (voids), especially when used as a substrate adhesive.

[0105] [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.

[0106] The photosensitive dry film (support film and photosensitive resin coating) is solid, and since the photosensitive resin coating does not contain solvents, there is no risk of bubbles remaining inside the photosensitive resin coating and between it and the uneven substrate due to its volatilization.

[0107] The thickness of the photosensitive resin coating is preferably 5 to 200 μm, and more preferably 10 to 100 μm, from the viewpoint of flatness on an uneven substrate, step coverage, and substrate stacking spacing.

[0108] Furthermore, the viscosity and fluidity of the photosensitive resin film are closely related. The photosensitive resin film can exhibit appropriate fluidity within an appropriate viscosity range, allowing it to penetrate deep into narrow gaps and strengthen adhesion to the substrate as the resin softens. Therefore, from the viewpoint of its fluidity, the viscosity of the photosensitive resin film is preferably 10 to 5000 Pa·s, more preferably 30 to 2000 Pa·s, and even more preferably 50 to 300 Pa·s at 80 to 120°C. In this invention, viscosity is measured using a rotational viscometer.

[0109] The photosensitive dry film of the present invention achieves high flatness when the photosensitive resin coating adheres to the uneven surface of a substrate. In particular, the photosensitive resin coating is characterized by low viscoelasticity, which allows for even higher flatness. Furthermore, adhering the photosensitive resin coating to the substrate under a vacuum environment can more effectively prevent the formation of gaps.

[0110] The photosensitive dry film of the present invention can be manufactured by applying the photosensitive resin composition onto a support film and drying it to form a photosensitive resin film. A film coater for manufacturing adhesive products can generally be used as the manufacturing apparatus for the photosensitive dry film. Examples of film coaters include comma coaters, comma reverse coaters, multi coaters, die coaters, lip coaters, lip reverse coaters, direct gravure coaters, offset gravure coaters, three-bottom reverse coaters, four-bottom reverse coaters, and the like.

[0111] A photosensitive dry film can be manufactured by unwinding a support film from the unwinding shaft of the film coater and passing it through the coater head of the film coater, applying the photosensitive resin composition to the support film to a predetermined thickness, then passing it through a hot air circulation oven at a predetermined temperature and time to dry it on the support film and form a photosensitive resin coating. Alternatively, if necessary, a photosensitive dry film with a protective film can be manufactured by passing the photosensitive dry film together with a protective film unwinding from another unwinding shaft of the film coater through a laminating roll at a predetermined pressure to bond the photosensitive resin coating on the support film with the protective film, and then winding it onto the winding shaft of the film coater. 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.

[0112] The support film may be a single-layer film consisting of a single film, or a multilayer film formed by laminating multiple films. Examples of materials for the film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Of these, polyethylene terephthalate is preferred due to its appropriate flexibility, mechanical strength, and heat resistance. These films may have undergone various treatments, such as corona treatment or release agent coating. Commercially available products can be used, such as Therapiel WZ(RX), Therapiel BX8(R) (both manufactured by Toray Film Processing Co., Ltd.), E7302, E7304 (both manufactured by Toyobo Co., Ltd.), Purex G31, Purex G71T1 (both manufactured by Teijin DuPont Films Ltd.), PET38×1-A3, PET38×1-V8, and PET38×1-X08 (all manufactured by Nippa Co., Ltd.).

[0113] As the protective film, the same type as the support film described above can be used, but polyethylene terephthalate and polyethylene are preferred due to their appropriate flexibility. Commercially available products can be used, and examples of polyethylene terephthalate include those already exemplified, while examples of polyethylene include GF-8 (manufactured by Tamapoly Co., Ltd.) and PE film type 0 (manufactured by Nipper Co., Ltd.).

[0114] The thickness of the support film and protective film is preferably 10 to 100 μm, more preferably 25 to 50 μm, from the viewpoint of stability in the production of the photosensitive dry film and prevention of curling on the core.

[0115] [Pattern formation method using photosensitive dry film] The pattern formation method using the photosensitive dry film of the present invention is: (i') A step of forming a photosensitive resin film on a substrate using the photosensitive dry film of the present invention, (ii) A step of exposing the photosensitive resin film, and (iii) A step of developing the exposed photosensitive resin film using a developer to form a pattern. It includes.

[0116] First, in step (i'), a photosensitive resin film is formed on the 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. If the photosensitive dry film has a protective film, the protective film is peeled off from the photosensitive dry film before attaching the photosensitive resin film of the photosensitive dry film to the substrate. The attachment can be performed, for example, using a film attachment device.

[0117] The substrate is the same as that described in the pattern formation method using a photosensitive resin composition. A vacuum laminator is preferred as the film bonding apparatus. For example, the protective film of the photosensitive dry film is peeled off, and the exposed photosensitive resin film is pressed onto the substrate on a table at a predetermined temperature using a bonding roll at a predetermined pressure in a vacuum chamber at a predetermined vacuum level. The temperature is preferably 60 to 120°C, the pressure is preferably 0 to 5.0 MPa, and the vacuum level is preferably 50 to 500 Pa.

[0118] To obtain a photosensitive resin coating of the required thickness, the film may be applied multiple times as needed. For example, by applying the film 1 to 10 times, a photosensitive resin coating with a thickness of 10 to 1000 μm, and especially 100 to 500 μm, can be obtained.

[0119] 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 needed. Pre-baking can be performed, for example, at 40 to 140°C for about 1 minute to 1 hour.

[0120] 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, similar to the pattern-forming method using the photosensitive resin composition. The support film of the photosensitive dry film is peeled off before pre-baking or PEB depending on the process, or removed by other means.

[0121] The coating obtained from the photosensitive resin composition and the photosensitive dry film exhibits excellent mechanical properties such as solder resistance, heat resistance, low warping of the substrate, and crack resistance, as well as copper migration resistance and adhesion to substrates, making it suitable for use as a protective coating for electrical and electronic components such as semiconductor devices and as a coating for substrate adhesion. [Examples]

[0122] 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. Mw was measured by GPC using monodisperse polystyrene as the standard, with a TSKgel Super HZM-H column (manufactured by Tosoh Corporation), a flow rate of 0.6 mL / min, elution solvent THF, and a column temperature of 40°C.

[0123] The compounds (S-1) to (S-6) used in the synthesis example are shown below. [ka]

[0124] [1] Synthesis of silicone resin [Synthesis Example 1] In a 3L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 215.0 g (0.5 mol) of compound (S-6) was added, followed by 2000 g of toluene, and the mixture was heated to 70°C. Then, 1.0 g of toluene chloroplatinate solution (platinum concentration 0.5% by mass) was added, along with 67.9 g (0.35 mol) of compound (S-4) and compound (S-5) (y 1453.0 g (0.15 mol) of =40 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups = 1 / 1 (molar ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and aged for 6 hours. Toluene was then removed from the reaction solution under reduced pressure to obtain silicone resin A-1. Silicone resin A-1 is, 1 ¹H-NMR (Bruker) confirmed that the material contained repeating units a1, a2, b1, and b2. The Mw of silicone resin A-1 was 62000, and the silicone content was 61.6% by mass.

[0125] [Synthesis Example 2] In a 3L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 53.00g (0.20 mol) of compound (S-2) and 117.6g (0.30 mol) of compound (S-1) were added, followed by the addition of 2000g of toluene, and the mixture was heated to 70°C. Subsequently, 1.0g of toluene chloroplatinate solution (platinum concentration 0.5% by mass) was added, along with 48.5g (0.25 mol) of compound (S-4) and compound (S-5) (y 1 755.0 g (0.25 mol) of =40 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups = 1 / 1 (molar ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and aged for 6 hours. Toluene was then removed from the reaction solution under reduced pressure to obtain silicone resin A-2. Silicone resin A-2 is, 1 ¹H-NMR (Bruker) confirmed that the material contained repeating units a1, a3, a4, b1, b3, and b4. The Mw of silicone resin A-2 was 83000, and the silicone content was 77.5% by mass.

[0126] [Synthesis Example 3] In a 3L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 27.9g (0.15 mol) of compound (S-3), 19.6g (0.05 mol) of compound (S-1), and 129.0g (0.30 mol) of compound (S-6) were added, followed by the addition of 2000g of toluene, and the mixture was heated to 70°C. Subsequently, 1.0g of toluene chloroplatinate solution (platinum concentration 0.5% by mass) was added, along with 87.3g (0.45 mol) of compound (S-4) and compound (S-5) (y 1 79.3 g (0.05 mol) of =20 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups = 1 / 1 (molar ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and aged for 6 hours. Toluene was then removed from the reaction solution under reduced pressure to obtain silicone resin A-3. Silicone resin A-3 is, 1 ¹H-NMR (Bruker) confirmed that the material contained repeating units a1, a2, a4, b1, b2, and b4. The Mw of silicone resin A-3 was 24000, and the silicone content was 31.2% by mass.

[0127] [2] Preparation of photosensitive resin composition [Examples 1-7 and Comparative Examples 1-20] Each component was mixed according to the proportions listed in Tables 1-3, then stirred and dissolved at room temperature. Finally, the mixture was microfiltered using a 1.0 μm Teflon® filter to prepare the photosensitive resin compositions of Examples 1-8 and Comparative Examples 1-20.

[0128] [Table 1]

[0129] [Table 2]

[0130] [Table 3]

[0131] In Tables 1-3, epoxy compounds B-1 to B-12 are as follows: [ka]

[0132] [ka]

[0133] [ka]

[0134] [ka]

[0135] In Tables 1-3, the photoacid generator PAG-1 is as follows: [ka]

[0136] In Tables 1-3, the crosslinking agent CL-1 is as follows: [ka]

[0137] In Tables 2 and 3, resin A'-1 is as follows: [ka]

[0138] [3] Preparation of photosensitive dry film A die coater was used as the film coater, and a polyethylene terephthalate film (38 μm thick) was used as the support film. The photosensitive resin compositions described in Tables 1 to 3 were applied to the support film. The films were then dried by passing them through a hot air circulation oven (4 m long) set to 100°C for 5 minutes to form a photosensitive resin film on the support film, obtaining a photosensitive dry film. A polyethylene film (50 μm thick) was then laminated onto the photosensitive resin film using 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 100 μm. The film thickness of the photosensitive resin film was measured using an optical interference film thickness analyzer (F50-EXR, manufactured by Filmetrics Co., Ltd.).

[0139] [4] Evaluation of resin coating (1) Pattern formation and evaluation thereof The photosensitive dry film with protective film was prepared by removing the protective film and using a vacuum laminator TEAM-100RF (manufactured by Takatori Co., Ltd.) to set the vacuum level in the vacuum chamber to 80 Pa. The photosensitive resin film on the support film was then pressed into contact with a migration test substrate (a comb-shaped electrode substrate with copper conductive material, conductive area spacing and width of 10 μm, and conductive area thickness of 4 μm). The temperature was set to 100°C. After returning to atmospheric pressure, the substrate was removed from the vacuum laminator and the support film was removed. Next, to improve adhesion to the substrate, preheating was performed at 120°C for 5 minutes using a hot plate. To form line-and-space patterns and contact hole patterns on the obtained photosensitive resin film, exposure was performed using a contact aligner type exposure apparatus with a wavelength of 365 nm through a mask. After exposure, PEB was performed at 140°C for 5 minutes using a hot plate, followed by cooling, and then spray development with PGMEA for 300 seconds to form the patterns.

[0140] The photosensitive resin film on the substrate, which had been patterned using the method described above, was post-cured in an oven at 180°C for 2 hours while purging with nitrogen. Subsequently, the cross-sections of the formed 300 μm, 150 μm, and 100 μm contact hole patterns were observed using a scanning electron microscope (SEM), and the smallest hole pattern in which the holes penetrated to the bottom of the film was defined as the limiting resolution. Furthermore, the perpendicularity of the 300 μm contact hole pattern was evaluated from the obtained cross-sectional images, with ◎ indicating a perfectly perpendicular pattern, ○ indicating slight reverse taper or fitting, △ indicating strong reverse taper or fitting, and × indicating poor opening. The results are shown in Tables 4-6.

[0141] (2) Evaluation of electrical properties (copper migration) A substrate with a pattern formed by method (1) was used as a substrate for evaluating copper migration, and tests were conducted. The copper migration test was performed under the conditions of a temperature of 121°C, humidity of 100%, and applied voltage of 10V, and the time during which a short circuit occurred was checked, with a maximum of 2000 hours. The results are shown in Tables 4 to 6.

[0142] (3) Evaluation of warping stress The fabricated film was laminated onto an 8-inch silicon wafer using a film laminator (TEAM-100, manufactured by Takatori Co., Ltd.), and preheated at 120°C for 5 minutes using a hot plate. Subsequently, the film was exposed using a contact aligner type exposure apparatus at a wavelength of 365 nm without a mask, and then cured by heating in an oven at 180°C for 2 hours. The warpage stress (at 25°C) was then measured using a thin-film stress measuring device (FLX-2320-S, manufactured by Toho Technology Co., Ltd.). The results are shown in Tables 4-6.

[0143] (4) Evaluation of reliability (adhesion, crack resistance) The aforementioned photosensitive dry film with protective film was prepared by removing the protective film and using a vacuum laminator TEAM-100RF (manufactured by Takatori Co., Ltd.) to set the vacuum level in the vacuum chamber to 80 Pa. The photosensitive resin film on the support film was then pressed into contact with a CCL substrate on which 10 mm x 10 mm square silicon chips were laminated. The temperature was set to 100°C. After returning to atmospheric pressure, the substrate was removed from the vacuum laminator and the support film was removed. Next, to improve adhesion to the substrate, preheating was performed at 120°C for 5 minutes using a hot plate. The resulting photosensitive resin film was exposed using a contact aligner type exposure apparatus at a wavelength of 365 nm without using a mask. After exposure, PEB was performed at 140°C for 5 minutes using a hot plate, followed by cooling. Post-curing was then performed at 180°C for 2 hours using an oven while purging with nitrogen. Subsequently, a dicing saw equipped with a dicing blade (DAD685, DISCO Corporation, spindle speed 40,000 rpm, cutting speed 20 mm / sec) was used to obtain 20 mm x 20 mm square test pieces 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 (held at -55°C for 10 minutes, held at 125°C for 10 minutes, repeated 1000 times), and the delamination state of the resin film from the wafer and the presence or absence of cracks were checked after the heat cycle test. ○ was used for pieces that showed no delamination or cracking at all, × for pieces that showed even one delamination, and × for pieces that showed even one crack. The presence or absence of delamination and cracking was confirmed by top-down observation with an optical microscope and cross-sectional SEM observation. The results are shown in Tables 4-6.

[0144] (5) Evaluation of adhesive strength (before heat resistance test) The substrate for warpage stress measurement prepared in (3) above was cut to a size of 2 mm × 2 mm using a dicing saw (DISCO DAD685) equipped with a dicing blade. The 2 mm × 2 mm chip was bonded to a separately prepared 15 mm × 15 mm silicon wafer (base substrate) via a resin film at 150°C and under a load of 50 mN. The resin film was then cured by heating at 180°C for 2 hours to obtain test specimens. Five test specimens were prepared and used for adhesion strength measurement tests. Adhesion strength was measured using a bond tester (Dage series 4000-PXY) to measure the resistance force when the semiconductor chip (2 mm × 2 mm) peeled off the base substrate (15 mm × 15 mm silicon wafer), and the adhesion strength of the resin film layer was evaluated. The test conditions were a test speed of 200 μm / sec and a test height of 50 μm. The results are shown in Tables 4 to 6. Note that the values ​​are the average of measurements taken from five test pieces, and a higher value indicates stronger adhesion.

[0145] (6) Evaluation of adhesive strength (after heat resistance test) The test specimens for measuring adhesive strength prepared in (5) above were placed in an oven heated to 220°C for 1000 hours. After removing the test specimens from the oven, they were subjected to the adhesive strength measurement test in the same manner as in (5). The results are shown in Tables 4 to 6.

[0146] (7) Evaluation of solder resistance (before moisture absorption test) After forming a pattern on a substrate using method (1), a water-soluble flux was applied and the substrate was immersed in a 260°C solder bath for 30 seconds, repeating this process three times. Then, the resist was visually inspected for any abnormalities. Substrates with no abnormalities in the coating were marked with ○, and those with even one blister or peeling were marked with ×. The results are shown in Tables 4-6.

[0147] (8) Evaluation of solder resistance (after moisture absorption test) The substrate on which the pattern was formed by the method of (1) was placed in a pressure cooker at a temperature of 121 °C and a humidity of 100% for 1 hour, after which a water-soluble flux was applied and immersed in a solder bath at 260 °C for 30 seconds three times in succession. Then, the presence or absence of abnormalities in the resist was visually observed, and those without abnormalities in the coating film were marked as ○, and those with even one bulge or peeling in the coating film were marked as ×. The results are shown in Tables 4 to 6.

[0148]

Table 4

[0149]

Table 5

[0150]

Table 6

[0151] From the above results, the photosensitive resin composition and the photosensitive dry film of the present invention can easily form a thick film and a fine vertical pattern, and exhibited sufficient characteristics as a photosensitive material. In addition, the photosensitive resin film obtained therefrom is excellent in solder resistance, heat resistance, low warpage of the substrate, copper migration resistance, and adhesion to the substrate and the like, and has high reliability such as crack resistance and adhesion as an insulating protective film, and can be suitably used as a forming material for various electrical and electronic component protective films 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 containing an acid crosslinkable group represented by the following formula (A1), (B) Epoxy compounds represented by the following formula (B1), and (C) Photoacid generator A photosensitive resin composition containing [a specific substance]. 【Chemistry 1】 (In the formula, R1 to R4 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 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.) 【Chemistry 2】 (In the formula, R 1 (This refers to a hydrogen atom, a saturated hydrocarbyl group having 1 to 4 carbon atoms, a phenyl group, a hydroxyphenyl group, or a halogen-substituted phenyl group.)

2. (A) The photosensitive resin composition according to claim 1, wherein the silicone resin comprises repeating units represented by the following formulas (a1) to (a4) and (b1) to (b4). 【Transformation 3】 [wherein, R 1 ~R 4 are each independently a hydrocarbyl group having 1 to 8 carbon atoms. k is an integer of 1 to 600. a 1 ~a 4 and b 1 ~b 4 represent the composition ratio (molar ratio) of each repeating unit, where 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. X 1 is a divalent group represented by the following formula (X1). X 2 is a divalent group represented by the following formula (X2). X 3 is a divalent group represented by the following formula (X3). X 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 Each of these is independently either a hydrogen atom or a methyl group. 13 and R 14 These are, independently, saturated hydrocarbyl groups having 1 to 4 carbon atoms or saturated hydrocarbyloxy groups having 1 to 4 carbon atoms. 1 and p 2 Each of these is an integer between 0 and 7, independently of the others. 1 and q 2 Each of these is an integer between 0 and 2, independently of the others. (The dashed lines represent combinations.) 【Transformation 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 Each of these is independently either a hydrogen atom or a methyl group. 23 and R 24 These are, independently, saturated hydrocarbyl groups having 1 to 4 carbon atoms or saturated hydrocarbyloxy groups having 1 to 4 carbon atoms. 1 and r 2 Each of these is an integer between 0 and 7, independently of the others. 1 and s 2 Each of these is an integer between 0 and 2, independently of the others. (The dashed lines represent combinations.) 【Transformation 6】 (In the formula, R 31 and R 32 Each of these is independently either a hydrogen atom or a methyl group. 1 and t 2 Each of these is an integer between 0 and 7, independently of the others. (The dashed lines represent combinations.) 【Transformation 7】 (In the formula, R 41 and R 42 Each of these is independently either a hydrogen atom or a methyl group. 43 and R 44 These are, independently, hydrocarbyl groups having 1 to 8 carbon atoms. 1 and u 2 Each of the integers is independently between 0 and 7. v is an integer between 0 and 600. The dashed line represents a combination.

3. The photosensitive resin composition according to claim 1, wherein the content of the epoxy compound in component (B) is 3 to 100 parts by mass per 100 parts by mass of component (A).

4. Furthermore, the photosensitive resin composition according to claim 1, further comprising (D) a crosslinking agent.

5. (D) The photosensitive resin composition according to claim 4, wherein the crosslinking agent is at least one selected from a nitrogen-containing compound selected from melamine compounds, guanamine compounds, glycoluryl compounds and urea compounds, an amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethyl groups per molecule, and an epoxy compound having an average of two or more epoxy groups per molecule.

6. Furthermore, the photosensitive resin composition according to claim 1, further comprising (E) a solvent.

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

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

9. (i) A step of forming a photosensitive resin film on a substrate using the photosensitive resin composition according to any one of claims 1 to 6, (ii) A step of exposing the photosensitive resin film, and (iii) A step of developing the exposed photosensitive resin film using a developer to form a pattern. A pattern formation method including the following.

10. (i') A step of forming a photosensitive resin film on a substrate using the photosensitive dry film described in claim 8, (ii) A step of exposing the photosensitive resin film, and (iii) A step of developing the exposed photosensitive resin film using a developer to form a pattern. A pattern formation method including the following.

11. Furthermore, the pattern forming method according to claim 9, further comprising the step of (iv) post-curing the photosensitive resin film, which has been patterned by development, at a temperature of 100 to 250°C.

12. A photosensitive resin composition according to any one of claims 1 to 6, which is a material for a protective coating for electrical and electronic components.

13. A photosensitive resin composition according to any one of claims 1 to 6, which is a material for a substrate bonding film for bonding two substrates together.

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