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

Abstract

To provide a photosensitive resin composition which enables formation of a resin film (resin layer) which facilitates fine vertical pattern formation with a thick film, is excellent in various film characteristics such as heat resistance, crack resistance, adhesion to a base material used in a substrate, an electronic component, a semiconductor element, especially, a circuit board, and low warpage of a substrate, and is excellent in reliability as a film for electric / electronic component protection and a film for substrate bonding, a photosensitive resin film, a photosensitive dry film, and a pattern formation method using them.SOLUTION: A photosensitive resin composition contains (A) an acid crosslinkable group-containing silicone resin, (B) an epoxy compound represented by a following formula (B), and (C) an optical acid generator. In the formula, R51 to R55 are each independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms.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 patterning method.

Background Art

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

[0003] On the other hand, a photosensitive silicone composition mainly composed of a silicone-type polymer containing a silphenylene skeleton has been proposed (Patent Document 2). Although this photosensitive silicone composition has improved chemical resistance to a photoresist stripper or the like, there are problems such as peeling of the cured product from the substrate after a heat resistance test or a decrease in the adhesive force to the substrate, and further improvement in reliability has been desired. In addition, with the progress of semiconductor technology, finer patterning has been required.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present invention has been made in view of the above circumstances, and can easily form a fine vertical pattern with a thick film, and has heat resistance, crack resistance, and adhesion to substrates, electronic components, semiconductor elements, etc., especially the base materials used for circuit boards, and various film properties such as low warpage of the substrate. An object of the present invention is to provide a photosensitive resin composition, a photosensitive resin film, a photosensitive dry film, and a pattern forming method using the same, which can form a resin film (resin layer) excellent in reliability as a film for protecting electrical and electronic components or a film for bonding substrates.

Means for Solving the Problems

[0006] As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by a photosensitive resin composition containing (A) a silicone resin containing an acid crosslinkable group, (B) an epoxy compound having a specific structure, and (C) a photoacid generator, and have completed the present invention.

[0007] Therefore, the present invention provides the following photosensitive resin composition, photosensitive resin film, photosensitive dry film, and pattern forming method. 1. A photosensitive resin composition containing (A) a silicone resin containing an acid crosslinkable group, (B) an epoxy compound represented by the following formula (B), and (C) a photoacid generator

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0008] The photosensitive resin composition of the present invention can form a film in a wide film thickness range, and further, by the pattern forming method described later, it is possible to easily form a thick film with a fine and excellent perpendicular pattern. The film obtained by using the photosensitive resin composition and the photosensitive dry film of the present invention is excellent in heat resistance and low warpage of the substrate, and also has excellent adhesion, mechanical properties such as flexibility and crack resistance, electrical properties such as low dielectric constant and low dielectric tangent, and copper migration resistance with respect to substrates, electronic components, semiconductor elements, etc., particularly 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 electric and electronic components such as circuit boards, semiconductor elements, and display elements, and a film forming material for bonding substrates. [Embodiments for Carrying Out the Invention]

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

[0010] [(A) Silicone Resin Containing Acid Crosslinkable Group] (A) The silicone resin contains an acid-crosslinkable group in the molecule. Here, the acid-crosslinkable group means a group capable of chemically bonding functional groups 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 contain only one of them, or may contain both of them.

[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 their structural isomers; 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 formulas (a1) and (b1), X 1 is a divalent group represented by the following formula (X1).

Chemical formula

[0016] In formula (X1), Y 1 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 11 and R 12 are each independently a hydrogen atom or a methyl group. R 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. p 1 and p 2 are each independently an integer from 0 to 7. q 1 and q 2 are each independently an integer from 0 to 2.)

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

[0018] In formulas (a2) and (b2), X 2 is a divalent group represented by the following formula (X2).

Chemical formula

[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 broken line is 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 is a number that satisfies = 1, where 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 A number that satisfies = 1 is more preferred, where 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 preferred. Further, from the perspective of the reaction, 0 < b 2 < 1 is preferred, and 0.2 ≤ b 2 ≤ 0.95 is more preferred, and 0.3 ≤ b 2More preferably, it is ≦0.9.

[0026] Each of the above-described repeating units may be bonded randomly or as a block polymer. Further, when there are two or more siloxane units in each repeating unit, all the siloxane units may be the same or may contain two or more different siloxane units. When two or more different siloxane units are included, the siloxane units may be bonded randomly or may include a plurality of blocks of the same kind of siloxane units. Further, in the silicone resin, the silicone (siloxane unit) content is preferably 30 to 80% by mass.

[0027] (A) The silicone resin of the component functions as a film-forming component. Further, the obtained resin film has good adhesion to a laminate, a substrate, etc., good pattern-forming ability, crack resistance and heat resistance.

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

[0029] [[Manufacturing method of (A) silicone resin]] (A) The silicone resin of the component can be produced by subjecting at least one selected from the compound represented by the following formula (1), the compound represented by the following formula (2), the compound represented by the following formula (3), the compound represented by the following formula (4) and the compound represented by the following formula (5) and, if necessary, the compound represented by the following formula (6) to addition polymerization in the presence of a metal catalyst. [Chemical formula] (In the formula, R 1 ~R 4 and k are the same as above.)

[0030] [Chemical formula] (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 described above.)

[0031] Examples of the metal catalyst include single platinum group metals such as platinum (including platinum black), rhodium, and palladium; salts of platinum group metals such as H2PtCl4·xH2O, H2PtCl6·xH2O, NaHPtCl6·xH2O, KHPtCl6·xH2O, Na2PtCl6·xH2O, K2PtCl4·xH2O, PtCl4·xH2O, PtCl2, Na2HPtCl4·xH2O (where x is preferably an integer from 0 to 6, particularly preferably 0 or 6), platinum chloride, chloroplatinic acid, and chloroplatinate; alcohol-modified chloroplatinic acid (e.g., those described in U.S. Patent No. 3,220,972); complexes of chloroplatinic acid and olefins (e.g., 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 carriers such as alumina, silica, and carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (so-called Wilkinson's catalyst); complexes of platinum chloride, chloroplatinic acid, or chloroplatinate with vinyl group-containing siloxane (particularly vinyl group-containing cyclic siloxane), etc. can be used.

[0032] The amount of the catalyst used is a catalytic amount, and usually, it is preferably 0.001 to 0.1 part by mass, more preferably 0.01 to 0.1 part by mass, based on 100 parts by mass of the total raw material compounds.

[0033] In the addition polymerization reaction, a solvent may be used as necessary. As the solvent, hydrocarbon solvents such as toluene and xylene are preferable, for example.

[0034] From the viewpoint that the catalyst is not deactivated and the polymerization can be completed in a short time, the polymerization temperature is preferably 40 to 150°C, more preferably 60 to 120°C. The polymerization time depends 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 completion of the reaction, when a solvent is used, the silicone resin of component (A) can be obtained by distilling off the solvent.

[0035] The reaction method is not particularly limited. 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), the compound represented by formula (4) and the compound represented by formula (5), and optionally a compound represented by formula (6), first, at least one selected from the compounds represented by formula (3), the compound represented by formula (4) and the compound represented by formula (5), and optionally a compound represented by formula (6) are mixed and heated, then a metal catalyst is added to the mixture, and then the compound represented by formula (1) and the compound represented by formula (2) are added dropwise over 0.1 to 5 hours.

[0036] Each compound is preferably formulated such that the total of the hydrosilyl groups of the compound represented by formula (1) and the compound represented by formula (2) is preferably 0.67 to 1.67, more preferably 0.83 to 1.25 in molar ratio with respect to the total of the alkenyl groups of at least one selected from the compounds 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 obtained 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.

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

[0039] In formula (B1), R 51 ~R 55 are each independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms. The saturated hydrocarbyl group may be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, hexyl group, and structural isomers thereof; and cyclic saturated hydrocarbyl groups having 3 to 6 carbon atoms such as cyclohexyl group. R 51 ~R 55 is preferably a hydrogen atom, a methyl group, or an ethyl group, more preferably a hydrogen atom or a methyl group.

[0040] As the alicyclic epoxy compound, the following are particularly preferred. [Chemical formula]

[0041] As the alicyclic epoxy compound, commercially available products can be used. For example, WHR-991S manufactured by Nippon Kayaku Co., Ltd. can be mentioned.

[0042] The content of component (B) is preferably 3 to 100 parts by mass, more preferably 3 to 75 parts by mass, and still more preferably 5 to 50 parts by mass with respect to 100 parts by mass of component (A). If the content of component (B) is within the above range, a better coating film can be obtained when made into a dry film, which is preferable. Component (B) may be used alone or in combination of two or more.

[0043] [(C) Photoacid generator] (C) The photoacid generator is not particularly limited as long as it decomposes upon light irradiation to generate an acid, but those that decompose upon light with a wavelength of 190 to 500 nm to generate an acid are preferred. The photoacid generator serves as a curing catalyst. Since the photosensitive resin composition of the present invention has excellent compatibility with the photoacid generator, a wide range of photoacid generators can be used.

[0044] Examples of the photoacid generator include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, sulfonic acid ester derivatives, imide-yl-sulfonate derivatives, oxime sulfonate derivatives, iminosulfonate derivatives, and the like.

[0045] Examples of the onium salt include sulfonium salts represented by the following formula (C1), iodonium salts represented by the following formula (C2), and the like.

Chemical formula

[0046] In formulas (C1) and (C2), R 101 ~R 105 are each independently a saturated hydrocarbyl group having 1 to 12 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms which may have a substituent. A - is a non-nucleophilic counter ion.

[0047] The saturated hydrocarbyl group may be linear, branched, or cyclic. Specific examples thereof include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, and structural isomers thereof; and cyclic saturated hydrocarbyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, norbornyl group, and adamantyl group. Examples of the aryl group include phenyl group, naphthyl group, biphenylyl group, and the like. Examples of the aralkyl group include benzyl group, phenethyl group, and the like.

[0048] Examples of the substituent include an oxo group, a saturated hydrocarbyl group having 1 to 12 carbon atoms, a saturated hydrocarbyloxy group having 1 to 12 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aralkyl group having 7 to 25 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, an arylthio group having 6 to 24 carbon atoms, etc. The hydrocarbyl moieties of the saturated hydrocarbyl group and the saturated hydrocarbyloxy group may be linear, branched, or cyclic. Specific examples thereof include those exemplified as the saturated hydrocarbyl group represented by R 101 ~R 105 and are the same as those exemplified.

[0049] R 101 ~R 105 Examples of R

[0050] include a saturated hydrocarbyl group which may have a substituent such as a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, a 2-oxocyclohexyl group; an aryl group which may have a substituent such as a phenyl group, a naphthyl group, a biphenylyl group, a 2-, 3- or 4-methoxyphenyl group, a 2-, 3- or 4-ethoxyphenyl group, a 3- or 4-tert-butoxyphenyl group, a 2-, 3- or 4-methylphenyl group, a 2-, 3- or 4-ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, a dimethylphenyl group, a terphenylyl group, a biphenylyloxyphenyl group, a biphenylylthiophenyl group; an aralkyl group which may have a substituent such as a benzyl group, a phenethyl group. Among these, an aryl group which may have a substituent and an aralkyl group which may have a substituent are more preferable.Examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; fluoroalkanesulfonate ions such as triflate ion, 1,1,1-trifluoroethanesulfonate ion, and nonafluorobutanesulfonate ion; arylsulfonate ions such as tosylate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion, and 1,2,3,4,5-pentafluorobenzenesulfonate ion; alkanesulfonate ions such as mesylate ion and butanesulfonate ion; fluoroalkanesulfonimide ions such as trifluoromethanesulfonimide ion; fluoroalkanesulfonylmethide ions such as tris(trifluoromethylsulfonyl)methide ion; borate ions such as tetrakisphenylborate ion and tetrakis(pentafluorophenyl)borate ion; phosphate ions such as hexafluorophosphate ion and tris(pentafluoroethyl)trifluorophosphate ion, etc.

[0051] Examples of the diazomethane derivative include compounds represented by the following formula (C3). [Chemical formula]

[0052] In formula (C3), R 111 and R 112 are each 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 a substituent, or an aralkyl group having 7 to 12 carbon atoms.

[0053] The saturated hydrocarbyl group may be linear, branched, or cyclic, and specific examples thereof include those similar to the saturated hydrocarbyl groups exemplified as the saturated hydrocarbyl groups represented by R 101 ~R 105 Examples of the halogenated saturated hydrocarbyl group include trifluoromethyl group, 1,1,1-trifluoroethyl group, 1,1,1-trichloroethyl group, nonafluorobutyl group, etc.

[0054] Examples of the aryl group which may have the above substituents include a phenyl group; alkoxyphenyl groups such as 2-, 3- or 4-methoxyphenyl group, 2-, 3- or 4-ethoxyphenyl group, 3- or 4-tert-butoxyphenyl group; alkylphenyl groups such as 2-, 3- or 4-methylphenyl group, 2-, 3- or 4-ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, dimethylphenyl group; halogenated aryl groups such as fluorophenyl group, chlorophenyl group, 1,2,3,4,5-pentafluorophenyl group and the like. Examples of the aralkyl group include a benzyl group, a phenethyl group and the like.

[0055] Specific examples of the onium salt include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyl iodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyl iodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium trifluoromethanesulfonate, 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, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, 4-(phenylthio)phenyl diphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tris(trifluoromethanesulfonyl)methide, triphenylsulfonium tetrakis(fluorophenyl)borate,Examples include tetrakis(fluorophenyl)boric acid tris[4-(4-acetylphenyl)thiophenyl]sulfonium, triphenylsulfonium tetrakis(pentafluorophenyl)borate, tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(pentafluorophenyl)borate, etc.

[0056] Specific examples of the diazomethane derivative 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(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, 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane, etc.

[0057] Specific examples of the glyoxime derivative 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-pentanedione glyoxime, bis-(p-toluenesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis-o-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis-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, bis-o-(camphorsulfonyl)-α-dimethylglyoxime, and the like.

[0058] Specific examples of the β-ketosulfone derivative include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane, 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane, and the like.

[0059] Specific examples of the disulfone derivative include diphenyldisulfone, dicyclohexyl disulfone, and the like.

[0060] Specific examples of the nitrobenzyl sulfonate derivative include 2,6-dinitrobenzyl p-toluenesulfonate, 2,4-dinitrobenzyl p-toluenesulfonate, and the like.

[0061] Specific examples of the sulfonic acid ester derivative include 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, 1,2,3-tris(p-toluenesulfonyloxy)benzene, and the like.

[0062] Specific examples of the imide-yl-sulfonate derivative include phthalimide-yl-triflate, phthalimide-yl-tosylate, 5-norbornene-2,3-dicarboxyimide-yl-triflate, 5-norbornene-2,3-dicarboxyimide-yl-tosylate, 5-norbornene-2,3-dicarboxyimide-yl-n-butyl sulfonate, n-trifluoromethylsulfonyloxynaphthylimide, and the like.

[0063] Specific examples of the oxime sulfonate derivative include α-(benzenesulfonium oxyimino)-4-methylphenylacetonitrile, α-(p-tolylsulfonium oxyimino)-p-methoxyphenylacetonitrile, and the like.

[0064] Specific examples of the iminosulfonate derivative include (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-(4-(4-methylphenylsulfonyloxy)phenyl)sulfonyloxyimino)-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, and the like.

[0065] In addition, 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane and the like can also be preferably used.

[0066] The content of component (C) is preferably 0.05 to 20 parts by mass, more preferably 0.05 to 5 parts by mass, based on 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. If it is 20 parts by mass or less, an increase in the absorbance of the photoacid generator itself can be suppressed, and there is no possibility of problems such as a decrease in transparency, which is preferable. Component (C) can be used alone or in combination of two or more.

[0067] [(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 component that can cause a condensation reaction with the phenolic hydroxy group in component (A) described above, or the saturated hydrocarbyloxy group represented by R 13 , R 14 , R 23 or R 24 to facilitate pattern formation and further increase the strength of the cured product.

[0068] Examples of the crosslinking agent include melamine compounds, guanamine compounds, glycoluril compounds, or urea compounds containing an average of two or more methylol groups and / or alkoxymethyl groups in one molecule; amino condensates modified with formaldehyde or formaldehyde-alcohol; phenolic compounds having an average of two or more methylol groups or alkoxymethyl groups in one molecule; and epoxy compounds having an average of two or more epoxy groups in one molecule.

[0069] Examples of the melamine compound include those represented by the following formula (D).

Chemical formula

[0070] In formula (D), R 201 ~R 206is independently a hydroxymethyl group, a saturated hydrocarbyloxymethyl group having 2 to 5 carbon atoms, or a hydrogen atom, provided that at least one is a hydroxymethyl group or a saturated hydrocarbyloxymethyl group. Examples of the saturated hydrocarbyloxymethyl group include alkoxymethyl groups such as a methoxymethyl group and an ethoxymethyl group.

[0071] Examples of the melamine compound represented by formula (D) include trimethoxymethylmonohydroxymethylmelamine, dimethoxymethylmonohydroxymethylmelamine, trimethylolmelamine, hexamethylolmelamine, hexamethoxymethylmelamine, hexaethoxymethylmelamine, and the like.

[0072] The melamine compound represented by formula (D) can be obtained, for example, by first modifying a melamine monomer by hydroxymethylation with formaldehyde according to a known method, or further modifying it by alkoxylation with an alcohol. The alcohol is preferably a lower alcohol, for example, an alcohol having 1 to 4 carbon atoms.

[0073] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, tetramethoxyethylguanamine, and the like.

[0074] Examples of the glycoluril compound include tetramethylolglycoluril, tetrakis(methoxymethyl)glycoluril, and the like.

[0075] Examples of the urea compound include tetramethylolurea, tetramethoxymethylurea, tetramethoxyethylurea, tetraethoxymethylurea, tetrapropoxymethylurea, and the like.

[0076] Examples of the amino condensate modified with the formaldehyde or formaldehyde-alcohol include a melamine condensate modified with formaldehyde or formaldehyde-alcohol, a urea condensate modified with formaldehyde or formaldehyde-alcohol, and the like.

[0077] Examples of the modified melamine condensate include those obtained by addition condensation polymerization of a compound represented by formula (D) or its multimer (for example, oligomer such as dimer and trimer) and formaldehyde until a desired molecular weight is reached. As the addition condensation polymerization method, a conventionally known method can be adopted. Further, the modified melamine represented by formula (D) can be used alone or in combination of two or more.

[0078] Examples of the urea condensate modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensate, ethoxymethylated urea condensate, propoxymethylated urea condensate, and the like.

[0079] The modified urea condensate can be obtained, for example, by modifying a urea condensate with a desired molecular weight with formaldehyde to form methylol groups or further modifying it with alcohol to form alkoxyl groups according to a known method.

[0080] Examples of the phenolic compound having an average of two or more methylol groups or alkoxymethyl groups in one molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2',6,6'-tetramethoxymethylbisphenol A, and the like.

[0081] Examples of the epoxy compound 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, novolak type epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin, triphenolalkane type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene-modified phenol novolak 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 type epoxy resin, and the like.

[0082] When containing component (D), its content is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, based on 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. If it is 50 parts by mass or less, the proportion of component (A) in the photosensitive resin composition will not decrease, so that a sufficient effect can be exhibited in the cured product. Component (D) may be used alone or in combination of two or more.

[0083] [(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 various additives described later, but an organic solvent is preferred because of its excellent solubility in these components.

[0084] 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; 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 a mixed solvent thereof, which have the most excellent solubility of the photoacid generator, are preferred. These organic solvents can be used alone or in combination of two or more.

[0085] (E) The content of the component 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 with respect to 100 parts by mass of the component (A) from the viewpoints of the compatibility and viscosity of the photosensitive resin composition. The component (E) may be used alone or in combination of two or more.

[0086] [Other Additives] The photosensitive resin composition of the present invention may contain other additives in addition to the above-described components. Examples of the other additives include surfactants commonly used to improve coatability.

[0087] As the surfactant, nonionic ones are preferable. Examples thereof include fluorosurfactants, specifically, perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkylamine oxides, fluorine-containing organosiloxane compounds, and the like. Commercially available products can be used, for example, Fluorad (registered trademark) FC-430 (manufactured by 3M Company), Surflon (registered trademark) S-141, S-145 (manufactured by AGC Seimi Chemical Co., Ltd.), Unidine (registered trademark) DS-401, DS-4031, DS-451 (manufactured by Daikin Industries, Ltd.), Megafac (registered trademark) F-8151 (manufactured by DIC Corporation), X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. Among these, Fluorad FC-430 and X-70-093 are preferable. The content of the surfactant is preferably 0.05 to 1 part by mass with respect to 100 parts by mass of the component (A).

[0088] The photosensitive resin composition of the present invention may contain a silane coupling agent as other additives. By including a silane coupling agent, the adhesion of the film obtained from the composition to the adherend can be further enhanced. Examples of the silane coupling agent include epoxy group-containing silane coupling agents and aromatic group-containing aminosilane coupling agents. 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% by mass in the photosensitive resin composition of the present invention.

[0089] The preparation of the photosensitive resin composition of the present invention is carried out by a conventional method. For example, the photosensitive resin composition of the present invention can be prepared by stirring and mixing the above-mentioned components and then filtering the solid content with a filter or the like as necessary.

[0090] 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 wirings, a coverlay film, a solder mask, a material for an insulating film for through electrodes (for TSV), and further as an adhesive between laminated substrates in three-dimensional lamination.

[0091] [Pattern Formation Method Using the Photosensitive Resin Composition] The pattern formation method using the photosensitive resin composition of the present invention (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 with a developer to form a pattern is included.

[0092] Step (i) is a step of forming a photosensitive resin film on a substrate using the photosensitive resin composition. Examples of the substrate include a silicon wafer, a silicon wafer for a through electrode, a silicon wafer thinned by back grinding, a plastic or ceramic substrate, and a substrate having a metal such as Ni or Au on the entire surface or a part of the substrate by an ion sputtering method, a plating method, or the like. Further, a substrate having irregularities may be used.

[0093] Examples of the method for forming the photosensitive resin film include a method of applying the photosensitive resin composition onto a substrate and performing preheating (pre-bake) as necessary. As the coating method, a known method may be used, and examples include a dip method, a spin coating method, and a roll coating method. The coating amount of the photosensitive resin composition can be appropriately selected according to the purpose, but it is preferably applied so that the film thickness of the obtained photosensitive resin film is preferably 0.1 to 200 μm, more preferably 1 to 150 μm.

[0094] For the purpose of improving the film thickness uniformity on the substrate surface, a solvent may be dropped onto the substrate before applying the photosensitive resin composition (pre-wet method). The solvent to be dropped and its amount can be appropriately selected according to the purpose. Examples of the solvent include alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, and glycols such as PGME, but it is also possible to use the solvent used in the photosensitive resin composition.

[0095] Here, in order to efficiently perform the photocuring reaction, pre-bake may be performed as necessary to evaporate the solvent and the like in advance. The pre-bake can be performed, for example, at 40 to 140 °C for about 1 minute to 1 hour.

[0096] Next, (ii) the photosensitive resin film is exposed. At this time, the exposure is preferably performed with light having a wavelength of 10 to 600 nm, more preferably with light having a wavelength of 190 to 500 nm. Examples of light having such a wavelength include light of various wavelengths generated by a radiation generator, such as ultraviolet rays such as g-line, h-line, and i-line, and far ultraviolet rays (248 nm, 193 nm), etc. Among these, light having a wavelength of 248 to 436 nm is particularly preferred. The exposure dose is preferably 10 to 10,000 mJ / cm 2 is preferred.

[0097] The exposure may be performed through a photomask. The photomask may be, for example, one having a desired pattern drilled therethrough. The material of the photomask is not particularly limited, but those that shield light of the above wavelength are preferred. For example, those provided with chromium or the like as a light-shielding film are preferably used.

[0098] Furthermore, in order to enhance the development sensitivity, post-exposure baking (PEB) may be performed. PEB is preferably carried out at 40 to 150 °C for 0.5 to 10 minutes. By PEB, the exposed portion is crosslinked to form an insolubilized pattern that is insoluble in the organic solvent that is the developer.

[0099] After exposure or after PEB, (iii) the photosensitive resin film is developed using 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 the solvent used in the photosensitive resin composition. Examples of the developing method include ordinary methods, such as a method of immersing the substrate on which the pattern is formed in the developer. By organic solvent development, the unexposed portion is dissolved and removed to form a pattern. Thereafter, washing, rinsing, drying, etc. are performed as necessary to obtain a resin film having a desired pattern.

[0100] Furthermore, the film formed with the pattern (iv) may be post-cured using an oven or a hot plate, preferably at 100 to 250°C, more preferably at 150 to 220°C. When the post-curing temperature is 100 to 250°C, the crosslinking 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, strength, electrical properties, and further adhesion strength. The post-curing time is preferably 10 minutes to 10 hours, and more preferably 10 minutes to 3 hours. By using the photosensitive resin composition of the present invention, a film excellent in various film properties can be obtained even with a post-curing at a relatively low temperature around 200°C. The film thickness of the film (cured film) after post-curing is usually 1 to 200 μm, preferably 5 to 50 μm.

[0101] When it is not necessary to form a pattern, for example, when it is desired to form merely a uniform film, in step (ii) of the above-described pattern forming method, film formation may be performed by exposing with light of an appropriate wavelength without passing through the photomask. 。

[0102] [Method for bonding substrates] The photosensitive resin composition of the present invention can also be used as an adhesive for bonding two substrates. As a method for bonding substrates, a method of bonding a substrate formed with a film of the photosensitive resin composition of the present invention to a second substrate so that an adhesive bond is formed between the two substrates under suitable conditions of heat and pressure can be mentioned. Either one or both of the substrate formed with the film and the second substrate may be diced into chips. As the bonding conditions, the heating temperature is preferably 50 to 200°C and 1 to 60 minutes. As a bonding apparatus, a wafer bonder apparatus can be used to bond wafers under reduced pressure while applying a load, or a chip-wafer or chip-chip bonding using a flip chip bonder apparatus can also be performed. The bonding layer formed between the substrates has its bonding strength increased by the post-curing treatment described later and becomes a permanent bond.

[0103] By subjecting the substrate after pasting (adhering) to post-curing under the same conditions as the above-described step (iv), the crosslink density of the film increases, and the substrate adhesion can be enhanced. Although a crosslink reaction occurs due to heating during adhesion, no side reaction accompanied by degassing occurs in the crosslink reaction. Therefore, especially when used as a substrate adhesive, no bonding defect (void) is induced.

[0104] [Photosensitive dry film] The photosensitive dry film of the present invention includes a support film and a photosensitive resin film obtained from the photosensitive resin composition on the support film.

[0105] 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 possibility that bubbles due to its volatilization remain inside the photosensitive resin film and between the uneven substrate.

[0106] From the viewpoints of flatness, step coverage, and substrate lamination interval on an uneven substrate, the film thickness of the photosensitive resin film is preferably 5 to 200 μm, more preferably 10 to 100 μm.

[0107] Also, 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, enter deep into a narrow gap, and strengthen the adhesiveness to the substrate by softening the resin. Therefore, from the viewpoint of its fluidity, the viscosity of the photosensitive resin film is preferably 10 to 5,000 Pa·s, more preferably 30 to 2,000 Pa·s, still more preferably 50 to 300 Pa·s at 80 to 120°C. In the present invention, the viscosity is a measured value by a rotational viscometer.

[0108] When the photosensitive dry film of the present invention is adhered to a substrate with irregularities, the photosensitive resin film can follow the irregularities and be coated, achieving high flatness. In particular, since the photosensitive resin film is characterized by low viscoelasticity, higher flatness can be achieved. Further, when the photosensitive resin film is adhered to the substrate in a vacuum environment, the generation of gaps between them can be more effectively prevented.

[0109] The photosensitive dry film of the present invention can be manufactured by applying the photosensitive resin composition on a support film and drying it to form a photosensitive resin film. As the manufacturing apparatus for the photosensitive dry film, generally, a film coater for manufacturing adhesive products can be used. Examples of the film coater include comma coater, comma reverse coater, multi-coater, die coater, lip coater, lip reverse coater, direct gravure coater, offset gravure coater, three-bottom reverse coater, four-bottom reverse coater, and the like.

[0110] 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 on the support film with a predetermined thickness, and then passed through a hot air circulation oven at a predetermined temperature and time to be dried on the support film to form a photosensitive resin film, thereby manufacturing a photosensitive dry film. Further, 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 and the protective film, and then wound around the winding shaft of the film coater to manufacture 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.

[0111] The support film may be a single-layer film composed of a single film or a multilayer film formed by laminating a plurality of 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 preferable in terms of having 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 can be used, for example, Serapil WZ(RX), Serapil 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 Co., Ltd.), PET38×1-A3, PET38×1-V8, PET38×1-X08 (all manufactured by Nippa Co., Ltd.), etc.

[0112] As the protective film, the same films as the support films described above can be used. However, polyethylene terephthalate and polyethylene are preferable in terms of having appropriate flexibility. Commercially available products can be used. For polyethylene terephthalate, those already exemplified can be used. For polyethylene, examples include GF-8 (manufactured by Tamapoly Co., Ltd.), PE Film 0 type (manufactured by Nippa Co., Ltd.), etc.

[0113] From the viewpoints of the stability of photosensitive dry film production, winding distortion with respect to the core, and prevention of so-called curling, the thicknesses of both the support film and the protective film are preferably 10 to 100 μm, more preferably 25 to 50 μm.

[0114] [Pattern formation method using a 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 which includes the above.

[0115] 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 a photosensitive resin film on the substrate. When the photosensitive dry film has a protective film, after peeling the protective film from the photosensitive dry film, 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.

[0116] Examples of the substrate include the same ones as those described in the pattern formation method using a photosensitive resin composition. As the film attachment device, a vacuum laminator is preferable. For example, after peeling the protective film of the photosensitive dry film, the exposed photosensitive resin film is brought into close contact with the substrate on a table at a predetermined temperature using an attachment roll at a predetermined pressure in a vacuum chamber at a predetermined vacuum degree. 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.

[0117] In order to obtain a photosensitive resin film with a required thickness, the film may be attached multiple times as necessary. The number of attachment times is, for example, about 1 to 10 times, and a photosensitive resin film with a film thickness of 10 to 1,000 μm, particularly about 100 to 500 μm, can be obtained.

[0118] In order to efficiently perform 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. The pre-baking can be performed, for example, at 40 to 140°C for about 1 minute to 1 hour.

[0119] The photosensitive resin film attached to the substrate can form a pattern by, in the same manner as in the case of the pattern formation method using the photosensitive resin composition, (ii) a step of exposing the photosensitive resin film, (iii) a step of developing the exposed photosensitive resin film with a developer to form a pattern, and, if necessary, (iv) performing a post-curing treatment. Note that the support film of the photosensitive dry film is peeled off before pre-baking or before PEB according to the process, or removed by other methods.

[0120] The films obtained from the photosensitive resin composition and the photosensitive dry film are excellent in heat resistance, flexibility, electrical insulation, mechanical properties, and adhesion to substrates and the like, and are suitably used as films for protecting electrical and electronic components such as semiconductor elements and films for substrate adhesion.

Examples

[0121] Hereinafter, the present invention will be described more specifically by showing 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 monodisperse polystyrene as a standard under the analysis conditions of using TSKgel Super HZM-H (manufactured by Tosoh Corporation) as a column, a flow rate of 0.6 mL / min, a elution solvent of THF, and a column temperature of 40°C.

[0122] Compounds (S-1) to (S-6) used in the synthesis examples are shown below.

Chemical formula

[0123] [1] Synthesis of silicone resin [Synthesis Example 1] After adding 215.0 g (0.5 mol) of compound (S-6) to a 3 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5 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 Shin-Etsu Chemical Co., Ltd. product was added dropwise over 1 hour (total amount of hydrosilyl groups / total amount of alkenyl groups = 1 / 1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100°C and aged for 6 hours. Then, toluene was distilled off under reduced pressure from the reaction solution to obtain silicone resin A-1. Silicone resin A-1 1 was confirmed to contain repeating units a1, a2, b1, and b2 by 1H-NMR (manufactured by Bruker). The Mw of silicone resin A-1 was 62,000, and the silicone content was 61.6 mass%.

[0124] [Synthesis Example 2] To a 3 L flask equipped with a stirrer, thermometer, nitrogen replacement device, and 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. Then, 2,000 g of toluene was added, and the mixture was heated to 70°C. Thereafter, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 48.5 g (0.25 mol) of compound (S-4) and compound (S-5) (y 1 40, manufactured by Shin-Etsu Chemical Co., Ltd.) 755.0 g (0.25 mol) was added dropwise over 1 hour (total amount of hydrosilyl groups / total amount of alkenyl groups = 1 / 1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100°C and aged for 6 hours. Then, toluene was distilled off under reduced pressure from the reaction solution to obtain silicone resin A-2. Silicone resin A-2 1 was confirmed to contain repeating units a1, a3, a4, b1, b3, and b4 by 1H-NMR (manufactured by Bruker). The Mw of silicone resin A-2 was 83,000, and the silicone content was 77.5 mass%.

[0125] [Synthesis Example 3] To a 3 L flask equipped with a stirrer, a thermometer, a nitrogen replacement 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. Then, 2,000 g of toluene was added and the mixture was heated to 70 °C. Thereafter, 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 = 20, manufactured by Shin-Etsu Chemical Co., Ltd.) 79.3 g (0.05 mol) were added dropwise over 1 hour (total of hydrosilyl groups / total of alkenyl groups = 1 / 1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100 °C and aged for 6 hours. Then, toluene was distilled off under reduced pressure from the reaction solution to obtain silicone resin A-3. Silicone resin A-3 1 was confirmed to contain repeating units a1, a2, a4, b1, b2, and b4 by 1H-NMR (manufactured by Bruker). The Mw of silicone resin A-3 was 24,000 and the silicone content was 31.2% by mass.

[0126] [2] Preparation of photosensitive resin composition [Examples 1 to 7 and Comparative Examples 1 to 20] Each component was blended according to the blending amounts shown in Tables 1 to 3, and then stirred and dissolved at room temperature. Thereafter, microfiltration was performed using a 1.0 μm filter made of Teflon (registered trademark) to prepare the photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 20.

[0127]

Table 1

[0128]

Table 2

[0129]

Table 3

[0130] In Tables 1 to 3, epoxy compounds B-1 to B-11 are as follows. [Chemical formula]

[0131] [Chemical formula]

[0132] [Chemical formula]

[0133] [Chemical formula]

[0134] In Tables 1 to 3, photoacid generator PAG-1 is as follows. [Chemical formula]

[0135] In Tables 1 to 3, crosslinking agent CL-1 is as follows. [Chemical formula]

[0136] In Tables 2 and 3, resin A'-1 is as follows. [Chemical formula]

[0137] [3] Preparation of photosensitive dry film Using a die coater as the film coater and a polyethylene terephthalate film (thickness 38 μm) as the support film, the photosensitive resin compositions described in Tables 1 to 3 were each coated on the support film. Next, it was dried by passing through a hot air circulation oven (length 4 m) set at 100 °C for 5 minutes to form a photosensitive resin film on the support film, and a photosensitive dry film was obtained. From above the photosensitive resin film, a polyethylene film (thickness 50 μm) as a protective film was laminated and bonded with a pressure of 1 MPa using a laminating roll 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 with an optical interference film thickness measuring machine (F50-EXR manufactured by Filmmetrics Co., Ltd.).

[0138] [4] Evaluation of Resin Film (1) Pattern Formation and Its Evaluation For the photosensitive dry film with a protective film, the protective film was peeled off, and using a vacuum laminator TEAM-100RF (manufactured by Takatori Co., Ltd.), the degree of vacuum in the vacuum chamber was set to 80 Pa, and the photosensitive resin film on the support film was adhered to a substrate for migration test (a comb-shaped electrode substrate with a conductive material of copper, a conductive part interval and width of 10 μm, and a conductive part thickness of 4 μm). The temperature condition was 100 °C. After returning to normal pressure, the substrate was taken out from the vacuum laminator, and the support film was peeled off. Next, in order to enhance the adhesion to the substrate, preheating was performed at 120 °C for 5 minutes using a hot plate. 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 apparatus under exposure conditions of a wavelength of 365 nm through a mask. After exposure, PEB was performed at 140 °C for 5 minutes using a hot plate and then cooled, and spray development was performed with PGMEA for 300 seconds to form a pattern.

[0139] The photosensitive resin film on the substrate formed with the pattern by the above method was post-cured at 200°C for 2 hours while purging with nitrogen using an oven. Thereafter, the cross-sections of the formed contact hole patterns of 300 μm, 150 μm, 100 μm, and 50 μm were observed with a scanning electron microscope (SEM), and the minimum hole pattern with the hole penetrating to the bottom of the film was defined as the limit resolution. Further, from the obtained cross-sectional photographs, the perpendicularity of the 300-μm contact hole pattern was evaluated. A perpendicular pattern was rated as ◎, a pattern with a slightly tapered shape or footing was rated as ○, a pattern with a strongly tapered shape or footing was rated as △, and a pattern with a defective opening was rated as ×. The results are shown in Tables 4 to 6.

[0140] (2) Evaluation of Electrical Characteristics (Copper Migration) The substrate formed with the pattern by the method of (1) was used as a substrate for copper migration evaluation, and a test was conducted. The conditions of the copper migration test were a temperature of 130°C, a humidity of 85%, and an applied voltage of 10 V, and the time until a short circuit occurred was confirmed with an upper limit of 2,000 hours. The results are shown in Tables 4 to 6.

[0141] (3) Evaluation of Warping Stress Using a film laminator (TEAM-100 manufactured by Takatori Corporation), the prepared film was laminated on an 8-inch silicon wafer, and preheating was performed at 120°C for 5 minutes using a hot plate. Thereafter, without using a mask, exposure was performed using a contact aligner type exposure apparatus under exposure conditions of a wavelength of 365 nm, and then the film was cured by heating at 200°C for 2 hours using an oven, and their warping stress (25°C) was measured using a thin film stress measuring apparatus (FLX-2320-S manufactured by Toho Technology Co., Ltd.). The results are shown in Tables 4 to 6.

[0142] (4) Evaluation of Reliability (Adhesion, Crack Resistance) The above-described photosensitive dry film with a protective film had the protective film peeled off, and using a vacuum laminator TEAM-100RF (manufactured by Takatori Corporation), the degree of vacuum in the vacuum chamber was set to 80 Pa, and the photosensitive resin film on the support film was adhered to a CCL substrate laminated with silicon chips of 10 mm × 10 mm square. The temperature condition was 100 °C. After returning to normal pressure, the substrate was taken out from the vacuum laminator, and the support film was peeled off. Next, in order to enhance the adhesion to the substrate, preheating was performed at 120 °C for 5 minutes using a hot plate. The obtained photosensitive resin film was exposed using a contact aligner type exposure apparatus under exposure conditions of a wavelength of 365 nm without passing through a mask. After exposure, PEB was performed at 140 °C for 5 minutes using a hot plate and then cooled, and post-curing was performed at 200 °C for 2 hours while purging with nitrogen using an oven. Thereafter, a test piece of 20 mm × 20 mm square was obtained using a dicing saw (DAD685 manufactured by DISCO, spindle rotation speed was 40,000 rpm, cutting speed was 20 mm / sec) equipped with a dicing blade so that the outer periphery of the silicon chip became 5 mm. The obtained test pieces (10 pieces each) were subjected to a heat cycle test (repeated 1,500 cycles of holding at -40 °C for 10 minutes and holding at 125 °C for 10 minutes). After the heat cycle test, the peeling state of the resin film from the wafer and the presence or absence of cracks were confirmed. Those with no peeling and no cracks were marked as ○, those with any peeling were marked as ×, and those with any cracks were marked as ×. 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.

[0143] (5) Evaluation of Adhesive Strength (3) The substrate for measuring the warping stress produced was cut into squares with a size of 2 mm × 2 mm using a dicing saw (DISCO DAD685) equipped with a dicing blade. Chips with a size of 2 mm × 2 mm were bonded onto a separately prepared silicon wafer (base substrate) with a size of 15 mm × 15 mm at 150 °C and a load of 50 mN through a resin film. Then, it was heated at 180 °C for 2 hours to cure the resin film, and test pieces were obtained. Five test pieces were manufactured for each case and subjected to an adhesive strength measurement test. For the adhesive strength measurement, a bond tester (Dage Dage series 4000 - PXY) was used to measure the resistance force when the semiconductor chip (2 mm × 2 mm) peeled off from the base substrate (silicon wafer with a size of 15 mm × 15 mm), and the adhesion 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 - 6. Note that the numerical values are the averages of the measured values for five test pieces each, and the higher the numerical value, the higher the adhesive strength.

[0144] (6) Evaluation of heat resistance The test pieces for measuring the adhesive strength prepared in (5) were placed in an oven heated to 200 °C for 1,000 hours, then taken out of the oven and subjected to an adhesive strength measurement test in the same manner as in (5). The results are shown in Tables 4 - 6.

[0145] (7) Evaluation of relative permittivity and dielectric loss tangent The photosensitive dry film with the protective film described above had the protective film peeled off and was exposed using a contact aligner type exposure apparatus under exposure conditions of a wavelength of 365 nm without passing through a mask. Then, it was post - cured at 200 °C for 2 hours using an oven while purging with nitrogen. After taking it out of the oven and peeling off the support film, the relative permittivity (10 GHz, 25 °C) and dielectric loss tangent (10 GHz, 25 °C) were measured. Note that the relative permittivity and dielectric loss tangent were measured by the cavity resonator method using an apparatus manufactured by AET. The results are shown in Tables 4 - 6.

[0146] (8) Evaluation of flexibility The cured film prepared in (7) was wound around a plastic cylinder with an outer diameter of 8.5 cm. After standing for 10 seconds, the film was returned to its original state, and it was checked whether there were any abnormalities on the film. If cracks or the like occurred, it was marked as "×", and if there was no change, it was marked as "○".

[0147]

Table 4

[0148]

Table 5

[0149]

Table 6

[0150] From the above results, the photosensitive resin composition and the photosensitive dry film of the present invention can easily form a thick film with fine vertical patterns and exhibit sufficient characteristics as photosensitive materials. In addition, the photosensitive resin films obtained from these have excellent flexibility, low dielectric constant and low dielectric tangent, high adhesiveness, high heat resistance, high resistance to copper migration, and low warpage of the substrate, and have high reliability such as crack resistance and adhesion as the insulating protective film, and can be suitably used as a forming material for protective films of various electrical and electronic components such as circuit boards, semiconductor elements, and display elements. According to the present invention, it is possible to provide a photosensitive resin composition and a photosensitive dry film with higher reliability.

Claims

1. A photosensitive resin composition comprising: (A) a silicone resin containing an acid-crosslinkable group represented by the following formula (A); (B) an epoxy compound represented by the following formula (B); and (C) a photoacid generator. 【Chemical 1】 (In the formula, R1 to R4 are each 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 hydroxy group.) 【Chemical 2】 (wherein, R 51 ~R 55 are each independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms.)

2. The photosensitive resin composition according to claim 1, wherein the (A) silicone resin contains repeating units represented by the following formulas (a1) to (a4) and (b1) to (b4). 【Chemical Formula 3】 [wherein, R 1 to R 4 are each independently a hydrocarbyl group having 1 to 8 carbon atoms. k is an integer of 1 to 600. a 1 to a 4 and b 1 to 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 4】 (wherein Y 1 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 11 and R 12 are each independently a hydrogen atom or a methyl group. R 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. p 1 and p 2 are each independently an integer from 0 to 7. q 1 and q 2 are each independently an integer from 0 to 2. The dashed line is a bond.). 【Chemical Formula 5】 (wherein 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. The dashed line is a bond.) 【Chemical Formula 6】 (wherein 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. The dashed line is a bond.) 【Chemical Formula 7】 (wherein, 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. The dashed line is a bond.) ]]

3. The photosensitive resin composition according to claim 1 or 2, wherein the content of the epoxy compound as the (B) component is 3 to 100 parts by mass with respect to 100 parts by mass of the (A) component.

4. The photosensitive resin composition according to any one of claims 1 to 3, further comprising (D) a crosslinking agent.

5. The photosensitive resin composition according to claim 4, wherein the (D) crosslinking agent is at least one selected from a nitrogen-containing compound selected from a melamine compound, a guanamine compound, a glycoluril compound, and a urea compound, formaldehyde, or an amino condensate modified with formaldehyde-alcohol, each containing on average 2 or more methylol groups and / or alkoxymethyl groups in one molecule; a phenol compound having on average 2 or more methylol groups or alkoxymethyl groups in one molecule; and an epoxy compound having on average 2 or more epoxy groups in one molecule.

6. The photosensitive resin composition according to any one of claims 1 to 5, 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 the photosensitive resin film according to claim 7 on the support film.

9. A method for forming a pattern, comprising: (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 with a developer to form a pattern.

10. (i') a step of forming a photosensitive resin film on a substrate using the photosensitive dry film according to claim 8; (ii) The step of exposing the photosensitive resin film, and (iii) The step of developing the exposed photosensitive resin film with a developer to form a pattern A pattern forming method comprising the steps.

11. Furthermore, the pattern forming method according to claim 9 or 10, further comprising (iv) a step of post-curing the photosensitive resin film formed into a pattern by development at a temperature of 100 to 250 °C.

12. The photosensitive resin composition according to any one of claims 1 to 6, which is a material for a film for protecting electric and electronic parts.

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

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