Photosensitive resin composition and pattern forming method

Abstract

The present invention provides a photosensitive resin composition and a method for forming a pattern thereon, which can form a fine pattern by exhibiting sufficient solubility in an alkaline aqueous solution and can provide a film with high adhesion. [Solution] (A) A silicone resin having a silphenylene skeleton, a polysiloxane skeleton and a fluorene skeleton in its main chain, and containing a urethane bond, a carboxyl group and an acryloyl group or a methacryloyl group in its side chain, and (B) a photosensitive resin composition containing a photoradical generator.

Description

[Technical Field]

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

[0002] Conventionally, 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 applicable to the protection of such substrates and circuits, a photosensitive silicone composition mainly composed of a silphenylene skeleton-containing silicone polymer, which has particularly excellent flexibility, has been proposed (Patent Document 1).

[0003] The cured film obtained from the above composition possesses high chemical resistance, copper migration resistance, and reliability. On the other hand, since crosslinking does not proceed without a post-exposure heating (PEB) process when forming patterns, the PEB process is essential, which means that the catalytic acid is thermally diffused to the unexposed areas, making it difficult to miniaturize patterns. Furthermore, while the introduction of a polysiloxane structure into the resin is effective in improving flexibility and film properties, it has the problem of reduced adhesion to the substrate. In addition, due to its low solubility in aqueous solvents, the developer in its lithography process was limited to organic solvents. Because the use of organic solvents has adverse effects on the human body due to inhalation, the risk of ignition, and a large burden on the environment, lithography processes using alkaline aqueous solutions as developers have become more preferred in recent years. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2023-001980 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] The present invention has been made in view of the above circumstances, and aims to provide a photosensitive resin composition and a method for forming a pattern thereof that can form a fine pattern by exhibiting sufficient solubility in an alkaline aqueous solution and that can provide a film with high adhesion. [Means for solving the problem]

[0006] As a result of repeated studies to achieve the above objective, the present inventors have found that the above objective can be achieved by a photosensitive resin composition containing a silicone resin having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in the main chain and a urethane bond in the side chain, as well as a photoradical generator, and have completed the present invention.

[0007] In other words, the present invention provides the following photosensitive resin composition and pattern forming method. 1. (A) A silicone resin having a sylphenylene skeleton, a polysiloxane skeleton and a fluorene skeleton in the main chain, and containing a urethane bond, a carboxyl group and an acryloyl group or a methacryloyl group in the side chain, and (B) Photoradical Generator A photosensitive resin composition containing [a specific substance]. 2. (A) A photosensitive resin composition in which the silicone resin is a polymer comprising repeating units represented by the following formula (A1) and repeating units represented by the following formula (A2), and may further comprise at least one selected from repeating units represented by the following formula (A3) and repeating units represented by the following formula (A4). [ka] [In the formula, R 1 ~R 4 Each of these is an independent hydrocarbyl group having 1 to 20 carbon atoms, which may contain heteroatoms. Each of these is an independent integer between 1 and 600. When m is an integer of 2 or more, each R 3 They may be the same or different from each other, and each R 4They may be the same as or different from each other. a, b, c, and d are numbers satisfying 0 < a < 1, 0 < b < 1, 0 ≤ c < 1, 0 ≤ d < 1, and a + b + c + d = 1. X 1 X is a divalent group represented by the following formula (X1). X 2 X is a divalent group represented by the following formula (X2).

Chemical formula

Chemical formula

[0008] The photosensitive resin composition of the present invention can form a fine pattern that could not be achieved with a conventional silicone resin containing an epoxy group or a phenol group in the side chain and a photosensitive resin composition containing a photoacid generator, and can exhibit sufficient solubility in an alkaline aqueous solution.

Embodiments for Carrying Out the Invention

[0009] [Photosensitive Resin Composition] The photosensitive resin composition of the present invention contains (A) a silicone resin having a silylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in the main chain and a urethane bond in the side chain, and (B) a photo radical generator.

[0010] [(A) Silicone Resin] The silicone resin of component (A) is a polymer having a silylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in the main chain and containing a urethane bond, a carboxy group, and an acryloyl group or a methacryloyl group in the side chain. Such a silicone resin is not particularly limited, but preferably contains a repeating unit represented by the following formula (A1) and a repeating unit represented by the following formula (A2), and may further contain at least one selected from a repeating unit represented by the following formula (A3) and a repeating unit represented by the following formula (A4).

Chemical Formula

[0011] In formulas (A1) to (A4), a, b, c, and d are numbers satisfying 0 < a < 1, 0 < b < 1, 0 ≤ c < 1, 0 ≤ d < 1, and a + b + c + d = 1, but preferably numbers satisfying 0.1 < a < 0.8, 0.1 < b < 0.8, 0 ≤ c < 0.15, 0 ≤ d < 0.15, and a + b + c + d = 1.

[0012] In formulas (A2) and (A4), R 1 ~R 4Each is independently a hydrocarbyl group having 1 to 20 carbon atoms, which may contain heteroatoms. Each is independently an integer from 1 to 600, preferably an integer from 8 to 100. When m is an integer of 2 or more, each R 3 They may be the same or different from each other, and each R 4 They may be the same or different from one another.

[0013] In formulas (A2) and (A4), if there are two or more siloxane units (i.e., when m is an integer of 2 or more), each siloxane unit may be identical, or it may contain two or more different types of siloxane units. If it contains two or more different types of siloxane units, the siloxane units may be randomly bonded, alternately bonded, or contain multiple blocks of the same type of siloxane unit.

[0014] In equations (A1) and (A2), X 1 This is a divalent group represented by the following formula (X1). The divalent group represented by the following formula (X1) is a group having a fluorene skeleton. [ka] (In the equation, dashed lines represent connections.)

[0015] In formula (X1), R 11 and R 12 Each of these is independently a hydrogen atom or a methyl group, but it is preferable that both are hydrogen atoms.

[0016] In formula (X1), n 1 and n 2 Each of these is an integer between 1 and 7, but it is preferably 1.

[0017] In formula (X1), L 1 ~L 4Each of these is independently a saturated hydrocarbylene group having 1 to 8 carbon atoms, and some of the -CH2- groups of the saturated hydrocarbylene group may be substituted with -O-, -S-, -SO2-, or -CO-. The -CH2- groups of the saturated hydrocarbylene group may be located at their terminal ends.

[0018] The saturated hydrocarbylene group may be linear, branched, or cyclic. Specific examples include C1-C8 alkanediyl groups such as methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, and octane-1,8-diyl; and C3-C8 cyclic saturated hydrocarbylene groups such as cyclopentanediyl, cyclohexanediyl, and norbornanediyl.

[0019] L 1 ~L 4 Preferably, all of these have one carbon atom (i.e., a methanediyl group).

[0020] In formula (X1), R 13 ~R 16 These are, independently, a hydrogen atom, a monovalent group represented by the following formula (Y), or a monovalent group represented by the following formula (Z). [ka] (In the equation, dashed lines represent connections.)

[0021] In formula (Y), L 5 This is a hydrocarbylene group having 2 to 14 carbon atoms, and some of the -CH2- groups of the hydrocarbylene group may be substituted with -O-, -S-, -SO2-, or -CO-. The -CH2- groups of the hydrocarbylene group may also be located at their terminal ends.

[0022] The hydrocarbylene group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples include ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,2-diyl group, pentane-1,2-diyl group, hexane-1,2-diyl group, heptane-1,2-diyl group, octane-1,2-diyl group, nonane-1,2-diyl group, decane-1,2-diyl group, and undecane-1 Alkane diyl groups with 2 to 14 carbon atoms, such as ,2-diyl group, dodecane-1,2-diyl, tridecane-1,2-diyl, and tetradecane-1,2-diyl group; cyclic saturated hydrocarbylene groups with 3 to 14 carbon atoms, such as cyclopentanediyl group, cyclohexanediyl group, norbornanediyl group, and adamantanediyl group; ethene-1,1-diyl group, ethene-1,2-diyl group, propene n-1,2-diyl group, 1-butene-1,2-diyl group, 1-pentene-1,2-diyl group, 1-hexene-1,2-diyl group, 1-heptene-1,2-diyl group, 1-octenene-1,2-diyl group, 3-octenene-1,2-diyl group, 1-nonene-1,2-diyl group, 1-decene-1,2-diyl group, 4-decene-1,2-diyl group, 1-undecene-1,2-diyl group Examples include C2-C14 alkenediyl groups such as 1-dodecene-1,2-diyl, 1-tridecene-1,2-diyl, and 1-tetradecene-1,2-diyl; C3-C14 cyclic unsaturated carbylene groups such as cyclohexenediyl and norbornenediyl; and C6-C14 aromatic hydrocarbylene groups such as phenylene, methylphenylene, and naphthalenediyl.

[0023] In formula (Y), R 17 This is either a hydrogen atom or a methyl group.

[0024] In formula (Z), L 6 This is a hydrocarbylene group having 2 to 14 carbon atoms, and some of the -CH2- groups of the hydrocarbylene group may be substituted with -O-, -S-, -SO2-, or -CO-. The -CH2- groups of the hydrocarbylene group may also be located at their terminal ends.

[0025] The hydrocarbylene group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples include ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,2-diyl group, pentane-1,2-diyl group, hexane-1,2-diyl group, heptane-1,2-diyl group, octane-1,2-diyl group, nonane-1,2-diyl group, decane-1,2-diyl group, and undecane-1 Alkane diyl groups with 2 to 14 carbon atoms, such as ,2-diyl group, dodecane-1,2-diyl, tridecane-1,2-diyl, and tetradecane-1,2-diyl group; cyclic saturated hydrocarbylene groups with 3 to 14 carbon atoms, such as cyclopentanediyl group, cyclohexanediyl group, norbornanediyl group, and adamantanediyl group; ethene-1,1-diyl group, ethene-1,2-diyl group, propene n-1,2-diyl group, 1-butene-1,2-diyl group, 1-pentene-1,2-diyl group, 1-hexene-1,2-diyl group, 1-heptene-1,2-diyl group, 1-octenene-1,2-diyl group, 3-octenene-1,2-diyl group, 1-nonene-1,2-diyl group, 1-decene-1,2-diyl group, 4-decene-1,2-diyl group, 1-undecene-1,2-diyl group Examples include C2-C14 alkenediyl groups such as 1-dodecene-1,2-diyl, 1-tridecene-1,2-diyl, and 1-tetradecene-1,2-diyl; C3-C14 cyclic unsaturated carbylene groups such as cyclohexenediyl and norbornenediyl; and C6-C14 aromatic hydrocarbylene groups such as phenylene, methylphenylene, and naphthalenediyl.

[0026] L 6 A hydrocarbylene group having 2 to 10 carbon atoms is preferred.

[0027] All R in the polymer 13 ~R 16 Of these, at least 10 mol% of R 13 ~R 16 The group is represented by formula (Y), but R is present in amounts of 20 mol% or more. 13 ~R 16 Preferably, the group is represented by formula (Y), and 25 mol% or more of R13 ~R 16 It is more preferable that the base is represented by formula (Y).

[0028] Also, all R in the polymer 13 ~R 16 Of these, at least 10 mol% of R 13 ~R 16 The group is represented by formula (Z), and contains 20 mol% or more of R 13 ~R 16 Preferably, the group is represented by formula (Z), and 25 mol% or more of R 13 ~R 16 It is more preferable that the base is represented by formula (Z).

[0029] In formulas (A3) and (A4), X 2 This is a divalent group represented by the following formula (X2). [ka] (The dashed lines represent connecting moves.)

[0030] In formula (X2), R 21 and R 22 Each of these is independently a hydrogen atom or a methyl group, but a hydrogen atom is preferred.

[0031] In formula (X2), R 23 and R 24 These are, independently, hydrocarbyl groups having 1 to 8 carbon atoms.

[0032] In formula (X2), k 1 and k 2 Each of these is an integer between 0 and 7, but it is preferably 0.

[0033] In equation (X2), p is an integer between 0 and 600, but is preferably an integer between 0 and 100, and more preferably an integer between 0 and 30. When p is an integer of 2 or more, each R 23 They may be the same or different from each other, and each R 24 They may be identical or different to each other.

[0034] The silicone resin of component (A) is preferably of a weight-average molecular weight (Mw) of 2,000 to 500,000, and more preferably of 4,000 to 100,000. If Mw is within the above range, a polymer can be obtained as a solid, and film-forming properties can also be ensured. In this invention, Mw is a polystyrene-converted value measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as the elution solvent.

[0035] The silicone resin of component (A) may be a random combination or an alternating combination of repeating units represented by formula (A1), formula (A2), formula (A3), and formula (A4), and may contain multiple blocks of each unit.

[0036] [(A) Method for manufacturing silicone resin] The method for producing the silicone resin of component (A) is not particularly limited, but for example, it can be produced by reacting a polymer (hereinafter also referred to as polymer B) which includes repeating units represented by the following formula (B1) and repeating units represented by the following formula (B2), and which may further include repeating units represented by the following formula (B3) and repeating units represented by the following formula (B4), with a compound represented by the following formula (1), and then reacting it with a compound represented by the following formula (2). [ka] (In the formula, R 1 ~R 4 , m, a, b, c, d and X 2 (This is the same as above.)

[0037] [ka] (In the formula, L 5 , L 6 and R 17 (This is the same as above.)

[0038] In equations (B1) and (B2), X 3 This is a divalent group represented by the following formula (X3). The divalent group represented by the following formula (X3) is a group having a fluorene skeleton. [ka] (In the formula, R 11 and R 12 , L 1 ~L 4 , n 1 and n 2 (The same as above. Dashed lines indicate connections.)

[0039] In formula (1), R 18 This is an isocyanate group or a blocked isocyanate group.

[0040] Specific examples of compounds represented by formula (1) include, but are not limited to, 2-isocyanatoethyl acrylate (Karenz AOI, manufactured by Resonaq Corporation), 2-isocyanatoethyl methacrylate (Karenz MOI, manufactured by Resonaq Corporation), 2-(2-methacryloyloxyethyloxy)ethyl isocyanate (Karenz MOI-EG, manufactured by Resonaq Corporation), 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Karenz MOI-BP, manufactured by Resonaq Corporation), 2-[0-(1'-methylpropylenedenamino)carboxyamino]ethyl methacrylate (Karenz MOI-BM, manufactured by Resonaq Corporation), and 1,1-(bisacryloyloxymethyl)ethyl isocyanate (Karenz BEI, manufactured by Resonaq Corporation).

[0041] Specific examples of compounds represented by formula (2) include succinic anhydride (Licacid SA, manufactured by Shin-Nippon Rika Co., Ltd.), maleic anhydride, hexahydrophthalic anhydride (Licacid HH, manufactured by Shin-Nippon Rika Co., Ltd.), 1,2,3,6-tetrahydrophthalic anhydride (Licacid TH, manufactured by Shin-Nippon Rika Co., Ltd.), 4-methylhexahydrophthalic anhydride (Licacid MH-700, manufactured by Shin-Nippon Rika Co., Ltd.), and others, but are not limited to these.

[0042] The reaction conditions are not particularly limited, but first, polymer B and the compound represented by formula (1) are mixed in a solvent and heated if necessary. As the solvent, it is preferable to use an aprotic polar solvent from the viewpoint of promoting the reaction while suppressing side reactions, and it is particularly preferable to use ketones such as cyclopentanone and cyclohexanone; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; and esters such as ethyl acetate and propylene glycol monomethyl ether acetate. The reaction temperature is preferably, for example, 30 to 100°C, and particularly preferably 30 to 60°C, from the viewpoint of preventing side reactions and enabling the reaction to be completed in a short time. The reaction time depends on the type and amount of reaction substrate, but is preferably about 0.5 to 50 hours, and particularly preferably 3 to 24 hours.

[0043] In the above reaction, the mixing ratio of polymer B and the compound represented by formula (1) is such that X is present in polymer B. 3 In relation to this, it is preferable to blend the compound represented by formula (1) in a molar ratio of 0.40 to 4.00, and more preferably in a molar ratio of 0.80 to 3.20. The compound represented by formula (1) may be a single compound or a combination of two or more compounds.

[0044] In the above reaction, a catalyst may be optionally used. Examples of such catalysts include amines such as triethylamine, triethylenediamine, bis-(2-dimethylaminoethyl) ether, and N-methylmorpholine; phosphines such as triphenylphosphine and tri(o-tolyl)phosphine; quaternary ammonium salts such as tetrabutylammonium chloride, benzyltriethylammonium chloride, and tetraethylhydroxylammonium; imidazoles such as imidazole and 2-ethyl-4-methylimidazole; pyridines such as pyridine, N,N-dimethyl-4-aminopyridine, and 2,6-lutidine; and potassium salts such as potassium carbonate, potassium acetate, and potassium octylate.

[0045] The amount of catalyst used is usually a catalytic amount, and X in polymer B 3It is preferably an amount that is 0.1 to 20 mol% with respect to [the relevant substance]. The catalyst may be used alone or in combination of two or more kinds.

[0046] In the said reaction, a polymerization inhibitor may optionally be used. As the said polymerization inhibitor, various phenols, hydroquinones, benzoquinones, catechols, hydroxyamines, nitroso compounds, etc. can be used. The amount of the said polymerization inhibitor used is not particularly limited, but an amount that is 0.001 to 10% by mass with respect to the compound represented by formula (1) is preferable, and an amount that is 0.01 to 5% by mass is more preferable.

[0047] After completion of the reaction, a solvent may optionally be added, followed by washing with water, and then the organic layer is heated under reduced pressure to distill off the solvent, whereby a reaction intermediate can be obtained.

[0048] Next, the said reaction intermediate and the compound represented by formula (2) are mixed in a solvent and heated. From the viewpoint of promoting the reaction while suppressing side reactions, it is preferable to use an aprotic polar solvent as the said solvent, and it is particularly preferable to use ketones such as cyclopentanone and cyclohexanone; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; esters such as ethyl acetate and propylene glycol monomethyl ether acetate. The reaction temperature is preferably, for example, 35 to 130 °C, particularly preferably 60 to 110 °C, from the viewpoint of preventing side reactions and enabling the reaction to be completed in a short time. The reaction time depends on the type and amount of the reaction substrate, but is preferably approximately 0.5 to 50 hours, particularly preferably 3 to 24 hours.

[0049] In the said reaction, the mixing ratio of polymer B and the compound represented by formula (2) is such that, with respect to X in polymer B 3 the compound represented by formula (2) is preferably formulated so as to have a molar ratio of 0.80 to 8.00, and more preferably so as to have a molar ratio of 1.60 to 6.40. The compound represented by formula (2) may use only one kind of compound, or may use a combination of two or more kinds of compounds.

[0050] In the above reaction, a catalyst may be optionally used. Examples of such catalysts include amines such as triethylamine, triethylenediamine, bis-(2-dimethylaminoethyl) ether, and N-methylmorpholine; phosphines such as triphenylphosphine and tri(o-tolyl)phosphine; quaternary ammonium salts such as tetrabutylammonium chloride, benzyltriethylammonium chloride, and tetraethylhydroxylammonium; imidazoles such as imidazole and 2-ethyl-4-methylimidazole; pyridines such as pyridine, N,N-dimethyl-4-aminopyridine, and 2,6-lutidine; and potassium salts such as potassium carbonate, potassium acetate, and potassium octylate.

[0051] The amount of catalyst used is usually a catalytic amount, and X in polymer B 3 The amount is preferably 0.1 to 20 mol% relative to the total amount. The catalyst may be used alone or in combination of two or more types.

[0052] In the above reaction, a polymerization inhibitor may be optionally used. Suitable polymerization inhibitors include various phenols, hydroquinones, benzoquinones, catechols, hydroxyamines, nitroso compounds, and the like. The amount of polymerization inhibitor used is not particularly limited, but is preferably 0.001 to 10% by mass relative to the amount of (meth)acrylic groups in the reaction intermediate, and more preferably 0.01 to 5% by mass.

[0053] After the reaction is complete, a solvent may be optionally added, followed by washing with water. The organic layer is then heated under reduced pressure to remove the solvent by distillation, thereby obtaining the fluorene skeleton-containing polymer of the present invention. Alternatively, an acidic aqueous solution such as hydrochloric acid may be used for washing with water.

[0054] The method for producing polymer B is not particularly limited, but for example, it can be produced by addition polymerization of a compound represented by formula (3), a compound represented by formula (4), a compound represented by formula (5), and optionally a compound represented by formula (6) in the presence of a metal catalyst. [Chemical formula] (In the formula, R 1 ~R 4 and m are the same as described above.)

[0055] [Chemical formula] (In the formula, R 11 and R 12 , n 1 , n 2 , L 1 ~L 4 are the same as described above.)

[0056] [Chemical formula] (In the formula, R 21 ~R 24 , k 1 , k 2 and p are the same as described above.)

[0057] Examples of the metal catalyst include platinum group metal simple substances such as platinum (including platinum black), rhodium, and palladium; salts of platinum 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), chloroplatinic acid, and chloroplatinate; alcohol-modified chloroplatinic acid (for example, those described in U.S. Patent No. 3,220,972); complexes of chloroplatinic acid and olefins (for example, those described in U.S. Patent No. 3,159,601, U.S. Patent No. 3,159,662, and U.S. Patent No. 3,775,452); platinum group metals such as platinum black and palladium supported on carriers such as alumina, silica, and carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (so-called Wilkinson catalyst); complexes of platinum chloride, chloroplatinic acid, or chloroplatinate with vinyl group-containing siloxane (particularly vinyl group-containing cyclic siloxane), etc. can be used.

[0058] The amount of catalyst used is a catalytic amount, and is usually preferably 0.001 to 0.1% by mass of platinum group metal relative to the total amount of the reaction polymer. In the polymerization reaction, a solvent may be used as needed. As the solvent, hydrocarbon solvents such as toluene and xylene are preferred. As for the polymerization conditions, from the viewpoint of preventing catalyst deactivation and enabling the polymerization to be completed in a short time, the polymerization temperature is preferably 40 to 150°C, and particularly preferably 60 to 120°C. The polymerization time depends on the type and amount of polymer, but to prevent moisture from entering the polymerization system, it is preferably about 0.5 to 100 hours, and particularly preferably 0.5 to 30 hours. After the polymerization reaction is complete, if a solvent was used, it can be removed by distillation to obtain the polymer.

[0059] The reaction method is not particularly limited, but it is preferable to first mix the compound represented by formula (4), the compound represented by formula (5), and optionally the compound represented by formula (6), heat the mixture, add a metal catalyst to the mixed solution, and then add the compound represented by formula (3) dropwise over 0.1 to 5 hours.

[0060] The raw material compounds are preferably blended such that the total number of hydrosilyl groups from the compounds represented by formula (3) and formula (4) is 0.67 to 1.67, and more preferably 0.83 to 1.25, relative to the total number of alkenyl groups from the compounds represented by formula (5) and formula (6). The Mw of the polymer of the present invention can be controlled by using a monoallyl compound such as o-allylphenol, or a monohydrosilane or monohydrosiloxane such as triethylhydrosilane, as a molecular weight modifier.

[0061] In the polymerization reaction described above, a polymerization inhibitor may be optionally used. Examples of polymerization inhibitors include various phenols, hydroquinones, benzoquinones, catechols, hydroxyamines, and nitroso compounds. The amount of polymerization inhibitor used is not particularly limited, but is preferably 0.001 to 10% by mass relative to the compound represented by formula (5), and more preferably 0.01 to 5% by mass.

[0062] After the reaction is complete, a solvent may be optionally added, followed by washing with water. The organic layer is then heated under reduced pressure to remove the solvent, thereby obtaining the fluorene skeleton-containing polymer of the present invention. Alternatively, during washing with water, an aqueous solution of a metal hydroxide such as sodium hydroxide or potassium hydroxide, or a metal carbonate or metal bicarbonate such as sodium carbonate, sodium bicarbonate, or potassium carbonate may be used.

[0063] Another method for producing polymer B is to use a repeating unit represented by the following formula (C1) and the following formula (C2) includes repeating units, and further includes repeating units represented by the following formula (C3) A polymer that may also contain repeating units represented by the following formula (C4) (hereinafter referred to as polymer C and Another example is the reaction between ( ) and the compound represented by the following formula (7). [ka] (In the formula, R 1 ~R 4 , m, a, b, c, d and X 2 (This is the same as above.)

[0064] [ka]

[0065] In equations (C1) and (C2), X 4 This is a divalent group represented by the following formula (X4). The divalent group represented by the following formula (X4) is a group having a fluorene skeleton. [ka] (In the formula, R 11 , R 12 , n 1 and n 2 (The same as above. Dashed lines indicate connections.)

[0066] In formula (7), L 7 This is a saturated hydrocarbylene group having 1 to 14 carbon atoms, wherein some of the -CH2- atoms of the saturated hydrocarbylene group may be substituted with -O-, -S-, -SO2-, -CO-, or -CONH-, and some or all of the hydrogen atoms of the saturated hydrocarbylene group may be substituted with hydroxyl groups. 7 The saturated hydrocarbylene group represented by may be linear, branched, or cyclic, but it is preferable that it has 1 to 7 carbon atoms.

[0067] In formula (7), L 8 This is a saturated hydrocarbylene group having 1 to 14 carbon atoms, wherein some of the -CH2- atoms of the saturated hydrocarbylene group may be substituted with -O-, -S-, -SO2-, -CO-, or -CONH-, and some or all of the hydrogen atoms of the saturated hydrocarbylene group may be substituted with hydroxyl groups. 8 The saturated hydrocarbylene group represented by may be linear, branched, or cyclic, but it is preferable that it has 1 to 7 carbon atoms.

[0068] Specific examples of compounds represented by formula (7) include, but are not limited to, glycidol (epiol OH®, manufactured by NOF Corporation).

[0069] The reaction conditions are not particularly limited, but typically polymer C and the compound represented by formula (7) are mixed in a solvent and heated. From the viewpoint of promoting the reaction, a polar solvent is preferred as the solvent, and an alcohol-based solvent such as propylene glycol monomethyl ether is particularly preferred. The reaction temperature is preferably 35 to 130°C, and particularly preferably 45 to 100°C, from the viewpoint of preventing side reactions and enabling the reaction to be completed in a short time. The reaction time depends on the type and amount of the reaction substrate, but is preferably about 0.5 to 50 hours, and particularly preferably 0.5 to 24 hours.

[0070] In the above reaction, each starting compound contains X in polymer C. 4 In contrast, the compound represented by formula (7) is preferably blended in a molar ratio of 1.0 to 8.0, and more preferably in a molar ratio of 4.0 to 6.0. The compound represented by formula (5) may be a single compound or a combination of two or more compounds.

[0071] In the above reaction, a catalyst may be optionally used. The catalyst may include amines such as triethylamine, triethylenediamine, bis-(2-dimethylaminoethyl) ether, and N-methylmorpholine; phosphines such as triphenylphosphine and tri(o-tolyl)phosphine; quaternary ammonium salts such as tetrabutylammonium chloride, benzyltriethylammonium chloride, and tetraethylhydroxylammonium; imidazoles such as imidazole and 2-ethyl-4-methylimidazole; pyridines such as pyridine, N,N-dimethyl-4-aminopyridine, and 2,6-lutidine; tin acetate, tin octylate, tin oleate, tin laurylate, dibutyltin diacetate, and dimethyltin. Examples include organotin compounds such as dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dilaurate (dibutyltin(IV) dilaurate), dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurylate, and dibutyltin dichloride; organolead compounds such as lead octanoate and lead naphthenate; organonickel compounds such as nickel naphthenate; organocobaltan compounds such as cobalt naphthenate; organocouvenir compounds such as copper octenoate; organobisum compounds such as bismuth octoate and bismuth neodecanoate; and potassium salts such as potassium carbonate, potassium acetate, and potassium octoate.

[0072] The amount of catalyst used is usually a catalytic amount, and X in polymer C. 4 The amount is preferably 0.1 to 20 mol% relative to the total amount. The catalyst may be used alone or in combination of two or more types.

[0073] In the above reaction, a polymerization inhibitor may be optionally used. Examples of polymerization inhibitors include various phenols, hydroquinones, benzoquinones, catechols, hydroxyamines, nitroso compounds, and the like. The amount of polymerization inhibitor used is not particularly limited, but is preferably 0.001 to 10% by mass relative to the compound represented by formula (7), and more preferably 0.01 to 5% by mass.

[0074] After the reaction is complete, a solvent may be optionally added, followed by washing with water. The organic layer is then heated under reduced pressure to remove the solvent, thereby obtaining the fluorene skeleton-containing polymer of the present invention. Alternatively, during washing with water, an aqueous solution of a metal hydroxide such as sodium hydroxide or potassium hydroxide, or a metal carbonate or metal bicarbonate such as sodium carbonate, sodium bicarbonate, or potassium carbonate may be used.

[0075] [(B) Photoradical Generator] The photoradical generator of component (B) is not particularly limited as long as it is a compound that generates radicals upon exposure. Specific examples include acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, oxime compounds, carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, non-imidazole compounds, fluorene compounds, etc. Of these, acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, or oxime compounds are preferred, with oxime compounds being more preferred.

[0076] Specific examples of the aforementioned acetophenone compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one.

[0077] Specific examples of the aforementioned benzophenone compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

[0078] Specific examples of the thioxanthone compounds mentioned above include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

[0079] Specific examples of the benzoin compounds mentioned above include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

[0080] Specific examples of the aforementioned triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-to Examples include lyazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-s-triazine, and 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine.

[0081] Specific examples of the aforementioned oxime compounds include 1,2-octanedione, O-acyl oxime compounds, 2-(O-benzoyl oxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyl oxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane, and O-ethoxycarbonyl-α-oxyamino-1-phenylpropane-1-one. Specific examples of the O-acyloxime compounds include 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine-4-ylphenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butan-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-one oxime-O-acetate, and 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O-acetate.

[0082] Specific examples of the phosphine oxide compounds mentioned above include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0083] In the photosensitive resin composition of the present invention, the content of (B) photoradical generator is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of component (A). When the content of the photoradical generator is within the above range, an excellent balance between sensitivity and developability during exposure is obtained, a pattern with excellent resolution without residual film is obtained, and in addition, a highly reliable cured film is obtained. (B) photoradical generator may be used alone or in combination of two or more types.

[0084] [(C) Crosslinking agent] The photosensitive resin composition of the present invention may further contain a crosslinking agent as component (C). The crosslinking agent (C) is a component that undergoes a crosslinking reaction with the silicone resin (A) to facilitate the formation of a pattern with a good shape, and a crosslinking agent having two or more (meth)acryloyl groups is preferred.

[0085] Specific examples of crosslinking agents having two or more (meth)acryloyl groups include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropyl glycol di(meth)acrylate, and trimethylolpropyl glycol di(meth)acrylate. Pantri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate (T)Acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate diglycidyl ester di(meth)acrylate, glycerin triacrylate, glyceryl Examples include polyglycidyl ether poly(meth)acrylate, urethane(meth)acrylate (i.e., reaction products of tolylene diisocyanate, trimethylhexamethylene diisocyanate or hexamethylene diisocyanate, etc. with 2-hydroxyethyl(meth)acrylate), methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, polyfunctional monomers such as condensates of polyhydric alcohols with N-methylol(meth)acrylamide, and triacrylic formal.

[0086] If the photosensitive resin composition of the present invention contains (C) a crosslinking agent, its content is preferably 0.5 to 100 parts by mass, and more preferably 1 to 50 parts by mass, per 100 parts by mass of component (A). The (C) crosslinking agent may be used alone or in combination of two or more types.

[0087] [(D) Silane coupling agent] The photosensitive resin composition of the present invention may further contain a silane coupling agent as component (D) in order to improve adhesion to the substrate.

[0088] (D) Examples of silane coupling agents include amino group-containing silane coupling agents, epoxy group-containing silane coupling agents, (meth)acryloyl group-containing silane coupling agents, mercapto group-containing silane coupling agents, vinyl group-containing silane coupling agents, ureido group-containing silane coupling agents, styryl group-containing silane coupling agents, and silane coupling agents having a cyclic anhydride structure, but among these, (meth)acryloyl group-containing silane coupling agents are preferred.

[0089] Specific examples of the amino group-containing silane coupling agent include KBM-602, KBM-603, KBM-903, and KBM-573 (manufactured by Shin-Etsu Chemical Co., Ltd.). Specific examples of the epoxy group-containing silane coupling agent include KBM-303, KBM-402, KBM-403, and KBE-402 (manufactured by Shin-Etsu Chemical Co., Ltd.). Specific examples of the (meth)acryloyl group-containing silane coupling agent include, for example, KBM-502, KBM-503, KBE-502, KBE-503, and KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.). Specific examples of the mercapto group-containing silane coupling agent include KBM-802 and KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.). Specific examples of the vinyl group-containing silane coupling agent include KBM-1003 and KBE-1003 (manufactured by Shin-Etsu Chemical Co., Ltd.). Specific examples of the ureido group-containing silane coupling agent include KBE-585A (manufactured by Shin-Etsu Chemical Co., Ltd.). Specific examples of the styryl group-containing silane coupling agent include KBM-1403 (manufactured by Shin-Etsu Chemical Co., Ltd.). Specific examples of the silane coupling agent having a cyclic anhydride structure include X-12-967C (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0090] If the photosensitive resin composition of the present invention contains (D) a silane coupling agent, its content is preferably 0.5 to 20 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of component (A). The (D) silane coupling agent may be used alone or in combination of two or more types.

[0091] [(E) Solvent] The photosensitive resin composition of the present invention may contain a solvent as component (E). The solvent (E) is not particularly limited as long as it can dissolve and disperse the aforementioned components (A) to (D) and other various additives.

[0092] (E) As solvents, organic solvents are preferred, for example, 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, 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, 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.

[0093] (E) As solvents, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclopentanone, and mixed solvents thereof are preferred, as they have particularly good solubility for (A) silicone resin and (B) photoradical generator.

[0094] (E) The content of component (E) is preferably 25 to 85% by mass, and more preferably 30 to 80% by mass, relative to the total amount of the photosensitive resin composition, from the viewpoint of compatibility and viscosity of the photosensitive resin composition. (E) Solvent may be used alone or as a mixture of two or more types.

[0095] The photosensitive resin composition of the present invention can be prepared by conventional methods. For example, the photosensitive resin composition of the present invention can be prepared by stirring and mixing the components, and then filtering out the solids as needed using a filter or the like.

[0096] The photosensitive resin composition of the present invention prepared in this manner can be suitably used, for example, as a protective film-forming material for various electrical and electronic components such as circuit boards, semiconductor elements, and display elements.

[0097] [Pattern formation method] The pattern forming method using the photosensitive resin composition of the present invention is: (i) A step of forming a photosensitive resin film on a substrate using the photosensitive resin composition of the present invention, (ii) A step of exposing the photosensitive resin film, and (iii) A step of developing the exposed photosensitive resin film using a developer to remove unexposed areas and form a pattern. It includes.

[0098] Step (i) is a step of forming a photosensitive resin film on a substrate using the photosensitive resin composition. Examples of the substrate include silicon wafers, silicon wafers for through electrodes, silicon wafers thinned by backside polishing, plastic or ceramic substrates, and substrates having metals such as Ni or Au on the entire surface or in part by ion sputtering or plating. In addition, substrates with uneven surfaces may also be used.

[0099] One method for forming a photosensitive resin film is to apply the photosensitive resin composition onto a substrate and preheat (pre-bake) it as needed. The application method can be any known method, such as the dip method, spin coating method, or roll coating method. The amount of the photosensitive resin composition applied can be appropriately selected depending on the purpose, but it is preferable to apply it so that the resulting photosensitive resin film thickness is preferably 0.1 to 200 μm, more preferably 1 to 150 μm.

[0100] To improve film thickness uniformity on the substrate surface, a solvent may be dropped onto the substrate before applying the photosensitive resin composition (pre-wetting method). The solvent to be dropped and its amount can be appropriately selected depending on the purpose. Preferred solvents include alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, and glycols such as PGME, but solvents used in photosensitive resin compositions can also be used.

[0101] To ensure efficient photocuring, pre-baking may be performed to evaporate solvents and other substances beforehand, if necessary. Pre-baking can be carried out, for example, at 40-140°C for 1 minute to 1 hour.

[0102] Next, (ii) the photosensitive resin film is exposed to light. At this time, exposure is preferably carried out with light of a wavelength of 10 to 600 nm, and more preferably with light of 190 to 500 nm. Examples of such wavelengths of light include various wavelengths of light generated by a radiation generator, such as ultraviolet rays (g-rays, h-rays, i-rays, etc.) and far-ultraviolet rays (248 nm, 193 nm). Of these, light of a wavelength of 248 to 436 nm is particularly preferred. The exposure amount is 10 to 10000 mJ / cm². 2 This is preferable. In this invention, even without performing the PEB process, the crosslinking reaction proceeds in the exposed area, forming an insoluble pattern that is insoluble in the organic solvent used as the developer. By not performing the PEB process, it is possible to prevent the catalyst species generated in the exposed area from thermally diffusing to the unexposed area, thereby enabling the refinement of the pattern.

[0103] Exposure may be performed via a photomask. The photomask may, for example, have a desired pattern cut out of it. The material of the photomask is not particularly limited, but it is preferably one that blocks light of the aforementioned wavelength, and for example, one that has chromium or the like as a light-shielding film is preferably used.

[0104] After exposure, (iii) the photosensitive resin film is developed using a developer to form a pattern. Both organic solvents and alkaline developers can be used as the developer, but using an alkaline developer allows for a finer pattern to be obtained. The type and concentration of the alkaline agent can be selected as appropriate, but a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred. Examples of development methods include conventional methods, such as immersing the patterned substrate in the developer. The unexposed areas are dissolved and removed by development, thereby forming the pattern. After that, washing, rinsing, drying, etc., are performed as necessary to obtain a resin film with the desired pattern.

[0105] Furthermore, the (iv) patterned film can be post-cured at 40-190°C using an oven or hot plate. A post-curing temperature of 40-190°C increases the crosslinking density of the photosensitive resin composition without damaging the laminated semiconductor elements, ensuring high chemical resistance, copper migration resistance, and reliability of the cured film. The post-curing time is preferably 10 minutes to 12 hours, and more preferably 1 hour to 6 hours. Using the photosensitive resin composition of the present invention, a film with excellent cured film properties can be obtained by post-curing at around 40-190°C. The film thickness of the cured film after post-curing is typically 1-200 μm, preferably 5-50 μm.

[0106] If it is not necessary to form a pattern, for example, if it is simply desired to form a uniform film, the film can be formed in step (ii) of the pattern formation method by exposing the material to light of an appropriate wavelength without using the photomask.

[0107] The film obtained from the photosensitive resin composition can ensure high chemical resistance, copper migration resistance, and reliability despite low-temperature curing, and can be suitably used as a protective film-forming material for various electrical and electronic components such as circuit boards, semiconductor elements, and display elements. [Examples]

[0108] The present invention will be specifically described below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples. In the following examples, Mw was measured by GPC using monodisperse polystyrene as the standard, with TSKgel Super HZM-H (manufactured by Tosoh Corporation) as the column, under analytical conditions of flow rate 0.6 mL / min, elution solvent THF, and column temperature 40°C.

[0109] The compounds used in the synthesis of the polymer are listed below. [ka]

[0110] [ka]

[0111] [ka]

[0112] [ka]

[0113] [ka]

[0114] [ka]

[0115] [ka]

[0116] [ka]

[0117] [Synthesis Example 1] Synthesis of Polymer b1 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 245.4 g (0.235 mol) of the compound represented by formula (S-2a) and 430.5 g (1.00 mol) of the compound represented by formula (S-3a) were added, followed by the addition of 1500 g of toluene, and the mixture was heated to 70°C. Then, 1.0 g of toluene chlorplatinate solution (platinum concentration 0.5% by mass) was added, and 142.9 g (0.735 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total hydrosilyl groups:total alkenyl groups = 0.97:1 (molar ratio)). After the dropwise addition was complete, the mixture was heated to 90°C and aged for 11 hours. Toluene was then removed from the reaction solution under reduced pressure to obtain the polymer. To this polymer, 2000 g of propylene glycol monomethyl ether was added and confirmed to be dissolved. Then, 444.5 g (6.00 mol) of the compound represented by formula (S-5) and 10.1 g (0.10 mol) of triethylamine were added, and the mixture was heated at 80°C for 12 hours. After the reaction was complete, the reaction solution was concentrated under reduced pressure, dissolved in cyclopentanone, and the reaction solution was washed with pure water. Subsequently, the organic layer was removed under reduced pressure to obtain polymer b1. The Mw of polymer b1 was 8000. Mw was measured by gel permeation chromatography (GPC) using tetrahydrofuran as the eluent, calculated in polystyrene equivalent. 1 ¹H-NMR (Bruker) confirmed that the polymer contains repeating units represented by formula (B1) and formula (B2).

[0118] [Synthesis Example 2] Synthesis of Polymer b2 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 530.5 g (0.18 mol) of the compound represented by formula (S-2b), 387.5 g (0.90 mol) of the compound represented by formula (S-3a), and 18.64 g (0.10 mol) of the compound represented by formula (S-4) were added. Then, 1500 g of toluene was added and the mixture was heated to 70°C. Subsequently, 1.0 g of toluene chloroplatinate solution (platinum concentration 0.5% by mass) was added, and 153.6 g (0.79 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total hydrosilyl groups:total alkenyl groups = 0.97:1 (molar ratio)). After the dropwise addition was complete, the mixture was heated to 90°C and aged for 11 hours. Then, toluene was removed from the reaction solution under reduced pressure to obtain the polymer. To this polymer, 2000 g of propylene glycol monomethyl ether was added and confirmed to be dissolved. Then, 400.0 g (5.40 mol) of the compound represented by formula (S-5) and 9.11 g (0.09 mol) of triethylamine were added, and the mixture was heated at 80°C for 12 hours. After the reaction was complete, the reaction solution was concentrated under reduced pressure, dissolved in cyclopentanone, and the reaction solution was washed with pure water. Subsequently, the organic layer was removed under reduced pressure to obtain polymer b2. The Mw of polymer b2 was 80000. Mw was measured by gel permeation chromatography (GPC) using tetrahydrofuran as the eluent, and the value was measured in polystyrene equivalent. 1 ¹H-NMR (Bruker) confirmed that the polymer contains repeating units represented by formula (B1), formula (B2), formula (B3), and formula (B4).

[0119] [Synthesis Example 3] Synthesis of Polymer A1 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 800 g of polymer b1 was added and dissolved in 2200 g of cyclopentanone. Then, 231.4 g (1.64 mol) of the compound represented by formula (S-6a) and 19.5 g (0.16 mol) of N,N-dimethyl-4-aminopyridine were added, and the mixture was heated at 50°C for 12 hours. After the reaction was complete, the reaction solution was washed with pure water, and the organic layer was removed by distillation under reduced pressure to obtain a reaction intermediate. Next, the reaction intermediate was dissolved in 2200 g of propylene glycol monomethyl ether acetate. Then, 328.2 g (3.28 mol) of the compound represented by formula (S-7a) and 16.2 g (0.16 mol) of triethylamine were added, and the mixture was heated at 100°C for 12 hours. After the reaction was complete, the reaction solution was washed with hydrochloric acid and pure water, and the organic layer was removed by distillation under reduced pressure to obtain polymer A1. The Mw of polymer A1 was 9000. Note that polymer A1 is... 1 ¹H-NMR (Bruker) confirmed that the polymer contains repeating units represented by formula (A1) and formula (A2). The introduction of the group represented by formula (Y) and the monovalent group represented by formula (Z) into the side chain was confirmed by the disappearance of the NMR peak originating from the alcoholic hydroxyl group of the side chain and the change in molecular weight before and after the reaction by GPC. In addition, the R in formula (X1) 13 ~R 16 Of which, 50 mol% R 13 ~R 16 The group is represented by formula (Y), and 50 mol% of R 13 ~R 16 The base was represented by equation (Z).

[0120] [Synthesis Example 4] Synthesis of Polymer A2 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 800 g of polymer b1 was added and dissolved in 2200 g of cyclopentanone. Then, 115.7 g (0.82 mol) of the compound represented by formula (S-6a) and 19.5 g (0.16 mol) of N,N-dimethyl-4-aminopyridine were added, and the mixture was heated at 50°C for 12 hours. After the reaction was complete, the reaction solution was washed with pure water, and the organic layer was removed by distillation under reduced pressure to obtain a reaction intermediate. Next, the reaction intermediate was dissolved in 2200 g of propylene glycol monomethyl ether acetate. Then, 492.3 g (4.92 mol) of the compound represented by formula (S-7a) and 16.2 g (0.16 mol) of triethylamine were added, and the mixture was heated at 100°C for 12 hours. After the reaction was complete, the reaction solution was washed with hydrochloric acid and pure water, and the organic layer was removed by distillation under reduced pressure to obtain polymer A2. The Mw of polymer A2 was 9000. Note that polymer A2 is... 1 ¹H-NMR (Bruker) confirmed that the polymer contains repeating units represented by formula (A1) and formula (A2). The introduction of the group represented by formula (Y) and the monovalent group represented by formula (Z) into the side chain was confirmed by the disappearance of the NMR peak originating from the alcoholic hydroxyl group of the side chain and the change in molecular weight before and after the reaction by GPC. In addition, the R in formula (X1) 13 ~R 16 Of which, 25 mol% R 13 ~R 16 The group is represented by formula (Y), and 75 mol% of R 13 ~R 16 The base was represented by equation (Z).

[0121] [Synthesis Example 5] Synthesis of Polymer A3 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 800 g of polymer b1 was added and dissolved in 2200 g of cyclopentanone. Then, 347.1 g (2.46 mol) of the compound represented by formula (S-6a) and 19.5 g (0.16 mol) of N,N-dimethyl-4-aminopyridine were added, and the mixture was heated at 50°C for 12 hours. After the reaction was complete, the reaction solution was washed with pure water, and the organic layer was removed by distillation under reduced pressure to obtain a reaction intermediate. Next, the reaction intermediate was dissolved in 2200 g of propylene glycol monomethyl ether acetate. Then, 164.1 g (1.64 mol) of the compound represented by formula (S-7a) and 16.2 g (0.16 mol) of triethylamine were added, and the mixture was heated at 100°C for 12 hours. After the reaction was complete, the reaction solution was washed with hydrochloric acid and pure water, and the organic layer was removed by distillation under reduced pressure to obtain polymer A3. The Mw of polymer A3 was 9000. Furthermore, polymer A3 is... 1 ¹H-NMR (Bruker) confirmed that the polymer contains repeating units represented by formula (A1) and formula (A2). The introduction of the group represented by formula (Y) and the monovalent group represented by formula (Z) into the side chain was confirmed by the disappearance of the NMR peak originating from the alcoholic hydroxyl group of the side chain and the change in molecular weight before and after the reaction by GPC. In addition, the R in formula (X1) 13 ~R 16 Of which, 75 mol% R 13 ~R 16 The group is represented by formula (Y), and 25 mol% of R 13 ~R 16 The base was represented by equation (Z).

[0122] [Synthesis Example 6] Synthesis of Polymer A4 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 800 g of polymer b1 was added and dissolved in 2200 g of cyclopentanone. Then, 254.4 g (1.64 mol) of the compound represented by formula (S-6b) and 19.5 g (0.16 mol) of N,N-dimethyl-4-aminopyridine were added, and the mixture was heated at 50°C for 12 hours. After the reaction was complete, the reaction solution was washed with pure water, and the organic layer was removed by distillation under reduced pressure to obtain a reaction intermediate. Next, the reaction intermediate was dissolved in 2200 g of propylene glycol monomethyl ether acetate. Then, 505.6 g (3.28 mol) of the compound represented by formula (S-7b) and 16.2 g (0.16 mol) of triethylamine were added, and the mixture was heated at 100°C for 12 hours. After the reaction was complete, the reaction solution was washed with hydrochloric acid and pure water, and the organic layer was removed by distillation under reduced pressure to obtain polymer A4. The Mw of polymer A4 was 10000. Note that polymer A4 is... 1 ¹H-NMR (Bruker) confirmed that the polymer contains repeating units represented by formula (A1) and formula (A2). The introduction of the group represented by formula (Y) and the monovalent group represented by formula (Z) into the side chain was confirmed by the disappearance of the NMR peak originating from the alcoholic hydroxyl group of the side chain and the change in molecular weight before and after the reaction by GPC. In addition, the R in formula (X1) 13 ~R 16 Of which, 50 mol% R 13 ~R 16 The group is represented by formula (Y), and 50 mol% of R 13 ~R 16 The base was represented by equation (Z).

[0123] [Synthesis Example 7] Synthesis of Polymer A5 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 800 g of polymer b1 was added and dissolved in 2200 g of cyclopentanone. Then, 254.4 g (1.64 mol) of the compound represented by formula (S-6b) and 19.5 g (0.16 mol) of N,N-dimethyl-4-aminopyridine were added, and the mixture was heated at 50°C for 12 hours. After the reaction was complete, the reaction solution was washed with pure water, and the organic layer was removed by distillation under reduced pressure to obtain a reaction intermediate. Next, the reaction intermediate was dissolved in 2200 g of propylene glycol monomethyl ether acetate. Then, 485.8 g (3.28 mol) of the compound represented by formula (S-7c) and 16.2 g (0.16 mol) of triethylamine were added, and the mixture was heated at 100°C for 12 hours. After the reaction was complete, the reaction solution was washed with hydrochloric acid and pure water, and the organic layer was removed by distillation under reduced pressure to obtain polymer A5. The Mw of polymer A5 was 10000. Note that polymer A5 is... 1 ¹H-NMR (Bruker) confirmed that the polymer contains repeating units represented by formula (A1) and formula (A2). The introduction of the group represented by formula (Y) and the monovalent group represented by formula (Z) into the side chain was confirmed by the disappearance of the NMR peak originating from the alcoholic hydroxyl group of the side chain and the change in molecular weight before and after the reaction by GPC. In addition, the R in formula (X1) 13 ~R 16 Of which, 50 mol% R 13 ~R 16 The group is represented by formula (Y), and 50 mol% of R 13 ~R 16 The base was represented by equation (Z).

[0124] [Synthesis Example 8] Synthesis of Polymer A6 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 800 g of polymer b2 was added and dissolved in 2200 g of cyclopentanone. Then, 166.5 g (1.18 mol) of the compound represented by formula (S-6a) and 14.7 g (0.12 mol) of N,N-dimethyl-4-aminopyridine were added, and the mixture was heated at 50°C for 12 hours. After the reaction was complete, the reaction solution was washed with pure water, and the organic layer was removed by distillation under reduced pressure to obtain a reaction intermediate. Next, the reaction intermediate was dissolved in 2200 g of propylene glycol monomethyl ether acetate. Then, 236.2 g (2.36 mol) of the compound represented by formula (S-7a) and 12.1 g (0.12 mol) of triethylamine were added, and the mixture was heated at 100°C for 12 hours. After the reaction was complete, the reaction solution was washed with hydrochloric acid and pure water, and the organic layer was removed by distillation under reduced pressure to obtain polymer A6. The Mw of polymer A6 was 82000. Note that polymer A6 is... 1 ¹H-NMR (Bruker) confirmed that the polymer contains repeating units represented by formula (A1), formula (A2), formula (A3), and formula (A4). The introduction of the group represented by formula (Y) and the monovalent group represented by formula (Z) into the side chain was confirmed by the disappearance of the NMR peak originating from the alcoholic hydroxyl group of the side chain and the change in molecular weight before and after the reaction by GPC. In addition, the R in formula (X1) 13 ~R 16 Of which, 50 mol% R 13 ~R 16 The group is represented by formula (Y), and 50 mol% of R 13 ~R 16 The base was represented by equation (Z).

[0125] [Synthesis Example 9] Synthesis of Polymer A7 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 800 g of polymer b2 was added and dissolved in 2200 g of cyclopentanone. Then, 183.1 g (1.18 mol) of the compound represented by formula (S-6b) and 14.7 g (0.12 mol) of N,N-dimethyl-4-aminopyridine were added, and the mixture was heated at 50°C for 12 hours. After the reaction was complete, the reaction solution was washed with pure water, and the organic layer was removed by distillation under reduced pressure to obtain a reaction intermediate. Next, the reaction intermediate was dissolved in 2200 g of propylene glycol monomethyl ether acetate. Then, 363.8 g (2.36 mol) of the compound represented by formula (S-7b) and 12.1 g (0.12 mol) of triethylamine were added, and the mixture was heated at 100°C for 12 hours. After the reaction was complete, the reaction solution was washed with hydrochloric acid and pure water, and the organic layer was removed by distillation under reduced pressure to obtain polymer A7. The Mw of polymer A7 was 82000. Note that polymer A7 is... 1 ¹H-NMR (Bruker) confirmed that the polymer contains repeating units represented by formula (A1), formula (A2), formula (A3), and formula (A4). The introduction of the group represented by formula (Y) and the monovalent group represented by formula (Z) into the side chain was confirmed by the disappearance of the NMR peak originating from the alcoholic hydroxyl group of the side chain and the change in molecular weight before and after the reaction by GPC. In addition, the R in formula (X1) 13 ~R 16 Of which, 50 mol% R 13 ~R 16 The group is represented by formula (Y), and 50 mol% of R 13 ~R 16 The base was represented by equation (Z).

[0126] [Synthesis Example 10] Synthesis of Polymer A8 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 800 g of polymer b2 was added and dissolved in 2200 g of cyclopentanone. Then, 183.1 g (1.18 mol) of the compound represented by formula (S-6b) and 14.7 g (0.12 mol) of N,N-dimethyl-4-aminopyridine were added, and the mixture was heated at 50°C for 12 hours. After the reaction was complete, the reaction solution was washed with pure water, and the organic layer was removed by distillation under reduced pressure to obtain a reaction intermediate. Next, the reaction intermediate was dissolved in 2200 g of propylene glycol monomethyl ether acetate. Then, 349.5 g (2.36 mol) of the compound represented by formula (S-7c) and 12.1 g (0.12 mol) of triethylamine were added, and the mixture was heated at 100°C for 12 hours. After the reaction was complete, the reaction solution was washed with hydrochloric acid and pure water, and the organic layer was removed by distillation under reduced pressure to obtain polymer A8. The Mw of polymer A8 was 82000. Note that polymer A8 is... 1 ¹H-NMR (Bruker) confirmed that the polymer contains repeating units represented by formula (A1), formula (A2), formula (A3), and formula (A4). The introduction of the group represented by formula (Y) and the monovalent group represented by formula (Z) into the side chain was confirmed by the disappearance of the NMR peak originating from the alcoholic hydroxyl group of the side chain and the change in molecular weight before and after the reaction by GPC. In addition, the R in formula (X1) 13 ~R 16 Of which, 50 mol% R 13 ~R 16 The group is represented by formula (Y), and 50 mol% of R 13 ~R 16 The base was represented by equation (Z).

[0127] [Comparative Synthesis Example 1] Synthesis of Comparative Polymer A'1 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 400 g of dimethyl carbonate was added and heated to 70°C. Then, 213.4 g (1.64 mol) of the compound represented by formula (S-8a), 164.2 g (1.64 mol) of the compound represented by formula (S-8b), 15.1 g (0.092 mol) of azobisisobutyronitrile, and 400 g of dimethyl carbonate were added dropwise over 1 hour. After the addition was complete, the mixture was heated to 80°C and aged for 12 hours. Dimethyl carbonate was then removed from the reaction solution under reduced pressure. It was then dissolved in 800 g of cyclopentanone. Then, 254.4 g (1.64 mol) of the compound represented by formula (S-6b) and 19.5 g (0.16 mol) of N,N-dimethyl-4-aminopyridine were added, and the mixture was heated at 50°C for 12 hours. After the reaction was complete, the reaction solution was washed with pure water, and the organic layer was removed by reduced pressure distillation to obtain comparative polymer A'1. The Mw of comparative polymer A'1 was 15000.

[0128] [Comparative Synthesis Example 2] Synthesis of Comparative Polymer A'2 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 400 g of dimethyl carbonate was added and heated to 70°C. Then, 164.2 g (1.64 mol) of the compound represented by formula (S-8b), 233.1 g (1.64 mol) of the compound represented by formula (S-8c), 15.9 g (0.097 mol) of azobisisobutyronitrile, and 400 g of dimethyl carbonate were added dropwise over 1 hour. After the addition was complete, the mixture was heated to 80°C and aged for 12 hours. Dimethyl carbonate was then removed from the reaction solution under reduced pressure. It was then dissolved in 800 g of cyclopentanone. Then, 213.4 g (1.64 mol) of the compound represented by formula (S-8a) and 16.2 g (0.16 mol) of triethylamine were added, and the mixture was heated at 90°C for 12 hours. After the reaction was complete, the reaction solution was washed with pure water, and the organic layer was removed by reduced-pressure distillation to obtain comparative polymer A'2. The Mw of comparative polymer A'2 was 16000.

[0129] [Comparative Synthesis Example 3] Synthesis of Comparative Polymer A'3 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 401 g (0.50 mol) of the compound represented by formula (S-2a), 488 g (0.90 mol) of the compound represented by formula (S-3b), and 18.6 g (0.10 mol) of the compound represented by formula (S-4) were added. Then, 1100 g of toluene was added and the mixture was heated to 80°C. Subsequently, 1.0 g of toluene chloroplatinate solution (platinum concentration 0.5% by mass) was added, and 95.3 g (0.49 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total hydrosilyl groups:total alkenyl groups = 0.99:1 (molar ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and aged for 6 hours. Toluene was then removed from the reaction solution under reduced pressure to obtain comparative polymer A'3. The Mw of comparative polymer A'3 was 12000.

[0130] [Comparative Synthesis Example 4] Synthesis of Comparative Polymer A'4 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 1362 g (0.45 mol) of the compound represented by formula (S-2b) and 430 g (1.00 mol) of the compound represented by formula (S-3a) were added, followed by the addition of 2100 g of toluene, and the mixture was heated to 70°C. Then, 2.0 g of toluene chloroplatinate solution (platinum concentration 0.5% by mass) was added, and 105 g (0.54 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total hydrosilyl groups:total alkenyl groups = 0.99:1 (molar ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and aged for 12 hours. Toluene was then removed from the reaction solution under reduced pressure to obtain comparative polymer A'4. The Mw of comparative polymer A'4 was 14000.

[0131] [2] Preparation of photosensitive resin composition [Examples 1-23 and Comparative Examples 1-12] Each component was mixed according to the proportions listed in Tables 1-3, then stirred and dissolved at room temperature. Finally, the mixture was microfiltered using a 1.0 μm Teflon® filter to prepare the photosensitive resin compositions of Examples 1-23 and Comparative Examples 1-12.

[0132] [Table 1]

[0133] [Table 2]

[0134] [Table 3]

[0135] In Tables 1-3, B1-B4 and B'1-B'2 are as follows: [ka]

[0136] In Tables 1-3, C1-C2 and C'1-C'2 are as follows: [ka]

[0137] In Tables 1-3, D1 is KBM-503 (3-methacryloxypropyltrimethoxysilane), manufactured by Shin-Etsu Chemical Co., Ltd., and D2 is KBM-403 (3-glycidoxypropyltrimethoxysilane), also manufactured by Shin-Etsu Chemical Co., Ltd.

[0138] [3] Evaluation of resin coating (1) Pattern formation and evaluation thereof Each photosensitive resin composition was coated to a thickness of 20 μm using a spin coater onto a migration test substrate (a comb-shaped electrode substrate with copper as the conductive material, conductive area spacing and conductive area width of 20 μm, and conductive area thickness of 4 μm). To remove the solvent from the composition, the substrate was heated and dried using a hot plate at 100°C for 5 minutes to obtain a photosensitive resin film. The obtained photosensitive resin film was then exposed to light at a wavelength of 365 nm at a rate of 500 mJ / cm² through a quartz mask having sets of lines and spaces with line widths ranging from 1 μm to 50 μm. 2The substrates were irradiated with the specified exposure dose. Exposure was performed using a Nikon Corporation stepper-type exposure system NSR-1755i7A. Subsequently, for Examples 1 to 23, the exposed photosensitive resin films were paddle-developed in a 2.38% by mass TMAH aqueous solution for 180 seconds to form patterns. For Comparative Examples 1 to 12, since they were insoluble in TMAH aqueous solution, spray development was performed with PGMEA for 180 seconds. However, since the exposed areas were all developed, post-exposure heat treatment (PEB) was performed. The PEB process was carried out under optimized conditions of 140°C for 5 minutes, and development was performed similarly. Finally, the photosensitive resin films on the patterned substrates were post-cured in an oven at 180°C for 2 hours while purging with nitrogen, and then observed. The pattern cross-section was observed by SEM, and the smallest pattern size that was resolved was defined as the limiting resolution. Furthermore, the verticality was evaluated from the obtained cross-sectional photographs, with ◎ indicating a perfectly vertical pattern, ○ indicating slight tapering or fitting, △ indicating strong tapering or fitting, and × indicating poor opening.

[0139] (2) Evaluation of electrical properties (copper migration) A substrate with a pattern formed by method (1) was used as a substrate for evaluating copper migration, and tests were conducted. The copper migration test was performed under the conditions of a temperature of 130°C, humidity of 85%, and applied voltage of 15V, and the time during which a short circuit occurred was confirmed, with a maximum of 1000 hours.

[0140] (3) Evaluation of electrical properties (dielectric breakdown strength) To evaluate the dielectric breakdown strength of photosensitive resin films obtained from photosensitive resin compositions, each photosensitive resin composition listed in Tables 1-3 was applied to a 13cm x 15cm, 0.7mm thick iron plate using a bar coater. The plate was exposed to light using a contact aligner type exposure apparatus at a wavelength of 405nm without a mask, and then heated in an oven at 180°C for 2 hours to obtain a photosensitive resin film. The photosensitive resin composition was applied so that the resulting film thickness was 0.2μm. Using this photosensitive resin film, a dielectric breakdown tester TM-5031AM (manufactured by Tama Densoku Co., Ltd.) was used to measure the voltage at which the test specimen broke down, starting with a voltage increase rate of 5V / sec. This voltage was then measured and defined as the dielectric breakdown strength of the film.

[0141] (4) Evaluation of solvent resistance To evaluate the solvent resistance to N-methyl-2-pyrrolidone (NMP), which is frequently used when forming semiconductor devices, a 15mm x 15mm pattern was formed on a silicon wafer using each of the photosensitive resin compositions listed in Tables 1-3, in the same manner as for wafer preparation for the copper migration test in (1). The wafer was then post-cured at 180°C for 2 hours while purging with nitrogen. After immersion of this wafer in NMP at 40°C for 1 hour, the change in film thickness and appearance were investigated, and the solvent resistance was evaluated. A ○ was used to indicate no change in appearance or film thickness, while a × was used to indicate swelling or film loss.

[0142] (5) Evaluation of adhesion Each photosensitive resin composition listed in Tables 1-3 was applied to a silicon wafer by spin coating, and a pre-bake was performed at 120°C for 2 minutes to produce a film (30 μm thick). A silicon wafer diced into 4 mm squares was thermocompressed onto each resulting film at 180°C, 2 MPa, and 600 seconds, and then post-cured at 180°C for 2 hours. Adhesion was evaluated by die shearing of these samples using a Nordson DAGE 4000 PXY bond tester at a measurement speed of 50.0 μm / sec and a measurement height of 50.0 μm. The average values ​​from 10 measurements for each composition are shown in Table 1.

[0143] The results are shown in Tables 4-6.

[0144] [Table 4]

[0145] [Table 5]

[0146] [Table 6]

[0147] From the above results, the photosensitive resin composition of the present invention, due to the presence of carboxyl groups and urethane bonds in the side chains, was able to form fine patterns that could not be achieved with conventional silicone resins containing epoxy or phenolic groups in the side chains and photosensitive resin compositions containing photoacid generators, and also exhibited high adhesion to the substrate. Furthermore, because the cured film has the above-mentioned properties, it can be suitably used as a protective film-forming material for various electrical and electronic components such as circuit boards, semiconductor elements, and display elements.

Claims

1. (A) A silicone resin having a sylphenylene skeleton, a polysiloxane skeleton and a fluorene skeleton in the main chain, and containing a urethane bond, a carboxyl group and an acryloyl group or a methacryloyl group in the side chain, and (B) Photoradical Generator A photosensitive resin composition containing [a specific substance].

2. (A) The photosensitive resin composition according to claim 1, wherein the silicone resin is a polymer comprising repeating units represented by the following formula (A1) and repeating units represented by the following formula (A2), and may further comprise at least one selected from repeating units represented by the following formula (A3) and repeating units represented by the following formula (A4). 【Chemistry 1】 [In the formula, R 1 ~R 4 Each is independently a hydrocarbyl group having 1 to 20 carbon atoms, which may contain heteroatoms. Each is independently an integer from 1 to 600. When m is an integer of 2 or more, each R 3 They may be the same or different from each other, and each R 4 They may be the same or different from each other. a, b, c, and d are numbers that satisfy 0 < a < 1, 0 < b < 1, 0 ≤ c < 1, 0 ≤ d < 1, and a + b + c + d = 1. X 1 X is a divalent group represented by the following formula (X1). 2 This is a divalent group represented by the following formula (X2). 【Chemistry 2】 (wherein, R 11 and R 12 are each independently a hydrogen atom or a methyl group. n 1 and n 2 are each independently an integer of 1 to 7. L 1 to L 4 are each independently a saturated hydrocarbylene group having 1 to 8 carbon atoms, and a part of -CH 2 - of the saturated hydrocarbylene group may be substituted with -O-, -S-, -SO 2 - or -CO-. In addition, -CH 2 - of the saturated hydrocarbylene group may be located at its terminal. R 13 to R 16 are each independently a hydrogen atom, a monovalent group represented by the following formula (Y) or a monovalent group represented by the following formula (Z), but all R 13 to R 16 among them, at least 10% of R 13 to R 16 are groups represented by the following formula (Y), and at least 10% of R 13 to R 16 are groups represented by the following formula (Z). The dashed line is a bond. 【Transformation 3】 (In the formula, L 5 This is a hydrocarbylene group having 2 to 14 carbon atoms, and the -CH of the hydrocarbylene group 2 Some of the hyphens are -O-, -S-, and -SO 2 It may be substituted with - or -CO-. Note that the -CH of the hydrocarbylene group 2 — may be located at the end of the sequence. R 17 L is a hydrogen atom or a methyl group. 6 This is a hydrocarbylene group having 2 to 14 carbon atoms, and the -CH of the hydrocarbylene group 2 Some of the hyphens are -O-, -S-, and -SO 2 It may be substituted with - or -CO-. Note that the -CH of the hydrocarbylene group 2 — may also indicate a terminal. A dashed line represents a joint. 【Chemistry 4】 (In the formula, R 21 and R 22 Each of these is independently either a hydrogen atom or a methyl group. 23 and R 24 These are, independently, hydrocarbyl groups having 1 to 8 carbon atoms. 1 and k 2 Each of the integers is independently between 0 and 7. p is an integer between 0 and 600. The dashed line represents a combination.

3. Furthermore, the photosensitive resin composition according to claim 1 further comprises a crosslinking agent having two or more (meth)acryloyl groups.

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

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

6. (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 5, (ii) A step of exposing the photosensitive resin film, and (iii) A step of developing the exposed photosensitive resin film using a developer to remove unexposed areas and form a pattern. A pattern formation method including the following.

7. Furthermore, the pattern forming method according to claim 6, further comprising the step of (iv) post-curing the photosensitive resin film, which has been patterned by development, at a temperature of 40 to 190°C.

8. A photosensitive resin composition according to any one of claims 1 to 5, which is a material for a protective coating for electrical and electronic components.

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