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

Abstract

A photosensitive resin composition comprising (A) a silicone resin containing an acid-crosslinkable group, (B) an alicyclic epoxy compound represented by the following formula (B1) or (B2), and (C) a photoacid generator is provided. (In the formula, R 11 ~R 46 each independently is a hydrogen atom or a saturated hydrocarbon group having a carbon number of 1 to 8.

Description

Technical Field

[0001] This invention relates to photosensitive resin compositions, photosensitive resin coatings, photosensitive dry films, and methods for pattern formation. Background Technology

[0002] To date, photosensitive polyimide compositions, photosensitive epoxy resin compositions, and photosensitive silicone compositions have been used as protective films for photosensitive semiconductor devices and insulating films for multilayer printed circuit boards. As a photosensitive material for protecting such substrates and circuits, a photosensitive silicone composition with excellent flexibility has been proposed (Patent Document 1). This photosensitive silicone composition can be cured at low temperatures and can form a coating with excellent reliability, such as moisture resistance and adhesion. However, it suffers from poor chemical resistance to photoresist stripping solutions with strong dissolving power, such as N-methyl-2-pyrrolidone.

[0003] In response, a photosensitive organosilicon composition with an organosilicon polymer containing a silymine backbone as the main component was proposed (Patent Document 2). This photosensitive organosilicon composition improves chemical resistance to photoresist stripping solutions, but it has problems such as the cured material peeling off from the substrate during thermal cycling tests and cracks forming in the cured material. Further improvements in reliability are desired.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2002-88158

[0007] Patent Document 2: Japanese Patent Application Publication No. 2008-184571 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] The present invention was made in view of the above-mentioned actual situation, and its object is to provide a photosensitive resin composition, a photosensitive resin coating, a photosensitive dry film, and a method for patterning using the above, which are capable of easily forming fine patterns in thick films and can form various film properties such as crack resistance and adhesion to substrates, electronic components, semiconductor elements, and especially circuit boards, and have excellent reliability as coatings for protecting electrical and electronic components, coatings for bonding substrates, etc.

[0010] Methods for solving problems

[0011] In order to achieve the above objectives, the inventors conducted in-depth research and found that the above objectives can be achieved by using a photosensitive resin composition comprising (A) an organosilicon resin containing acid crosslinking groups, (B) a specific alicyclic epoxy compound, and (C) a photoacid-generating agent, thus completing the present invention.

[0012] Therefore, the present invention provides the following photosensitive resin composition, photosensitive resin coating, photosensitive dry film, and pattern forming method.

[0013] 1. A photosensitive resin composition comprising: (A) an organosilicon resin containing acid crosslinking groups, (B) an alicyclic epoxy compound represented by formula (B1) or (B2) below, and (C) a photoacid-generating agent.

[0014] [Chemistry 1]

[0015]

[0016] (where R is in the formula) 11 ~R 46 Each group consists independently of a hydrogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms.

[0017] 2. The photosensitive resin composition according to 1, wherein (A) the organosilicon resin is represented by the following formula (A).

[0018] [Chemistry 2]

[0019]

[0020] (where R is in the formula) 1 ~R 4 Each is an independent hydrocarbon group with 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, which 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.

[0021] 3. The photosensitive resin composition according to 2, wherein (A) the silicone resin comprises repeating units represented by the following formulas (a1) to (a4) and (b1) to (b4).

[0022] [Chemistry 3]

[0023]

[0024] (where R is in the formula) 1 ~R 4 Each group is an independent hydrocarbon group with 1 to 8 carbon atoms. k is an integer from 1 to 600. a 1 ~a 4 and b 1 ~b 4The molar ratio of each repeating unit is expressed as 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 A number equal to 1. X 1 X is a divalent group represented by the following formula (X1). 2 X is a divalent group represented by the following formula (X2). 3 X is a divalent group represented by the following formula (X3). 4 (This refers to a divalent group represented by the following formula (X4).)

[0025] [Chemistry 4]

[0026]

[0027] (where Y) 1 It is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl, or fluorene-9,9-diyl. R 11 and R 12 Each can be independently a hydrogen atom or a methyl group. R 13 and R 14 Each is independently a saturated hydrocarbon group or a saturated hydrocarbon oxygen group with 1 to 4 carbon atoms. 1 and p 2 Each is an independent integer from 0 to 7. q 1 and q 2 Each element is an independent integer between 0 and 2. (The dashed lines represent the bond ends.)

[0028] [Chemistry 5]

[0029]

[0030] (where Y) 2It is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl, or fluorene-9,9-diyl. R 21 and R 22 Each can be independently a hydrogen atom or a methyl group. R 23 and R 24 Each is independently a saturated hydrocarbon group or a saturated hydrocarbon oxygen group having 1 to 4 carbon atoms. 1 and r 2 Each is an independent integer from 0 to 7. 1 and s 2 Each element is an independent integer between 0 and 2. (The dashed lines represent the bond ends.)

[0031] [Chemistry 6]

[0032]

[0033] (where R is in the formula) 31 and R 32 Each can be independently a hydrogen atom or a methyl group. 1 and t 2 Each element is an independent integer from 0 to 7. (The dashed lines represent the bond ends.)

[0034] [Chemistry 7]

[0035]

[0036] (where R is in the formula) 41 and R 42 Each can be independently a hydrogen atom or a methyl group. R 43 and R 44 Each is an independent hydrocarbon group with 1 to 8 carbon atoms. 1 and u 2 Each is an independent integer from 0 to 7. v is an integer from 0 to 600. (The dashed line indicates the bond end.)

[0037] 4. The photosensitive resin composition according to any one of 1 to 3, wherein the content of the epoxy compound in component (B) is 3 to 100 parts by weight relative to 100 parts by weight of component (A).

[0038] 5. The photosensitive resin composition according to any one of 1 to 4, further comprising (D) a crosslinking agent.

[0039] 6. The photosensitive resin composition according to claim 5, wherein (D) the crosslinking agent is at least one selected from nitrogen-containing compounds selected from melamine compounds, guanidine compounds, glycourea compounds and urea compounds, amino condensates modified with formaldehyde or formaldehyde-alcohol, phenolic compounds having an average of more than 2 hydroxymethyl or alkoxymethyl groups in one molecule, and epoxy compounds having an average of more than 2 epoxy groups in one molecule.

[0040] 7. The photosensitive resin composition according to any one of 1 to 6, further comprising (E) solvent.

[0041] 8. A photosensitive resin coating obtained from the photosensitive resin composition according to any one of 1 to 7.

[0042] 9. A photosensitive dry film comprising: a support film and a photosensitive resin coating according to 8 on the support film.

[0043] 10. A method for forming a pattern, comprising:

[0044] (i) A process of forming a photosensitive resin coating on a substrate using the photosensitive resin composition according to any one of 1 to 7;

[0045] (ii) the process of exposing the photosensitive resin coating; and

[0046] (iii) The process of developing the exposed photosensitive resin coating with a developing solution to form a pattern.

[0047] 11. A method for forming a pattern, comprising:

[0048] (i') A process of forming a photosensitive resin coating on a substrate using the photosensitive dry film according to 9;

[0049] (ii) the process of exposing the photosensitive resin coating; and

[0050] (iii) The process of developing the exposed photosensitive resin coating with a developing solution to form a pattern.

[0051] 12. The pattern forming method according to 10 or 11 further comprises: (iv) a step of post-curing the photosensitive resin coating on which a pattern has been formed by development at a temperature of 100 to 250°C.

[0052] 13. The photosensitive resin composition according to any one of 1 to 7, which is a material for a protective coating for electrical and electronic components.

[0053] 14. The photosensitive resin composition according to any one of 1 to 7, wherein it is a substrate bonding coating material for bonding two substrates.

[0054] The effects of the invention

[0055] The photosensitive resin composition of the present invention can form coatings with a wide range of film thicknesses and exhibits good storage stability. Furthermore, it can be used to form fine patterns with excellent verticality in thick films using the patterning method described later. The coatings obtained using the photosensitive resin composition and photosensitive dry film of the present invention have high chemical resistance to photoresist stripping solutions, etc. In addition, they exhibit excellent adhesion, mechanical properties, electrical insulation, and copper migration resistance to substrates, electronic components, semiconductor elements, and especially circuit boards. Furthermore, the above-mentioned coatings have high reliability as insulating protective films and are suitable for use as materials for forming protective coatings for various electrical and electronic components such as circuit boards, semiconductor elements, and display elements, as well as materials for forming coatings for substrate bonding. Detailed Implementation

[0056] [Photosensitive Resin Composition]

[0057] The photosensitive resin composition of the present invention comprises (A) an organosilicon resin containing acid crosslinking groups, (B) a specified epoxy resin and (C) a photoacid-generating agent.

[0058] [(A) Organosilicon resin containing acid crosslinking groups]

[0059] (A) The silicone resin contains acid-crosslinking groups in its molecule. Here, an acid-crosslinking group refers to a group in which functional groups can be chemically bonded directly or via a crosslinking agent using the action of an acid. Epoxy groups and phenolic hydroxyl groups are preferred as such acid-crosslinking groups. Regarding epoxy groups and phenolic hydroxyl groups, only one or both may be included.

[0060] The organosilicon resin containing acid crosslinking groups described above is preferably represented by the following formula (A).

[0061] [Chemistry 8]

[0062]

[0063] In formula (A), R 1 ~R 4 Each is independently a hydrocarbon group having 1 to 8 carbon atoms, preferably a hydrocarbon group having 1 to 6 carbon atoms. k is an integer from 1 to 600, preferably an integer from 1 to 400, and more preferably an integer from 1 to 200. a and b represent the composition ratio (molar ratio) of each repeating unit, and are numbers that satisfy 0 < a < 1, 0 < b < 1, and a + b = 1. X is a divalent organic group containing an epoxy group and / or a phenolic hydroxyl group.

[0064] Regarding the aforementioned hydrocarbon groups, straight-chain, branched, and cyclic hydrocarbon groups are all acceptable. Specific examples include alkyl groups such as methyl, ethyl, propyl, hexyl, and their isomers; cyclic saturated hydrocarbon groups such as cyclohexyl; and aryl groups such as phenyl. Among these, methyl and phenyl are preferred based on the ease of obtaining the raw materials.

[0065] As an organosilicon resin represented by formula (A), it is particularly preferred to contain 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).

[0066] [Chemistry 9]

[0067]

[0068] (where R is in the formula) 1 ~R 4 (And k is the same as above.)

[0069] In equations (a1) and (b1), X 1 X1 is a divalent group represented by the following formula (X1).

[0070] [Chemistry 10]

[0071]

[0072] (In the formula, the dashed lines represent the bonding ends.)

[0073] In equation (X1), Y 1 It is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl, or fluorene-9,9-diyl. R 11 and R 12 Each can be independently a hydrogen atom or a methyl group. R 13 and R 14 Each is independently a saturated hydrocarbon group or a saturated hydrocarbon oxygen group with 1 to 4 carbon atoms. 1 and p 2 Each is an independent integer from 0 to 7. q 1 and q 2 Each is an independent integer between 0 and 2.

[0074] Regarding the aforementioned saturated hydrocarbon groups, straight-chain, branched, and cyclic hydrocarbon groups are all acceptable. Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, and their isomers; and cyclic saturated hydrocarbon groups such as cyclopropyl and cyclobutyl. Similarly, regarding the aforementioned saturated hydrocarbon oxygen groups, straight-chain, branched, and cyclic hydrocarbon oxygen groups are all acceptable. Specific examples include alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, and their isomers; and cyclic saturated hydrocarbon oxygen groups such as cyclopropoxy and cyclobutoxy.

[0075] In equations (a2) and (b2), X 2 X2 is a divalent group represented by the following formula (X2).

[0076] [Chemistry 11]

[0077]

[0078] (In the formula, the dashed lines represent the bonding ends.)

[0079] In equation (X2), Y 2 It is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl, or fluorene-9,9-diyl. R 21 and R 22 Each can be independently a hydrogen atom or a methyl group. R 23 and R 24 Each is independently a saturated hydrocarbon group or a saturated hydrocarbon oxygen group having 1 to 4 carbon atoms. 1 and r 2 Each is an independent integer from 0 to 7. 1 and s 2 Each is an independent integer from 0 to 2. As examples of the aforementioned saturated hydrocarbon groups and saturated hydrocarbon oxygen groups, those related to R can be listed. 13 and R 14 The same group as the group illustrated in the description.

[0080] In equations (a3) ​​and (b3), X 3 It is a divalent group represented by the following formula (X3).

[0081] [Chemistry 12]

[0082]

[0083] (In the formula, the dashed lines represent the bonding ends.)

[0084] In equation (X3), R 31 and R 32 Each can be independently a hydrogen atom or a methyl group. 1 and t 2 Each is an integer from 0 to 7.

[0085] In equations (a4) and (b4), X 4 X4 is a divalent group represented by the following formula (X4).

[0086] [Chemistry 13]

[0087]

[0088] (In the formula, the dashed lines represent the bonding ends.)

[0089] In equation (X4), R 41 and R 42 Each can be independently a hydrogen atom or a methyl group. R 43 and R 44 Each is an independent hydrocarbon group with 1 to 8 carbon atoms. 1 and u 2 Each is an integer from 0 to 7. v is an integer from 0 to 600, preferably an integer from 0 to 400, and more preferably an integer from 0 to 200. Examples of hydrocarbon groups mentioned above include those related to R. 1 ~R 4 The same group as the group illustrated in the description.

[0090] Regarding the silicone resin of component (A), its weight-average molecular weight (Mw) is preferably 3,000 to 500,000, more preferably 5,000 to 200,000. It should be noted that in this invention, Mw is the converted value of polystyrene determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as the elution solvent.

[0091] In equations (a1)~(a4) and (b1)~(b4), a 1 ~a 4 and b 1 ~b 4 The molar ratio of each repeating unit is expressed as 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 A number equal to 1 is preferred to satisfy 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 equal to 1 are further preferred to satisfy 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 equal to 1. Furthermore, from the perspective of reaction, 0 < b is preferred. 2 <1, more preferably 0.2≤b 2 ≤0.95, more preferably 0.3≤b 2 ≤0.9.

[0092] The aforementioned repeating units can be randomly combined or combined as block polymers. Furthermore, when there are two or more siloxane units in each repeating unit, all siloxane units can be identical, or they can contain two or more different siloxane units. When two or more different siloxane units are included, the siloxane units can be randomly combined, or they can contain blocks of multiple identical siloxane units. Additionally, in the aforementioned organosilicon resin, the organosilicon (siloxane unit) content is preferably 30-80% by mass.

[0093] (A) The silicone resin of component A functions as a resin that imparts film-forming ability. In addition, the resulting resin film has good adhesion to laminates, substrates, etc., good pattern-forming ability, crack resistance and heat resistance.

[0094] (A) One type of silicone resin can be used alone, or two or more types can be used together.

[0095] [(A) Manufacturing method of organosilicon resin]

[0096] (A) The silicone resin of component (A) can be manufactured by addition polymerization of at least one of the following compounds represented by formula (1), formula (2), formula (3), formula (4), and formula (5), and, as needed, formula (6), in the presence of a metal catalyst.

[0097] [Chemistry 14]

[0098]

[0099] (where R is in the formula) 1 ~R 4 (And k is the same as above.)

[0100] [Chemistry 15]

[0101]

[0102] (where R is in the formula) 11 ~R 14 R 21 ~R 24 R 31 R 32 R 41 ~R 44 Y 1 Y 2 p 1 p 2 q 1 q 2 r 1 r 2 s 1 s 2 t 1 t 2 u 1 u 2 (and v are the same as above.)

[0103] As the aforementioned metal catalysts, platinum group metals such as platinum (including platinum black), rhodium, and palladium can be used; platinum chloride, chloroplatinic acid, and chloroplatinates 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, particularly preferably 0 or 6); and alcohol-modified chloroplatinic acid (e.g., US Patent No. 3,22). The following are examples of complexes: those described in specification 0,972; complexes of chloroplatinic acid with alkenes (e.g., those described in U.S. Patent Nos. 3,159,601, 3,159,662, and 3,775,452); products in which platinum group metals such as platinum black and palladium are supported on supports such as alumina, silica, and carbon; rhodium-olefin complexes; triphenylphosphine chlororhodium (so-called Wilkinson catalysts); complexes of platinum chloride, chloroplatinic acid, or chloroplatinate with vinyl-containing siloxanes (especially vinyl-containing cyclic siloxanes), etc.

[0104] The amount of catalyst used is the catalytic amount, which is usually 0.001 to 0.1 parts by mass relative to 100 parts by mass of the raw material compound, and more preferably 0.01 to 0.1 parts by mass.

[0105] In the above addition polymerization reaction, a solvent may be used as needed. Hydrocarbon solvents such as toluene and xylene are preferred as solvents.

[0106] From the viewpoint of preventing catalyst deactivation and enabling polymerization to be completed in a short time, the polymerization temperature is preferably 40–150°C, more preferably 60–120°C. The polymerization time also depends on the type and amount of resin obtained; to prevent moisture from entering the polymerization system, it is preferably about 0.5–100 hours, more preferably 0.5–30 hours. After the reaction is complete, if a solvent is used, it is removed by distillation to obtain the silicone resin of component (A).

[0107] There are no particular limitations on the reaction method. For example, when reacting at least one of the compounds represented by formula (1), formula (2), formula (3), formula (4), and formula (5) with a compound represented by formula (6) as needed, the following method can be listed: First, mix and heat at least one of the compounds represented by formula (3), formula (4), and formula (5) with a compound represented by formula (6) as needed, then add a metal catalyst to the mixture, and then dropwise add the compounds represented by formula (1) and formula (2) over a period of 0.1 to 5 hours.

[0108] For each compound, the total amount of alkenyl groups contained in at least one of the compounds represented by formula (3), the compounds represented by formula (4), and the compounds represented by formula (5), and the compound represented by formula (6) used as needed, is preferably mixed in a molar ratio of 0.67 to 1.67, more preferably 0.83 to 1.25, for the compounds represented by formula (1) and the compounds represented by formula (2).

[0109] The molecular weight (Mw) of the obtained resin can be controlled by using monoallyl compounds such as o-allylphenol or monohydrosilanes and monohydrosiloxanes such as triethylhydrosilane as molecular weight regulators.

[0110] (B) Alicyclic epoxides

[0111] (B) The alicyclic epoxy compound of component (B) is represented by the following formula (B1) or (B2).

[0112] [Chemistry 16]

[0113]

[0114] In equation (B), R 11 ~R 46 Each is independently a hydrogen atom or a saturated hydrocarbon group with 1 to 8 carbon atoms.

[0115] Regarding the aforementioned saturated hydrocarbon groups, straight-chain, branched, and cyclic saturated hydrocarbon groups are all acceptable. Specific examples include alkyl groups with 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, hexyl, and their isomers; and cyclic saturated hydrocarbon groups with 3 to 8 carbon atoms, such as cyclohexyl.

[0116] As R 11 ~R 46 Preferably, hydrogen atoms, methyl or ethyl, more preferably hydrogen atoms or methyl.

[0117] As an alicyclic epoxy compound represented by formula (B1), it is preferred to be represented by the following formula (B1'), and as an alicyclic epoxy compound represented by formula (B2), it is preferred to be represented by the following formula (B2').

[0118] [Chemistry 17]

[0119]

[0120] (In the formula, p, p', q, q', r, and r' are each independently 0, 1, or 2.)

[0121] The alicyclic epoxy compound described above is particularly preferred to be represented by any one of the following formulas (B-1) to (B-4).

[0122] [Chemistry 18]

[0123]

[0124] As the aforementioned alicyclic epoxy compounds, commercially available products can be used, such as DE-102 and DE-103 manufactured by ENEOS Co., Ltd.

[0125] The content of component (B) relative to 100 parts by weight of component (A) is preferably 3 to 100 parts by weight, more preferably 3 to 75 parts by weight, and even more preferably 5 to 50 parts by weight. If the content of component (B) is within the above range, a better coating film is obtained when the dry film is formed, and therefore it is preferred. Component (B) can be used alone or in combination of two or more.

[0126] [(C) Photoacid-producing agents]

[0127] (C) The photoacid-producing agent is not particularly limited as long as it decomposes and produces acid upon light irradiation, but it is preferred to decompose it using light with a wavelength of 190-500 nm. The aforementioned photoacid-producing agent serves as a curing catalyst. Because of the excellent compatibility of the photoacid-producing agent in the photosensitive resin composition of the present invention, a wide range of photoacid-producing agents can be used.

[0128] Examples of photoacid-producing agents include onium salts, diazomethane derivatives, dioxime derivatives, β-ketosulfonate derivatives, disulfonate derivatives, nitrobenzylsulfonate derivatives, sulfonate derivatives, imide sulfonate derivatives, oxime sulfonate derivatives, and iminosulfonate derivatives.

[0129] Examples of onion salts include matte salts represented by the following formula (C1) and iodomonium salts represented by the following formula (C2).

[0130] [Chemistry 19]

[0131]

[0132] In equations (C1) and (C2), R 101 ~R 105 Each can be independently a saturated hydrocarbon group having 1 to 12 carbon atoms that may have substituents, an aryl group having 6 to 12 carbon atoms that may have substituents, or an aralkyl group having 7 to 12 carbon atoms that may have substituents. A - It is a non-nucleophilic counterion.

[0133] Regarding the aforementioned saturated hydrocarbon groups, straight-chain, branched, and cyclic saturated hydrocarbon groups are all acceptable. Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and their isomers; and cyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl. As for the aforementioned aryl groups, examples include phenyl, naphthyl, and biphenyl. As for the aforementioned aralkyl groups, examples include benzyl and phenethyl.

[0134] Examples of substituents include oxo groups, saturated hydrocarbon groups with 1 to 12 carbon atoms, saturated alkyloxy groups with 1 to 12 carbon atoms, aryl groups with 6 to 24 carbon atoms, aralkyl groups with 7 to 25 carbon atoms, aryloxy groups with 6 to 24 carbon atoms, and arylthio groups with 6 to 24 carbon atoms. Furthermore, regarding the hydrocarbon group and saturated alkyloxy group, the hydrocarbon base can be linear, branched, or cyclic. Specific examples include those related to R... 101 ~R 105 The saturated hydrocarbon group shown is the same group as the group illustrated.

[0135] As R 101 ~R 105 Preferably, saturated hydrocarbon groups with substituents, such as methyl, ethyl, propyl, butyl, cyclohexyl, norbornyl, adamantyl, and 2-oxocyclohexyl; aryl groups with substituents, such as phenyl, naphthyl, biphenyl, 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, terphenyl, biphenyloxyphenyl, and biphenylthiophenyl; and aralkyl groups with substituents, such as benzyl and phenethyl. Among these, aryl groups with substituents and aralkyl groups with substituents are more preferred.

[0136] Examples of non-nucleophilic counterions include halide ions such as chloride and bromide ions; fluoroalkane sulfonates such as trifluoromethanesulfonate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate; aryl sulfonates such as toluenesulfonate, benzenesulfonate, 4-fluorobenzenesulfonate, and 1,2,3,4,5-pentafluorobenzenesulfonate; alkane sulfonates such as methanesulfonate and butanesulfonate; fluoroalkane sulfonylimide ions such as trifluoromethanesulfonylimide; fluoroalkane sulfonyl methyl ions such as tri(trifluoromethanesulfonyl)methyl ions; borate ions such as tetraphenylborate and tetra(pentafluorophenyl)borate; and phosphate ions such as hexafluorophosphate and tri(pentafluoroethyl)trifluorophosphate.

[0137] As the aforementioned diazomethane derivatives, compounds represented by the following formula (C3) can be listed.

[0138] [Chemistry 20]

[0139]

[0140] In equation (C3), R 111 and R 112 Each can be independently a saturated hydrocarbon group with 1 to 12 carbon atoms, a halo-saturated hydrocarbon group with 1 to 12 carbon atoms, an aryl group with 6 to 12 carbon atoms or an aralkyl group with 7 to 12 carbon atoms that may have substituents.

[0141] Regarding the aforementioned saturated hydrocarbon groups, straight-chain, branched, and cyclic saturated hydrocarbon groups are all acceptable. Specific examples include those derived from R... 101 ~R 105 The saturated hydrocarbon group represented is the same group as the one shown above. Examples of the above-mentioned halo-saturated hydrocarbon groups include trifluoromethyl, 1,1,1-trifluoroethyl, 1,1,1-trichloroethyl, and nonafluorobutyl.

[0142] Examples of aryl groups that may have substituents include phenyl; alkoxyphenyls such as 2-, 3-, or 4-methoxyphenyl, 2-, 3-, or 4-ethoxyphenyl, and 3-, or 4-tert-butoxyphenyl; alkylphenyls such as 2-, 3-, or 4-methylphenyl, 2-, 3-, or 4-ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, and dimethylphenyl; and halogenated aryl groups such as fluorophenyl, chlorophenyl, and 1,2,3,4,5-pentafluorophenyl. Examples of aralkyl groups include benzyl and phenethyl.

[0143] Specifically, examples of the aforementioned ononium salts include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyliodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium trifluoromethanesulfonate, and trifluoromethanesulfonate... Tris(p-tert-butoxyphenyl)sulfonium, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutyrate, triphenylsulfonate, trimethyltrifluoromethanesulfonate, trimethyltrimethyltrifluoromethanesulfonate, cyclohexylmethyltrifluoromethanesulfonate 2-Oxocyclohexyl)sulfonium, p-toluenesulfonate cyclohexylmethyl(2-oxocyclohexyl)sulfonium, dimethylphenyltrifluoromethanesulfonate, p-toluenesulfonate dimethylphenylsulfonium, dicyclohexylphenyltrifluoromethanesulfonate, p-toluenesulfonate dicyclohexylphenylsulfonium, bis(4-tert-butylphenyl)iodomonium hexafluorophosphate, 4-(phenylthio)phenyldiphenylsulfonium tri(pentafluoroethyl)trifluorophosphate, diphenyl(4- Thiophenoxyphenyl)sulfonium hexafluoroantimonate, [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium tri(trifluoromethanesulfonyl)methyl compound, triphenylsulfonium tetra(fluorophenyl)borate, tri[4-(4-acetylphenyl)phenylthio]sulfonium tetra(fluorophenyl)borate, triphenylsulfonium tetra(pentafluorophenyl)borate, tri[4-(4-acetylphenyl)phenylthio]sulfonium tetra(pentafluorophenyl)borate, etc.

[0144] Specifically, examples of the aforementioned diazonium methane 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, and bis(isopropylsulfonyl)diazomethane. Acyl)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.

[0145] As specific examples of the aforementioned dioxime derivatives, bis-o-(p-toluenesulfonyl)-α-dimethyldioxime, bis-o-(p-toluenesulfonyl)-α-diphenyldioxime, bis-o-(p-toluenesulfonyl)-α-dicyclohexyldioxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedione dioxime, and bis-(p-toluenesulfonyl)-2 -Methyl-3,4-pentanedione glycoxime, bis-o-(n-butanesulfonyl)-α-dimethylglycoxime, bis-o-(n-butanesulfonyl)-α-diphenylglycoxime, bis-o-(n-butanesulfonyl)-α-dicyclohexylglycoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedione glycoxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4- Glutendione oxime, 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-(perfluorooctyl)-α-dimethylglyoxime, bis-o-(cyclohexanesulfon ... Hexanesulfonyl)-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, etc.

[0146] Specific examples of the aforementioned β-ketosulfonyl derivatives include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane.

[0147] Specifically, diphenyl disulfone, dicyclohexyl disulfone, etc. can be listed as disulfone derivatives.

[0148] Specifically, examples of the aforementioned nitrobenzyl sulfonate derivatives include 2,6-dinitrobenzyl p-toluenesulfonic acid and 2,4-dinitrobenzyl p-toluenesulfonic acid.

[0149] Specific examples of the aforementioned sulfonate derivatives include 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene.

[0150] Specifically, examples of the aforementioned imide sulfonate derivatives include phthalimide trifluoromethanesulfonate, phthalimide toluenesulfonate, 5-norbornene-2,3-dicarboximide trifluoromethanesulfonate, 5-norbornene-2,3-dicarboximide toluenesulfonate, 5-norbornene-2,3-dicarboximide n-butylsulfonate, and n-trifluoromethanesulfonyloxynaphthalimide.

[0151] Examples of the aforementioned oxime sulfonate derivatives include α-(phenylsulfonoxyimino)-4-methylphenylacetonitrile and α-(p-tolylsulfonoxyimino)-p-methoxyphenylacetonitrile.

[0152] As examples of the aforementioned iminosulfonate derivatives, specific examples include (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile and (5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophen-2-ylidene)-(2-methylphenyl)-acetonitrile, etc.

[0153] Alternatively, 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane can also be preferred.

[0154] Regarding the content of component (C), from the viewpoint of photocurability, 0.05 to 20 parts by mass, more preferably 0.05 to 5 parts by mass, are preferred relative to 100 parts by mass of component (A). 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, the increase in absorbance of the photoacid-generating agent itself can be suppressed, and there is no need to worry about problems such as reduced transparency. Therefore, it is preferred. Component (C) can be used alone or in combination of two or more.

[0155] [(D) Crosslinking agent]

[0156] The photosensitive resin composition of the present invention preferably further comprises a crosslinking agent as component (D). The crosslinking agent is used to react with the phenolic hydroxyl groups in component (A) above, or is derived from R... 13 R 14 R 23 or R 24 The saturated hydrocarbon oxygen groups represent components that undergo condensation reactions, readily enabling pattern formation and further enhancing the strength of the cured product.

[0157] As the aforementioned crosslinking agent, preferred crosslinking agents include melamine compounds, guanidine compounds, glycourea compounds, or urea compounds that contain an average of two or more hydroxymethyl and / or alkoxymethyl groups per molecule; amino condensates modified with formaldehyde or formaldehyde-alcohol; phenolic compounds that have an average of two or more hydroxymethyl or alkoxymethyl groups per molecule; and epoxy compounds that have an average of two or more epoxy groups per molecule.

[0158] Examples of the melamine compounds mentioned above include those represented by the following formula (D1).

[0159] [Chemistry 21]

[0160]

[0161] In equation (D1), R 201 ~R 206 Each of the following components is independently hydroxymethyl, a saturated hydroxyloxymethyl group with 2 to 5 carbon atoms, or a hydrogen atom, with at least one being hydroxymethyl or a saturated hydroxyloxymethyl group. Examples of saturated hydroxyloxymethyl groups include methoxymethyl, ethoxymethyl, and other alkoxymethyl groups.

[0162] Examples of melamine compounds represented by formula (D1) include trimethoxymethyl monohydroxymethyl melamine, dimethoxymethyl monohydroxymethyl melamine, trihydroxymethyl melamine, hexahydroxymethyl melamine, hexamethoxymethyl melamine, and hexaethoxymethyl melamine.

[0163] The melamine compound represented by formula (D1) can be obtained, for example, by first modifying the melamine monomer with formaldehyde by hydroxymethylation according to a known method, or by further modifying it by alkoxylation with an alcohol. Furthermore, as the aforementioned alcohol, a lower alcohol, such as an alcohol having 1 to 4 carbon atoms, is preferred.

[0164] Examples of the aforementioned guanidine compounds include tetrahydroxymethylguanidine, tetramethoxymethylguanidine, and tetramethoxyethylguanidine.

[0165] Examples of the aforementioned glycourea compounds include tetrahydroxymethylglycourea and tetra(methoxymethyl)glycourea.

[0166] Examples of the aforementioned urea compounds include tetrahydroxymethylurea, tetramethoxymethylurea, tetramethoxyethylurea, tetraethoxymethylurea, and tetrapropoxymethylurea.

[0167] 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.

[0168] As the modified melamine condensate described above, examples include products obtained by adding and condensing a compound represented by formula (D1) or its polymers (e.g., dimers, trimers, or other oligomers) with formaldehyde until the desired molecular weight is achieved. Furthermore, conventionally known methods can be used as the addition condensation polymerization method described above. Additionally, the modified melamine represented by formula (D1) can be used alone or in combination of two or more compounds.

[0169] Examples of urea condensates modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensates, ethoxymethylated urea condensates, and propoxymethylated urea condensates.

[0170] The modified urea condensate can be obtained by, for example, by hydroxymethylating a urea condensate of the desired molecular weight with formaldehyde according to a known method, or by further alkoxylating it with an alcohol.

[0171] Examples of phenolic compounds that have an average of two or more hydroxymethyl or alkoxymethyl groups in one molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol and 2,2',6,6'-tetramethoxymethylbisphenol A.

[0172] Examples of epoxy compounds having an average of two or more epoxy groups per molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenolic varnish type epoxy resin, cresol phenolic varnish type epoxy resin, triphenol alkane type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene modified phenolic varnish 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, and heterocyclic epoxy resin.

[0173] When component (D) is included, its content is preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight, relative to 100 parts by weight of component (A). If it is 0.5 parts by weight or more, sufficient curability is obtained upon light irradiation; if it is 50 parts by weight or less, the proportion of component (A) in the photosensitive resin composition is not reduced, thus enabling the cured product to exhibit sufficient effect. Component (D) can be used alone or in combination of two or more.

[0174] [(E) solvent]

[0175] The photosensitive resin composition of the present invention may further include a solvent as component (E). As for the solvent, there is no particular limitation as long as it is a solvent that can dissolve components (A) to (D) and the various additives described later, but organic solvents are preferred based on the excellent solubility of these components.

[0176] Examples of organic solvents mentioned above include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monotert-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 for photoacid-producing agents. These organic solvents can be used individually or in combination of two or more.

[0177] Regarding the amount of component (E), from the viewpoint of compatibility and viscosity of the photosensitive resin composition, it is preferable to use 50 to 2,000 parts by weight, more preferably 50 to 1,000 parts by weight, and particularly preferably 50 to 100 parts by weight, relative to 100 parts by weight of component (A).

[0178] [Other Additives]

[0179] In addition to the components described above, the photosensitive resin composition of the present invention may contain other additives. Examples of such additives include surfactants commonly used to improve coatability.

[0180] As the aforementioned surfactant, nonionic surfactants are preferred, such as fluorinated surfactants, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkyl amine oxides, and fluorinated organosiloxane compounds. Commercially available products can be used, such as Fluorad FC-430 (manufactured by 3M Corporation), SURFLON S-141 and S-145 (manufactured by AGC SEMI CHEMICAL Co., Ltd.), Takatori Corp. DS-401, DS-4031, and DS-451 (manufactured by Daikin Industries, Ltd.), MEGAFAC F-8151 (manufactured by DIC Co., Ltd.), and X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.). Among these, Fluorad FC-430 and X-70-093 are preferred. Regarding the content of the aforementioned surfactant, 0.05 to 1 part by weight is preferred relative to 100 parts by weight of component (A).

[0181] The photosensitive resin composition of the present invention may include a silane coupling agent as another additive. By including a silane coupling agent, the adhesion between the coating obtained from the composition and the substrate can be further improved. Examples of silane coupling agents include silane coupling agents containing epoxy groups and aminosilane coupling agents containing aromatic groups. These can be used alone or in combination of two or more. There is no particular limitation on the content of the above-mentioned silane coupling agent, but when included, it is preferably 0.01 to 5% by mass in the photosensitive resin composition of the present invention.

[0182] The photosensitive resin composition of the present invention can be prepared using conventional methods. 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 components using a filter or the like as needed.

[0183] The photosensitive resin composition of the present invention prepared in this way is suitable for use as, for example, a protective film for semiconductor elements, a protective film for wiring, a cover film, a solder mask, a material for insulating films for through electrodes (for TSVs), and an adhesive between stacked substrates in a three-dimensional stack.

[0184] [A method for forming patterns using a photosensitive resin composition]

[0185] The pattern forming method using the photosensitive resin composition of the present invention includes:

[0186] (i) A process of forming a photosensitive resin coating on a substrate using the photosensitive resin composition of the present invention;

[0187] (ii) The process of exposing the above-mentioned photosensitive resin coating; and

[0188] (iii) The process of developing the exposed photosensitive resin coating with a developing solution to form a pattern.

[0189] Step (i) is the process of forming a photosensitive resin coating on a substrate using the aforementioned photosensitive resin composition. Examples of substrates include silicon wafers, silicon wafers with through electrodes, silicon wafers thinned by back-side grinding, plastic or ceramic substrates, and substrates with metals such as Ni or Au on the entire surface or a portion of the substrate using ion sputtering, plating, or other methods. Additionally, substrates with uneven surfaces are sometimes used.

[0190] Methods for forming the photosensitive resin coating include, for example, coating the aforementioned photosensitive resin composition onto a substrate and preheating (pre-baking) it as needed. Known coating methods include dip coating, spin coating, and roll coating. The coating amount of the aforementioned photosensitive resin composition can be appropriately selected according to the purpose, and preferably, the resulting photosensitive resin coating should have a film thickness of 0.1 to 200 μm, more preferably 1 to 150 μm.

[0191] To improve the uniformity of film thickness on the substrate surface, a solvent can be dropped onto the substrate before coating the photosensitive resin composition (pre-wetting method). The solvent dropped and its amount can be appropriately selected according to the purpose. As such solvents, alcohols such as isopropanol (IPA), ketones such as cyclohexanone, and diols such as PGME are preferred, and the solvents used in the photosensitive resin composition can also be used.

[0192] In order to efficiently carry out the photocuring reaction, pre-baking can be performed as needed to evaporate the solvents and other components. Pre-baking can be carried out at 40-140°C for approximately 1 minute to 1 hour.

[0193] Next, (ii) the photosensitive resin coating is exposed. Exposure is preferably performed using light with a wavelength of 10–600 nm, more preferably using light with a wavelength of 190–500 nm. Examples of such wavelengths include light of various wavelengths generated by a radiation generating device, such as gamma rays, h-rays, i-rays, ultraviolet light, and far-ultraviolet light (248 nm, 193 nm). Among these, light with a wavelength of 248–436 nm is particularly preferred. The exposure dose is preferably 10–10,000 mJ / cm². 2 .

[0194] Exposure can be performed via a photomask. The photomask can, for example, have the desired pattern running through it. Furthermore, there are no particular limitations on the material of the photomask, but a material that blocks the aforementioned wavelengths of light is preferred. For example, as a light-shielding film, a light-shielding film containing chromium or the like is preferred.

[0195] Furthermore, to improve development sensitivity, post-exposure heat treatment (PEEB) can be performed. PEB is preferably performed at 40–150°C for 0.5–10 minutes. Through PEB, the exposed portions crosslink, forming insoluble patterns that are insoluble in the organic solvent used as the developer.

[0196] After exposure or PEB, (iii) the photosensitive resin coating is developed using a developing solution to form a pattern. As the developing solution, organic solvents such as alcohols like IPA, ketones like cyclohexanone, and diols like PGME are preferred; solvents used in the photosensitive resin composition can also be used. Common methods can be listed as development methods, such as immersing the patterned substrate in the aforementioned developing solution. By developing with an organic solvent, the unexposed areas dissolve and are removed, thereby forming a pattern. Then, as needed, washing, rinsing, and drying are performed to obtain a resin coating with the desired pattern.

[0197] Furthermore, (iv) for the patterned coating, an oven or hot plate can be used for post-curing, preferably at 100–250°C, more preferably at 130–220°C. A post-curing temperature of 100–250°C increases the crosslinking density of the photosensitive resin composition and removes residual volatile components, which is preferable from the viewpoint of adhesion to the substrate, heat resistance, strength, electrical properties, and adhesive strength. The post-curing time is preferably 10 minutes to 10 hours, more preferably 10 minutes to 3 hours. Using the photosensitive resin composition of the present invention, even post-curing at lower temperatures below 200°C can yield coatings with various excellent film properties. The thickness of the post-cured coating (cured coating) is typically 1–200 μm, preferably 5–50 μm.

[0198] In cases where it is not necessary to form a pattern, such as when it is desirable to form only a uniform coating, in step (ii) of the pattern forming method described above, the coating can be formed by exposing light of an appropriate wavelength without passing through the photomask described above.

[0199] [Substrate bonding method]

[0200] The photosensitive resin composition of the present invention can also be used as an adhesive for bonding two substrates. Examples of substrate bonding methods include bonding a coated substrate to a second substrate using the photosensitive resin composition of the present invention under appropriate heat and pressure conditions to form an adhesive bond between the two substrates. Either or both of the coated substrate and the second substrate are sometimes formed into slices using slicing or similar processes. As bonding conditions, a heating temperature of 50–200°C is preferred, and the process is carried out for 1–60 minutes. As bonding apparatus, a wafer bonding apparatus can be used to bond wafers under reduced pressure while applying load, or chip-to-wafer or chip-to-chip bonding using a flip-chip bonding apparatus can be performed. The adhesive layer formed between the substrates undergoes a post-curing treatment described later, resulting in improved bonding strength and a permanent bond.

[0201] By subjecting the bonded substrate to post-curing treatment under the same conditions as in step (iv) described above, the cross-linking density of the coating is increased, thereby improving the substrate adhesion. Furthermore, the heating during bonding causes a cross-linking reaction, and no side reaction accompanied by degassing occurs during this cross-linking reaction. Therefore, especially when used as a substrate adhesive, it does not induce bonding defects (voids).

[0202] [Photosensitive dry film]

[0203] The photosensitive dry film of the present invention comprises: a support film, and a photosensitive resin coating obtained on the support film from the above-described photosensitive resin composition.

[0204] The aforementioned photosensitive dry film (support film and photosensitive resin coating) is a solid. Since the photosensitive resin coating does not contain solvent, there is no need to worry about bubbles generated by its evaporation remaining inside the photosensitive resin coating and between it and the substrate with uneven surfaces.

[0205] Regarding the film thickness of the aforementioned photosensitive resin coating, from the viewpoints of flatness on a substrate with unevenness, coverage of step height differences, and substrate stacking spacing, 5 to 200 μm is preferred, and 10 to 100 μm is more preferred.

[0206] Furthermore, the viscosity of the aforementioned photosensitive resin coating is closely related to its flowability. Within an appropriate viscosity range, the photosensitive resin coating can exhibit suitable flowability, allowing it to penetrate narrow gaps or enhance adhesion to the substrate through resin softening. Therefore, from the viewpoint of its flowability, the viscosity of the aforementioned photosensitive resin coating at 80–120°C is preferably 10–5,000 Pa·s, more preferably 30–2,000 Pa·s, and even more preferably 50–300 Pa·s. In this invention, the viscosity is a value measured using a rotational viscometer.

[0207] When the photosensitive dry film of the present invention is bonded to a substrate with uneven surfaces, the photosensitive resin coating follows the unevenness and is covered, achieving high flatness. In particular, the photosensitive resin coating has low viscoelasticity, thus enabling even higher flatness. Furthermore, if the photosensitive resin coating is bonded to the substrate under vacuum, the formation of gaps between them can be prevented more effectively.

[0208] The photosensitive dry film of the present invention can be manufactured by coating and drying the above-mentioned photosensitive resin composition onto a support film to form a photosensitive resin coating. As the manufacturing apparatus for the above-mentioned photosensitive dry film, a film coater generally used for manufacturing pressure-sensitive adhesive products can be used. Examples of such film coaters include, for instance, a corner roller coater, a corner roller reverse coater, a multi-roller coater, a molding coater, a lip coater, a lip reverse coater, a direct gravure photogravure coater, an offset gravure coater, a three-bottom reverse roller coater, and a four-bottom reverse roller coater.

[0209] The support film is wound from the roll-out shaft of the film coater. As it passes through the coater head of the film coater, the photosensitive resin composition is applied to the support film at a predetermined thickness. Then, it is dried on the support film in a hot air circulating oven at a predetermined temperature and time to form a photosensitive resin coating, thereby enabling the manufacture of a photosensitive dry film. Alternatively, if necessary, the photosensitive dry film, together with a protective film wound from another roll-out shaft of the film coater, is passed through a laminating roller at a predetermined pressure to bond the photosensitive resin coating on the support film to the protective film. Afterward, it is wound onto the winding shaft of the film coater, thereby enabling the manufacture of a photosensitive dry film with a protective film. In this case, the preferred temperature is 25–150°C, the preferred time is 1–100 minutes, and the preferred pressure is 0.01–5 MPa.

[0210] The aforementioned support membrane can be a single-layer membrane composed of a single membrane or a multilayer membrane composed of multiple membranes stacked together. Examples of materials for these membranes include synthetic resin membranes such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Among these, polyethylene terephthalate is preferred due to its moderate flexibility, mechanical strength, and heat resistance. These membranes can be membranes that have undergone various treatments such as corona treatment and release agent coating. Commercially available products can be used, such as Cerapeel WZ(RX), Cerapeel BX8(R) (manufactured by Toray Film Processing Co., Ltd.), E7302, E7304 (manufactured by Toyobo Co., Ltd.), Purex G31, Purex G71T1 (manufactured by Teijin DuPont Film Co., Ltd.), PET38X1-A3, PET38X1-V8, and PET38X1-X08 (manufactured by Nippa Co., Ltd.).

[0211] As the aforementioned protective film, the same film as the aforementioned support film can be used. From the perspective of having appropriate flexibility, polyethylene terephthalate and polyethylene are preferred. These can be commercially available products. Examples of polyethylene terephthalate products already exemplified can be cited, and examples of polyethylene include GF-8 (manufactured by Tamapoly Co., Ltd.) and PE film type O (manufactured by Nippa Co., Ltd.).

[0212] Regarding the thickness of the aforementioned support film and protective film, from the viewpoint of ensuring the stability of the photosensitive dry film manufacturing and preventing easy winding of the core, i.e., curling, it is preferred to be 10 to 100 μm, and more preferably 25 to 50 μm.

[0213] [Pattern Formation Method Using Photosensitive Dry Film]

[0214] The patterning method using the photosensitive dry film of the present invention includes:

[0215] (i') A process of forming a photosensitive resin coating on a substrate using the photosensitive dry film of the present invention;

[0216] (ii) the process of exposing the above-mentioned photosensitive resin coating; and

[0217] (iii) The process of developing the exposed photosensitive resin coating with a developing solution to form a pattern.

[0218] First, in step (i'), a photosensitive resin coating is formed on a substrate using a photosensitive dry film. Specifically, a photosensitive resin coating is formed on the substrate by adhering the photosensitive resin coating of the photosensitive dry film to the substrate. Furthermore, if the photosensitive dry film has a protective film, the photosensitive resin coating of the photosensitive dry film is adhered to the substrate after peeling off the protective film. Adhesion can be performed, for example, using a film adhesion apparatus.

[0219] As the aforementioned substrate, the same substrate described in the pattern forming method using a photosensitive resin composition can be cited. As the aforementioned film bonding apparatus, a vacuum laminator is preferred. For example, the protective film of the aforementioned photosensitive dry film is peeled off, the exposed photosensitive resin film is placed in a vacuum chamber with a specified vacuum level, and a bonding roller with a specified pressure is used to bond it tightly to the aforementioned substrate on a table at a specified temperature. Furthermore, the aforementioned temperature is preferably 60–120°C, the aforementioned pressure is preferably 0–5.0 MPa, and the aforementioned vacuum level is preferably 50–500 Pa.

[0220] To obtain the necessary thickness of the photosensitive resin coating, the film can be applied multiple times as needed. For example, 1 to 10 applications can yield a photosensitive resin coating with a thickness of 10 to 1,000 μm, particularly 100 to 500 μm.

[0221] To efficiently perform the photocuring reaction of the photosensitive resin coating and to improve the adhesion between the photosensitive resin coating and the substrate, pre-baking can be performed as needed. Pre-baking can be carried out, for example, at 40–140°C for about 1 minute to 1 hour.

[0222] Similarly, in the pattern-forming method using the aforementioned photosensitive resin composition, the photosensitive resin coating adhered to the substrate is patterned by performing (ii) the step of exposing the photosensitive resin coating, (iii) the step of developing the exposed photosensitive resin coating with a developer to form a pattern, and (iv) the step of performing a post-curing treatment as needed. Furthermore, the support film of the photosensitive dry film is peeled off before pre-baking or before PEB, or removed by other methods, depending on the process.

[0223] The coating obtained from the above-mentioned photosensitive resin composition and photosensitive dry film has excellent heat resistance, flexibility, electrical insulation, mechanical properties and adhesion to substrates, etc., and is suitable for use as a protective coating for electrical and electronic components such as semiconductor elements and a coating for substrate bonding.

[0224] Example

[0225] The following examples, embodiments, and comparative examples illustrate the invention in more detail, but the invention is not limited to the examples described below. Furthermore, Mw used a TSKgel Super HZM-H column (manufactured by Tosoh Corporation) as the column and performed GPC analysis using monodisperse polystyrene as the standard under analytical conditions of a flow rate of 0.6 mL / min, elution solvent THF, and column temperature of 40°C.

[0226] The following are examples of compounds (S-1) to (S-6) used in the synthesis.

[0227] [Chemistry 22]

[0228]

[0229] [1] Synthesis of organosilicon resins

[0230] [Synthesis example 1]

[0231] In a 3L flask equipped with a stirrer, thermometer, nitrogen purging apparatus, and reflux condenser, 215.0 g (0.5 mol) of compound (S-6) was added, followed by 2,000 g of toluene, and the mixture was heated to 70°C. Then, 1.0 g of toluene chloroplatinic acid solution (0.5% by mass platinum) was added dropwise over 1 hour, followed by 67.9 g (0.35 mol) of compound (S-4) and compound (S-5) (y 1 =40. 453.0 g (0.15 mol) of Shin-Etsu Chemical Co., Ltd. (total silane group / total alkenyl group = 1 / 1 (molar ratio)). After the addition was complete, the mixture was heated to 100°C and aged for 6 hours. Toluene was then removed from the reaction solution by vacuum distillation to obtain organosilicon resin A-1. Organosilicon resin A-1 was used... 1 ¹H-NMR (Bruker assay) confirmed the presence of repeating units a1, a2, b1, and b2. The Mw of silicone resin A-1 was 62,000, and the silicone content was 61.6% by mass.

[0232] [Synthesis example 2]

[0233] In a 3L flask equipped with a stirrer, thermometer, nitrogen purging apparatus, 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, followed by 2,000 g of toluene. The mixture was heated to 70°C. Then, 1.0 g of toluene chloroplatinic acid solution (0.5% by mass platinum) was added dropwise over 1 hour, followed by 48.5 g (0.25 mol) of compound (S-4) and compound (S-5) (y 1 =40. 755.0 g (0.25 mol) of Shin-Etsu Chemical Co., Ltd. (total silane group / total alkenyl group = 1 / 1 (molar ratio)). After the dripping was completed, the mixture was heated to 100°C and aged for 6 hours. Toluene was then removed from the reaction solution by vacuum distillation to obtain organosilicon resin A-2. Organosilicon resin A-2 was used... 1 ¹H-NMR (Bruker assay) confirmed the presence of repeating units a1, a3, a4, b1, b3, and b4. The Mw of silicone resin A-2 was 83,000, and the silicone content was 77.5% by mass.

[0234] [Synthesis example 3]

[0235] In a 3L flask equipped with a stirrer, thermometer, nitrogen purging apparatus, and reflux condenser, 27.9 g (0.15 mol) of compound (S-3), 19.6 g (0.05 mol) of compound (S-1), and 129.0 g (0.30 mol) of compound (S-6) were added, followed by 2,000 g of toluene. The mixture was heated to 70°C. Then, 1.0 g of toluene chloroplatinic acid solution (0.5% by mass platinum) was added, and over a period of 1 hour, 87.3 g (0.45 mol) of compound (S-4) and compound (S-5) were added dropwise. 1 =20, Shin-Etsu Chemical Industry Co., Ltd.) 79.3 g (0.05 mol) (total of hydrosilyl groups / total of alkenyl groups = 1 / 1 (molar ratio)). After the dropwise addition was completed, the mixture was heated to 100°C and aged for 6 hours. Toluene was then removed from the reaction solution by vacuum distillation to obtain organosilicon resin A-3. Organosilicon resin A-3 was confirmed to contain repeating units a1, a2, a4, b1, b2, and b4 by 1H-NMR (Bruker preparation). The Mw of organosilicon resin A-3 was 24,000, and the organosilicon content was 31.2% by mass.

[0236] [2] Preparation of photosensitive resin composition

[0237] [Examples 1-8 and Comparative Examples 1-20]

[0238] The components were mixed according to the mixing amounts recorded in Tables 1-3, and then stirred and dissolved at room temperature. The mixtures were then precisely filtered using a 1.0 μm filter made of Teflon (registered trademark) to prepare the photosensitive resin compositions of Examples 1-8 and Comparative Examples 1-20.

[0239] [Table 1]

[0240]

[0241] [Table 2]

[0242]

[0243] [Table 3]

[0244]

[0245] In Tables 1 to 3, the epoxy compounds B-1 to B-12 are described below.

[0246] [Chemistry 23]

[0247]

[0248] [Chemistry 24]

[0249]

[0250] [Chemistry 25]

[0251]

[0252] The photoacid-producing agent PAG-1 in Tables 1-3 is described below.

[0253] [Chemistry 26]

[0254]

[0255] In Tables 1-3, the crosslinking agent CL-1 is described below.

[0256] [Chemistry 27]

[0257]

[0258] In Tables 2 and 3, resin A'-1 is described as follows.

[0259] [Chemistry 28]

[0260]

[0261] [3] Preparation of photosensitive dry film

[0262] A molding 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 1-3 were coated onto the support film. Next, the film was dried in a hot air circulating oven (4 m long) set to 100°C for 5 minutes to form a photosensitive resin coating, resulting in a photosensitive dry film. A polyethylene film (50 μm thick) as a protective film was then laminated onto the photosensitive resin coating using a laminating roller at a pressure of 1 MPa to produce a photosensitive dry film with a protective film. The thickness of each photosensitive resin coating was 150 μm. It should be noted that the film thickness of the photosensitive resin coating was measured using an optical interferometric film thickness gauge (F50-EXR manufactured by Fi lmetrics Co.).

[0263] [4] Evaluation of resin coating

[0264] (1) Pattern formation and its evaluation

[0265] For the aforementioned photosensitive dry film with a protective film, the protective film was peeled off, and a vacuum chamber was set to 80 Pa using a TEAM-100RF vacuum laminator (manufactured by Takatori Corp.). This allowed the photosensitive resin coating on the support film to adhere tightly to the migration test substrate (a comb-shaped electrode substrate with copper conductive material, 20 μm spacing and width of conductive parts, and 4 μm thickness of conductive parts). The temperature was set to 100°C. After returning to normal pressure, the substrate was removed from the vacuum laminator, and the support film was peeled off. Next, to improve adhesion to the substrate, a hot plate was used for preheating at 120°C for 5 minutes. To form line-gap patterns and contact hole patterns on the resulting photosensitive resin coating, exposure was performed using a contact alignment type exposure apparatus at a wavelength of 365 nm via a mask. After exposure, the film was subjected to PEB treatment at 140°C for 5 minutes using a hot plate, then cooled, and spray-developed with PGMEA for 300 seconds to form the pattern.

[0266] The photosensitive resin coating formed on the patterned substrate using the above method was cured in an oven at 150°C for 4 hours after nitrogen purging. Then, the cross-sections of the formed 300μm, 150μm, and 100μm contact hole patterns were observed using a scanning electron microscope (SEM). The smallest hole pattern with holes penetrating to the bottom of the film was set as the limiting resolution. The perpendicularity of the 300μm contact hole pattern was evaluated from the obtained cross-sectional images. A perpendicular pattern was marked with ◎, an inverted conical shape with slight seepage was marked with ○, an inverted conical shape with significant seepage was marked with △, and a poorly formed opening was marked with ×. The results are shown in Tables 4-6.

[0267] (2) Evaluation of electrical properties (copper migration)

[0268] A patterned substrate formed using method (1) was used as a substrate for copper migration evaluation, and tests were conducted. The copper migration test conditions were 130°C, 85% humidity, and 10V applied voltage, with an upper limit of 1,000 hours, to determine the time at which a short circuit occurred. The results are shown in Tables 4-6.

[0269] (3) Evaluation of electrical properties (insulation breaking strength)

[0270] To evaluate the dielectric breaking strength of photosensitive resin films composed of photosensitive resin compositions, the photosensitive resin compositions listed in Tables 1-3 were coated onto a 13cm × 15cm, 0.7mm thick iron plate using a rod coater and preheated at 120°C for 5 minutes using a hot plate. Then, without a mask, the film was exposed at a wavelength of 405nm using a contact alignment type exposure apparatus, followed by heating at 150°C for 4 hours in an oven to obtain the photosensitive resin film. The coating thickness of the photosensitive resin composition was 0.2μm. Using this photosensitive resin film, an insulation breakdown tester TM-5031AM (manufactured by Tama Electric Testing Co., Ltd.) was used. A voltage was applied starting at a voltage ramp rate of 5V / second, and the voltage at which the test specimen broke was measured as the dielectric breaking strength of the film. The results are shown in Tables 4-6.

[0271] (4) Evaluation of reliability (sealing, crack resistance)

[0272] For the aforementioned photosensitive dry film with a protective film, the protective film was peeled off, and a vacuum laminator TEAM-100RF (manufactured by Takatori Co., Ltd.) was used. The vacuum level in the vacuum chamber was set to 80 Pa, allowing the photosensitive resin coating on the support film to adhere tightly to the CCL substrate on which 10mm × 10mm square silicon chips were stacked. The temperature was set to 100°C. After returning to normal pressure, the substrate was removed from the vacuum laminator, and the support film was peeled off. Next, to improve the adhesion to the substrate, a hot plate was used for preheating at 120°C for 5 minutes. The resulting photosensitive resin coating was exposed without a mask using a contact aligner type exposure device at a wavelength of 365nm. After exposure, it was subjected to PEB treatment at 140°C for 5 minutes using a hot plate, then cooled, and cured in an oven at 150°C with nitrogen purging for 4 hours. Then, for the substrate, a cutting saw with a cutting blade (DAD685, DISCO, spindle speed 40,000 rpm, cutting speed 20 mm / s) was used to obtain 20 mm × 20 mm square test pieces with an outer perimeter of 5 mm for the silicon chip. Ten of these test pieces were subjected to thermal cycling tests (1,000 cycles of holding at -30°C for 10 minutes and at 130°C for 10 minutes each) to confirm the peeling state of the resin film from the wafer and the presence or absence of cracks after the thermal cycling test. Cases with no peeling or cracks were marked as ○, cases with more than one peeling were marked as ×, and cases with more than one crack were marked as ×. Furthermore, 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 4–6.

[0273] (5) Evaluation of inter-substrate bonding performance

[0274] To evaluate the adhesion performance between substrates, the protective film on the aforementioned photosensitive dry film was peeled off. A vacuum laminator, TEAM-100RF (manufactured by Takatori Co., Ltd.), was used, with the vacuum level in the vacuum chamber set to 80 Pa to ensure adhesion between the photosensitive resin coating on the support film and the 8-inch silicon wafer. The temperature was set to 100°C. After returning to normal pressure, the substrate was removed from the vacuum laminator, and the support film was peeled off. Next, to improve adhesion to the substrate, preheating was performed at 120°C for 5 minutes using a hot plate. For the resulting photosensitive resin coating, to form a 300 μm line-gap pattern, exposure was performed using a contact aligner-type exposure apparatus at a wavelength of 405 nm via a mask. After exposure, PEB was applied 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 pattern. The substrates were then bonded to untreated 8-inch quartz glass or Tempax glass, and a temporary bonding heating was performed at 160°C for 5 minutes using a hot plate. Post-curing was then carried out in an oven at 150°C for 4 hours to form an inter-substrate adhesive layer. The bonded wafers were exposed to 130°C and 85% humidity for 1,000 hours to confirm the absence of induced bonding defects. The results are shown in Tables 4–6.

[0275] (6) Evaluation of solvent resistance

[0276] To evaluate the solvent resistance of N-methyl-2-pyrrolidone (NMP), which is commonly used in the formation of semiconductor devices, a 15 mm × 15 mm pattern was formed on a silicon wafer using the same method as that used in the copper migration test in (1) for the photosensitive resin compositions of Examples 1-8 and Comparative Examples 1-20. After immersing the wafer in NMP at 40°C for 1 hour, the change in film thickness and appearance were examined to evaluate the solvent resistance. Cases with no change in appearance or film thickness were marked as ○, and cases with swelling were marked as ×. The results are shown in Tables 4-6.

[0277] (7) Evaluation of relative permittivity and dielectric loss tangent

[0278] For the aforementioned photosensitive dry film with a protective film, the protective film was peeled off, and the film was exposed without a mask using a contact alignment type exposure apparatus at a wavelength of 405 nm. Then, it was cured in an oven at 150°C for 4 hours with nitrogen purging. After removal from the oven, the support film was peeled off, and the relative permittivity (10 GHz, 25°C) and dielectric loss tangent (10 GHz, 25°C) were measured. Furthermore, the relative permittivity and dielectric loss tangent were measured using a cavity resonator method with an apparatus manufactured by AET Corporation. The results are shown in Tables 4–6.

[0279] [Table 4]

[0280]

[0281] [Table 5]

[0282]

[0283] [Table 6]

[0284]

[0285] As can be seen from the above results, the photosensitive resin composition and photosensitive dry film of the present invention can be easily patterned into fine designs even in thick films, exhibiting sufficient properties as photosensitive materials. Furthermore, the photosensitive resin coatings obtained from them exhibit high chemical resistance to photoresist stripping solutions and the like during low-temperature curing at 150°C. In addition, they possess excellent adhesion, electrical insulation, and resistance to copper migration, making them highly reliable as insulating protective films. They are suitable for forming coatings for various electrical and electronic components such as circuit boards, semiconductor devices, and display elements. According to the present invention, photosensitive resin compositions and photosensitive dry films with higher reliability can be provided.

Claims

1. A photosensitive resin composition comprising: (A) an organosilicon resin containing acid crosslinking groups, (B) an alicyclic epoxy compound represented by formula (B1) or (B2), and (C) a photoacid-generating agent. [Chemistry 1] In the formula, R 11 ~R 46 Each is independently a hydrogen atom or a saturated hydrocarbon group with 1 to 8 carbon atoms.

2. The photosensitive resin composition according to claim 1, wherein, (A) Organosilicon resin is represented by the following formula (A). [Chemistry 2] In the formula, R 1 ~R 4 Each is an independent hydrocarbon group with 1 to 8 carbon atoms, k is an integer from 1 to 600, a and b represent the composition ratio (molar ratio) of each repeating unit, and are numbers that satisfy 0 < a < 1, 0 < b < 1 and a + b = 1; X is a divalent organic group containing an epoxy group and / or a phenolic hydroxyl group.

3. The photosensitive resin composition according to claim 2, wherein, (A) The silicone resin contains repeating units represented by the following formulas (a1) to (a4) and (b1) to (b4). [Chemistry 3] In the formula, R 1 ~R 4 Each is an independent hydrocarbon group with 1 to 8 carbon atoms, k is an integer from 1 to 600, and a 1 ~a 4 and b 1 ~b 4 The molar ratio of each repeating unit is expressed as 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 A number equal to 1, X 1 X is a divalent group represented by the following formula (X1), where X 2 X is a divalent group represented by the following formula (X2), 3 X is a divalent group represented by the following formula (X3), 4 For a divalent group represented by the following formula (X4), [Chemistry 4] In the formula, Y 1 For single bonds, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl, R 11 and R 12 Each is independently a hydrogen atom or a methyl group, R 13 and R 14 Each is independently a saturated hydrocarbon group or a saturated hydroxyl group having 1 to 4 carbon atoms, p 1 and p 2 Each is an independent integer from 0 to 7, q 1 and q 2 Each is an independent integer from 0 to 2, and the dashed lines represent the bonding ends. [Chemistry 5] In the formula, Y 2 For single bonds, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl, R 21 and R 22 Each is independently a hydrogen atom or a methyl group, R 23 and R 24 Each is independently a saturated hydrocarbon group or a saturated hydroxyl group having 1 to 4 carbon atoms, r 1 and r 2 Each is an independent integer from 0 to 7, s 1 and s 2 Each is an independent integer from 0 to 2, and the dashed lines represent the bonding ends. [Chemistry 6] In the formula, R 31 and R 32 Each is independently a hydrogen atom or a methyl group, t 1 and t 2 Each is an independent integer from 0 to 7, and the dashed line represents the bonding end. [Chemistry 7] In the formula, R 41 and R 42 Each is independently a hydrogen atom or a methyl group, R 43 and R 44 Each is independently a hydrocarbon group with 1 to 8 carbon atoms, u 1 and u 2 Each is an integer from 0 to 7, v is an integer from 0 to 600, and the dashed line is the bond end.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein, The content of epoxy compounds in component (B) is 3 to 100 parts by mass relative to 100 parts by mass of component (A).

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

6. The photosensitive resin composition according to claim 5, wherein, (D) The crosslinking agent is at least one selected from nitrogen-containing compounds selected from melamine compounds, guanidine compounds, glycourea compounds and urea compounds, amino condensates modified with formaldehyde or formaldehyde-alcohol, phenolic compounds having an average of more than 2 hydroxymethyl and / or alkoxymethyl groups in one molecule, and epoxy compounds having an average of more than 2 epoxy groups in one molecule.

7. The photosensitive resin composition according to any one of claims 1 to 6, further comprising (E) a solvent.

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

9. Photosensitive dry films, comprising: The support film, and the photosensitive resin coating according to claim 8 on the support film.

10. A method for forming a pattern, comprising: (i) The process of forming a photosensitive resin coating on a substrate using the photosensitive resin composition according to any one of claims 1 to 7; (ii) the process of exposing the photosensitive resin coating; and (iii) The process of developing the exposed photosensitive resin coating with a developing solution to form a pattern.

11. A method for forming a pattern, comprising: (i') A process of forming a photosensitive resin coating on a substrate using the photosensitive dry film according to claim 9; (ii) the process of exposing the photosensitive resin coating; and (iii) The process of developing the exposed photosensitive resin coating with a developing solution to form a pattern.

12. The pattern forming method according to claim 10 or 11, further comprising: (iv) a step of post-curing the patterned photosensitive resin coating formed by development at a temperature of 100 to 250°C.

13. The photosensitive resin composition according to any one of claims 1 to 7, wherein it is a material for a protective coating for electrical and electronic components.

14. The photosensitive resin composition according to any one of claims 1 to 7, wherein it is a substrate bonding coating material for bonding two substrates.

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