Photosensitive resin composition and pattern forming process

Abstract

To provide a photosensitive resin composition in which a fine pattern can be formed and a cured film has high chemical resistance or copper migration resistance even when cured at a low temperature below 150°C, and a pattern forming process thereof.SOLUTION: A photosensitive resin composition includes: (A) a silicone resin that has a silphenylene structure, a polysiloxane structure, and a fluorene structure at a main chain and has an acryloyl group or a methacryloyl group at a side chain; and (B) a photoradical generator.SELECTED DRAWING: None

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, photosensitive silicone compositions, etc. have been used as photosensitive semiconductor element protective films and insulating films for multilayer printed circuit boards. As a photosensitive material applied to the protection of such substrates and circuits, a photosensitive silicone composition mainly composed of a silicone polymer containing a silphenylene skeleton, which is particularly excellent in flexibility, has been proposed (Patent Document 1).

[0003] The cured film obtained from the composition has high chemical resistance, copper migration resistance, and reliability. On the other hand, since the PEB process is essential for forming a pattern because crosslinking does not proceed unless a post-exposure bake process (PEB process) is performed, the acid catalyst thermally diffuses to the unexposed area, making it difficult to fine the pattern. In addition, in recent years, low-temperature curing at less than 150°C has often been required to reduce the thermal load on the device side. However, when the composition is post-cured at 150°C or higher after development, it has high chemical resistance and copper migration resistance, but on the other hand, when the composition is post-cured at less than 150°C, there is a problem that the chemical resistance and copper migration resistance are significantly reduced. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2023-001980 A Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive resin composition capable of forming a fine pattern and capable of producing a cured film having high chemical resistance and copper migration resistance even when cured at a low temperature of less than 150°C, and a method for forming a pattern using the same. [Means for solving the problem]

[0006] Means for Solving the Problems The present inventors have conducted extensive research to achieve the above-mentioned object, and as a result have found that the above-mentioned object can be achieved by a photosensitive resin composition containing a silicone resin having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in its main chain and an acryloyl group or a methacryloyl group in its side chain, and a photoradical generator, and have thus completed the present invention.

[0007] That is, the present invention provides the following photosensitive resin composition and pattern forming method. 1. (A) a silicone resin having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in the main chain and an acryloyl group or a methacryloyl group in the side chain; and (B) Photoradical generator A photosensitive resin composition comprising: 2. A photosensitive resin composition according to claim 1, wherein the silicone resin (A) is a polymer containing 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 repeating unit selected from the group consisting of a repeating unit represented by the following formula (A3) and a repeating unit represented by the following formula (A4). [ka] (In the formula, R 1 ~R 4 are each independently a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. Each m is independently an integer of 1 to 600. When m is an integer of 2 or more, each R 3 may be the same or different, and each R 4may be the same as 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 ) 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 fine patterns that could not be achieved with conventional photosensitive resin compositions containing a silicone resin having an epoxy group or a phenol group in the side chain and a photoacid generator, and can give a cured film having high chemical resistance and copper migration resistance even when cured at a low temperature of less than 150° C. In addition, since the cured film has the above-mentioned properties, it can be suitably used as a film-forming material for protecting various electric and electronic parts such as circuit boards, semiconductor elements, and display elements. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] [Photosensitive resin composition] The photosensitive resin composition of the present invention contains (A) a silicone resin having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in its main chain and an acryloyl group or a methacryloyl group in its side chain, and (B) a photoradical generator.

[0010] [(A) Silicone resin] (A) The silicone resin is a polymer having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in the main chain and an acryloyl group or a methacryloyl group in the side chain. Such a silicone resin is not particularly limited, but preferably includes a repeating unit represented by the following formula (A1) and a repeating unit represented by the following formula (A2), and further includes 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 < 0.3, 0 ≤ d < 0.3, and a + b + c + d = 1, and more preferably numbers satisfying 0.35 < a < 0.75, 0.35 < b < 0.75, 0 ≤ c < 0.15, 0 ≤ d < 0.15, and a + b + c + d = 1.

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

[0013] In formulas (A2) and (A4), when there are two or more siloxane units (that is, when m is an integer of 2 or more), each siloxane unit may all be the same, or may contain two or more different siloxane units. When containing two or more different siloxane units, the siloxane units may be randomly bonded, alternately bonded, or may contain a plurality of blocks of the same kind of siloxane unit.

[0014] In formulas (A1) and (A2), X 1 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] (The dashed lines represent bonds.)

[0015] In formula (X1), R 11 ~R 14 are each independently a hydrogen atom or a methyl group, R 11 and R 12 and R are preferably both hydrogen atoms.

[0016] In formula (X1), n 1 and n 2 are each independently an integer of 1 to 7, and preferably 1.

[0017] In formula (X1), L 1 and L 2 are each independently a saturated hydrocarbylene group having 1 to 15 carbon atoms, a part of the -CH2- of the saturated hydrocarbylene group may be substituted with -O-, -S-, -SO2-, -CO- or -CONH-, and a part or all of the hydrogen atoms of the saturated hydrocarbylene group may be substituted with a hydroxy group. The -CH2- of the saturated hydrocarbylene group may be located at its terminal.

[0018] The saturated hydrocarbylene group may be linear, branched, or cyclic. Specific examples thereof include a methanediyl group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,2-diyl group, a hexane-1,3-diyl group, a hexane-1,4-diyl group, a hexane-1,5-diyl group, a hexane-1,6-diyl group, a hexane-1,7-diyl group, a hexane-1,8-diyl group, a hexane-1,9-diyl group, a hexane-1,8-diyl group, a hexane-1,9-diyl group, a hexane-1,9-diyl group, a hexane-1,8-diyl group, a hexane-1,9-diyl group, a hexane-1,9-diyl group, a hexane-1,9-diyl group, a hexane-1,9-diyl group, a hexane-1,1 ... alkanediyl groups having 1 to 15 carbon atoms, such as 1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl group, and pentadecane-1,15-diyl; and cyclic saturated hydrocarbylene groups having 3 to 15 carbon atoms, such as cyclopentanediyl group, cyclohexanediyl group, norbornanediyl group, and adamantanediyl group.

[0019] L 1 and L 2 Preferably, both of these have 1 to 8 carbon atoms, and more preferably, one or more hydrogen atoms are substituted with a hydroxy group, or one or more -CH2- are substituted with -CONH-.

[0020] In formulas (A3) and (A4), X 2 is a divalent group represented by the following formula (X2). [ka] (The dashed lines represent bonds.)

[0021] In formula (X2), R 21 and R 22 are each independently a hydrogen atom or a methyl group, and preferably a hydrogen atom.

[0022] In formula (X2), R 23 and R 24 are each independently a hydrocarbyl group having 1 to 8 carbon atoms.

[0023] In formula (X2), k 1 and k 2are each independently an integer of 0 to 7, and are preferably 0.

[0024] In formula (X2), p is an integer of 0 to 600, preferably an integer of 0 to 100, and more preferably an integer of 0 to 30. When p is an integer of 2 or more, each R 23 may be the same or different, and each R 24 They may be the same or different.

[0025] The silicone resin (A) preferably has a weight average molecular weight (Mw) of 2000 to 500000, more preferably 4000 to 100000. If the Mw is within the above range, the polymer can be obtained as a solid, and film-forming properties can be ensured. In the present invention, the Mw is a value measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an elution solvent.

[0026] The (A) silicone resin may be a repeating unit represented by formula (A1), a repeating unit represented by formula (A2), a repeating unit represented by formula (A3), and a repeating unit represented by formula (A4) that are bonded randomly or alternately, or may contain a plurality of blocks of each unit.

[0027] [(A) Method for producing silicone resin] The method for producing the (A) silicone resin is not particularly limited, but the resin can be produced, for example, by addition polymerization of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3), and, if necessary, a compound represented by the following formula (4), in the presence of a metal catalyst. [ka] (In the formula, R 1 ~R 4 and m are the same as above.)

[0028] [ka] (In the formula, R 11 ~R 14 , n 1 , n 2 , L 1 and L 2 is the same as above.)

[0029] [ka] (In the formula, R 21 ~R 24 , k 1 , k 2 and p is the same as above.

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

[0031] The amount of the catalyst used is a catalytic amount, and is usually preferably 0.001 to 0.1 mass% as platinum group metal relative to the total amount of the reaction polymer. In the polymerization reaction, a solvent may be used as necessary. For example, a hydrocarbon solvent such as toluene or xylene is preferable. As the polymerization conditions, from the viewpoint of not deactivating the catalyst and being able to complete the polymerization in a short time, the polymerization temperature is preferably, for example, 40 to 150°C, and particularly preferably 60 to 120°C. The polymerization time depends on the type and amount of the polymer, but is preferably about 0.5 to 100 hours, and particularly preferably 0.5 to 30 hours, in order to prevent moisture from entering the polymerization system. After the polymerization reaction is completed, if a solvent is used, it can be distilled off to obtain the silicone resin (A).

[0032] The reaction method is not particularly limited, but it is preferable to mix and heat the compound represented by formula (3) and, if necessary, the compound represented by formula (4), add a metal catalyst to the mixed solution, and then dropwise add the compound represented by formula (1) and the compound represented by formula (2) over 0.1 to 5 hours.

[0033] The raw material compounds are preferably blended so that the molar ratio of the total of the hydrosilyl groups in the compound represented by formula (1) and the compound represented by formula (2) to the total of the alkenyl groups in the compound represented by formula (3) and the compound represented by formula (4) is 0.67 to 1.67, more preferably 0.83 to 1.25. The Mw of the (A) silicone resin can be controlled by using a monoallyl compound such as o-allylphenol, or a monohydrosilane or monohydrosiloxane such as triethylhydrosilane as a molecular weight regulator.

[0034] In the polymerization reaction, a polymerization inhibitor may be used optionally. Examples of the polymerization inhibitor include various phenols, hydroquinones, benzoquinones, catechols, hydroxyamines, and nitroso compounds. The amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 5% by mass, based on the compound represented by formula (3).

[0035] After the reaction is completed, a solvent is optionally added, the mixture is washed with water, and the organic layer is heated under reduced pressure to remove the solvent, thereby obtaining silicone resin (A). When washing with water, an aqueous solution of a metal hydroxide such as sodium hydroxide or potassium hydroxide, or a metal carbonate or metal hydrogen carbonate such as sodium carbonate, sodium hydrogen carbonate, or potassium carbonate may be used.

[0036] Another method for producing the silicone resin (A) includes a reaction between a polymer (hereinafter also referred to as polymer B) which contains a repeating unit represented by the following formula (B1) and a repeating unit represented by the following formula (B2), and which may further contain at least one repeating unit selected from a repeating unit represented by the following formula (B3) and a repeating unit represented by the following formula (B4), and a compound represented by the following formula (5). [ka] (In the formula, R 1 ~R 4 , m, a, b, c, d and X 2 is the same as above.) [ka]

[0037] In formulas (B1) and (B2), X 3 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 , R12 , n 1 and n 2 is the same as above. The dashed lines indicate bonds.)

[0038] In formula (5), R 31 is a hydrogen atom or a methyl group.

[0039] In formula (5), L 3 is a saturated hydrocarbylene group having 1 to 14 carbon atoms, some of the -CH2- 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 hydroxy groups. 3 The saturated hydrocarbylene group represented by the following formula (1) may be linear, branched, or cyclic, but preferably has 1 to 7 carbon atoms.

[0040] Specific examples of the compound represented by formula (5) include, but are not limited to, 2-acryloyloxyethyl isocyanate (Karenz AOI (registered trademark) manufactured by Showa Denko K.K.), 2-methacryloyloxyethyl isocyanate (Karenz MOI (registered trademark) manufactured by Showa Denko K.K.), and 2-(2-methacryloyloxyethyloxy)ethyl isocyanate (Karenz MOI-EG (registered trademark) manufactured by Showa Denko K.K.).

[0041] The reaction conditions are not particularly limited, but usually, the polymer B and the compound represented by formula (5) are mixed in a solvent and heated. As the solvent, from the viewpoint of promoting the reaction while suppressing side reactions, it is preferable to use an aprotic polar solvent, 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. From the viewpoint of preventing side reactions and being able to complete the reaction in a short time, the reaction temperature is preferably, for example, 35 to 130°C, and particularly preferably 45 to 100°C. The reaction time, which depends on the type and amount of the reaction substrate, is preferably about 0.5 to 50 hours, and particularly preferably 0.5 to 24 hours.

[0042] In the reaction, the compounding ratio of the polymer B and the compound represented by formula (5) is 3 The compound represented by formula (5) is preferably blended in such an amount that the molar ratio of the compound represented by formula (5) is 1.80 to 2.20, and more preferably 1.95 to 2.10, relative to the total amount of the compound represented by formula (5). Only one type of compound may be used, or two or more types of compounds may be used in combination.

[0043] In the reaction, a catalyst may be used optionally. Examples of the catalyst 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 laurate, dibutyltin diacetate, and dimethyltin. organic tin compounds such as dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dilaurate (dibutyltin(IV) dilaurate), dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, and dibutyltin dichloride; organic lead compounds such as lead octoate and lead naphthenate; organic nickel compounds such as nickel naphthenate; organic cobalt compounds such as cobalt naphthenate; organic copper compounds such as copper octoate; organic bismuth compounds such as bismuth octoate and bismuth neodecanoate; and potassium salts such as potassium carbonate, potassium acetate, and potassium octoate.

[0044] The amount of the catalyst used is usually a catalytic amount, and X in the polymer B 3The amount of the catalyst is preferably 0.1 to 20 mol % based on the total amount of the catalyst. The catalyst may be used alone or in combination of two or more kinds.

[0045] In the reaction, a polymerization inhibitor may be used optionally. Examples of the polymerization inhibitor include various phenols, hydroquinones, benzoquinones, catechols, hydroxyamines, and nitroso compounds. The amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.001 to 10% by mass, and more preferably 0.01 to 5% by mass, based on the compound represented by formula (3).

[0046] After the reaction is completed, a solvent is optionally added, the mixture is washed with water, and the organic layer is heated under reduced pressure to remove the solvent, thereby obtaining silicone resin (A). When washing with water, an aqueous solution of a metal hydroxide such as sodium hydroxide or potassium hydroxide, or a metal carbonate or metal hydrogen carbonate such as sodium carbonate, sodium hydrogen carbonate, or potassium carbonate may be used.

[0047] Furthermore, another method for producing the silicone resin (A) includes a reaction between a polymer B and a compound represented by the following formula (6). [ka]

[0048] In formula (6), R 41 is a hydrogen atom or a methyl group.

[0049] In formula (6), L 4 is a divalent saturated hydrocarbylene group having 1 to 13 carbon atoms, some of the -CH2- groups 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 hydroxy groups. 3 The saturated hydrocarbylene group represented by the following formula (1) may be linear, branched, or cyclic, but preferably has 1 to 6 carbon atoms.

[0050] The reaction conditions are not particularly limited, but usually, the polymer B and the compound represented by formula (6) are mixed in a solvent and heated. As the solvent, from the viewpoint of promoting the reaction while suppressing side reactions, it is preferable to use an aprotic polar solvent, 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. From the viewpoint of preventing side reactions and being able to complete the reaction in a short time, the reaction temperature is, for example, preferably 35 to 130°C, and particularly preferably 45 to 100°C. The reaction time, which depends on the type and amount of the reaction substrate, is preferably about 0.5 to 50 hours, and particularly preferably 0.5 to 24 hours.

[0051] In the reaction, the compounding ratio of the polymer B and the compound represented by formula (6) is 3 The compound represented by formula (6) is preferably blended in such an amount that the molar ratio of the compound represented by formula (6) is 1.60 to 3.00, and more preferably 1.90 to 2.00, relative to the total amount of the compound represented by formula (6). Only one type of compound represented by formula (6) may be used, or two or more types of compounds may be used in combination.

[0052] In the reaction, a catalyst may be used as desired. Examples of the catalyst 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; potassium salts such as potassium hydroxide, potassium carbonate, potassium acetate, and potassium octylate; and sodium salts such as sodium hydroxide, sodium carbonate, sodium acetate, and sodium octylate.

[0053] The amount of the catalyst used is usually a catalytic amount, and X in the polymer B3 The amount of the catalyst is preferably 0.1 to 20 mol % based on the total amount of the catalyst. The catalyst may be used alone or in combination of two or more kinds.

[0054] In the reaction, a polymerization inhibitor may be used optionally. Examples of the polymerization inhibitor that can be used include various phenols, hydroquinones, benzoquinones, catechols, hydroxyamines, and nitroso compounds. The amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 5% by mass, based on the compound represented by formula (6).

[0055] After the reaction is completed, a solvent is optionally added, the mixture is washed with water, and the organic layer is heated under reduced pressure to remove the solvent, thereby obtaining silicone resin (A). When washing with water, an aqueous solution of a metal hydroxide such as sodium hydroxide or potassium hydroxide, or a metal carbonate or metal hydrogen carbonate such as sodium carbonate, sodium hydrogen carbonate, or potassium carbonate may be used.

[0056] Another method for producing the silicone resin (A) includes a reaction between a polymer (hereinafter also referred to as polymer C) that contains a repeating unit represented by the following formula (C1) and a repeating unit represented by the following formula (C2), and that may further contain at least one repeating unit selected from a repeating unit represented by the following formula (C3) and a repeating unit represented by the following formula (C4), and acrylic acid or methacrylic acid. [ka] (In the formula, R 1 ~R 4 , m, a, b, c, d and X 2 is the same as above.)

[0057] In formulas (C1) and (C2), X 4 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 is the same as above. The dashed lines indicate bonds.)

[0058] In formula (X4), L 5 and L 6 are each independently a saturated hydrocarbylene group having 1 to 13 carbon atoms, in which some of the -CH2- groups 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 hydroxy groups. 5 and L 6 The saturated hydrocarbylene group represented by the following formula (1) may be linear, branched, or cyclic, but preferably has 1 to 6 carbon atoms.

[0059] The reaction conditions are not particularly limited, but usually, the polymer C and acrylic acid or methacrylic acid are mixed in a solvent and heated. As the solvent, from the viewpoint of promoting the reaction, it is preferable to use a polar solvent, and it is particularly preferable to use an alcohol solvent such as propylene glycol monomethyl ether. From the viewpoint of preventing side reactions and enabling the reaction to be completed in a short time, the reaction temperature is preferably, for example, 35 to 130°C, and particularly preferably 60 to 110°C. 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.

[0060] In the above reaction, the compounding ratio of polymer C and acrylic acid or methacrylic acid is X in polymer C. 4 The molar ratio of acrylic acid or methacrylic acid to the total amount of the monomer is preferably 2.00 to 10.00, and more preferably 3.00 to 8.00. Either acrylic acid or methacrylic acid may be used alone, or both may be used in combination.

[0061] In the reaction, a catalyst may be used optionally. Examples of the catalyst 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; and imidazoles such as imidazole and 2-ethyl-4-methylimidazole.

[0062] The amount of catalyst used is usually a catalytic amount, and X in polymer C 4 The amount of the catalyst is preferably 0.1 to 20 mol % based on the total amount of the catalyst. The catalyst may be used alone or in combination of two or more kinds.

[0063] In the reaction, a polymerization inhibitor may be used optionally. Examples of the polymerization inhibitor include various phenols, hydroquinones, benzoquinones, catechols, hydroxyamines, and nitroso compounds. The amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.001 to 10% by mass, and more preferably 0.01 to 5% by mass, based on the acrylic acid or methacrylic acid.

[0064] After the reaction is completed, a solvent is optionally added, the mixture is washed with water, and the organic layer is heated under reduced pressure to remove the solvent, thereby obtaining silicone resin (A). When washing with water, an aqueous solution of a metal hydroxide such as sodium hydroxide or potassium hydroxide, or a metal carbonate or metal hydrogen carbonate such as sodium carbonate, sodium hydrogen carbonate, or potassium carbonate may be used.

[0065] [(B) Photoradical generator] The photoradical generator (B), component, is not particularly limited as long as it is a compound that generates radicals upon exposure to light. Specific examples thereof include acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, benzoin-based compounds, triazine-based compounds, and oxime-based compounds.

[0066] Specific examples of the acetophenone-based 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, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and the like.

[0067] Specific examples of the benzophenone-based compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

[0068] Specific examples of the thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

[0069] Specific examples of the benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

[0070] Specific examples of the triazine-based compound 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, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, riazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-s-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, and the like.

[0071] Specific examples of the oxime compounds include 1,2-octanedione, O-acyloxime compounds, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, and the like. Specific examples of the O-acyloxime compound include 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1-one oxime-O-acetate, and 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O-acetate.

[0072] Specific examples of the phosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like.

[0073] In addition to the above-mentioned compounds, the (B) photoradical generator may also be a carbazole-based compound, a diketone compound, a sulfonium borate-based compound, a diazo-based compound, an imidazole-based compound, a non-imidazole-based compound, a fluorene-based compound, or the like.

[0074] In the photosensitive resin composition of the present invention, the content of the photoradical generator (B) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the component (A). When the content of the photoradical generator is within the above range, a well-balanced sensitivity and developability during exposure can be obtained, a pattern with excellent resolution can be obtained without residual film, and a cured film with high reliability can be obtained. The photoradical generator (B) may be used alone or in combination of two or more kinds.

[0075] [(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 is preferably a crosslinking agent having two or more functional (meth)acryloyl groups.

[0076] Specific examples of crosslinking agents having two or more functional (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, trimethylolpropanediol di(meth)acrylate, and ethylene glycol di(meth)acrylate. Pentaerythritol tri(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 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, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glyceryl Examples of suitable monomers include polyfunctional monomers such as polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., a reaction product of tolylene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, or the like, with 2-hydroxyethyl (meth)acrylate), methylene bis(meth)acrylamide, (meth)acrylamide methylene ether, and a condensation product of a polyhydric alcohol and N-methylol (meth)acrylamide, as well as triacryl formal.

[0077] When the photosensitive resin composition of the present invention contains a crosslinking agent (C), the content thereof is preferably 0.5 to 100 parts by mass, and more preferably 1 to 50 parts by mass, per 100 parts by mass of the component (A). The crosslinking agent (C) may be used alone or in combination of two or more kinds.

[0078] [(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 a substrate.

[0079] Examples of the (D) silane coupling agent 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. Among these, (meth)acryloyl group-containing silane coupling agents are preferred.

[0080] 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 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.).

[0081] When the photosensitive resin composition of the present invention contains a silane coupling agent (D), the content thereof is preferably 0.5 to 20 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of the component (A). The silane coupling agent (D) may be used alone or in combination of two or more kinds.

[0082] [(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 above-mentioned components (A) to (D) and other various additives.

[0083] The (E) solvent is preferably an organic solvent, and examples thereof 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, 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, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether acetate, and γ-butyrolactone.

[0084] As the (E) solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclopentanone, and mixed solvents thereof are preferable, which have excellent solubility for the (A) silicone resin and the (B) photoradical generator.

[0085] The content of the component (E) is preferably 25 to 85% by mass, and more preferably 30 to 80% by mass, based on the total amount of the photosensitive resin composition, from the viewpoints of compatibility and viscosity of the photosensitive resin composition. The solvent (E) may be used alone or in combination of two or more kinds.

[0086] The photosensitive resin composition of the present invention can be prepared by a conventional method, for example, by stirring and mixing the above-mentioned components, and then filtering the solid content with a filter or the like as necessary.

[0087] The photosensitive resin composition of the present invention thus prepared can be suitably used as a film-forming material for protecting various electric and electronic parts such as circuit boards, semiconductor elements, and display elements.

[0088] [Pattern formation method] The pattern forming method using the photosensitive resin composition of the present invention comprises the steps of: (i) forming a photosensitive resin film on a substrate using the photosensitive resin composition of the present invention; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to form a pattern. It includes.

[0089] Step (i) is a step of forming a photosensitive resin film on a substrate using the photosensitive resin composition. Examples of the substrate include silicon wafers, silicon wafers for through-hole electrodes, silicon wafers thinned by backside polishing, plastic or ceramic substrates, and substrates having metals such as Ni and Au on the entire surface or part of the substrate by ion sputtering or plating. Substrates having irregularities may also be used.

[0090] The photosensitive resin film may be formed, for example, by applying the photosensitive resin composition onto a substrate and pre-heating (pre-baking) as necessary. The application method may be a known method, such as a dip method, a spin coating method, or a roll coating method. The amount of the photosensitive resin composition applied may be appropriately selected depending on the purpose, but it is preferable to apply the composition so that the thickness of the resulting photosensitive resin film is preferably 0.1 to 200 μm, more preferably 1 to 150 μm.

[0091] In order to improve the film thickness uniformity on the substrate surface, a solvent may be dropped onto the substrate before applying the photosensitive resin composition (pre-wetting method). The solvent and the amount of the dropped solvent can be appropriately selected depending on the purpose. As the solvent, for example, alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, glycols such as PGME, etc. are preferable, but it is also possible to use a solvent used in the photosensitive resin composition.

[0092] Here, in order to efficiently carry out the photocuring reaction, pre-baking may be carried out as necessary to evaporate the solvent etc. Pre-baking can be carried out, for example, at 40 to 140° C. for about 1 minute to 1 hour.

[0093] Next, (ii) the photosensitive resin film is exposed to light. In this case, the exposure is preferably performed with light having a wavelength of 10 to 600 nm, and more preferably with light having a wavelength of 190 to 500 nm. Examples of light having such wavelengths include light of various wavelengths generated by a radiation generator, such as ultraviolet rays such as g-rays, h-rays, and i-rays, and far ultraviolet rays (248 nm, 193 nm). Of these, light having a wavelength of 248 to 436 nm is particularly preferred. The exposure dose is 10 to 10,000 mJ / cm. 2 In the present invention, the crosslinking reaction proceeds in the exposed area even without the PEB step, and an insolubilized pattern that is insoluble in an organic solvent, which is a developer, is formed. By not performing the PEB step, the catalytic species generated in the exposed area is prevented from thermally diffusing to the unexposed area, and thus finer patterns can be achieved.

[0094] The exposure may be performed through a photomask. The photomask may be, for example, a photomask having a desired pattern cut out. The material of the photomask is not particularly limited, but is preferably one that blocks light of the wavelengths. For example, a photomask having a light-shielding film made of chromium or the like is preferably used.

[0095] After exposure, (iii) the photosensitive resin film is developed with a developer to form a pattern. As the developer, for example, organic solvents such as alcohols such as IPA, ketones such as cyclohexanone, and glycols such as PGME are preferable, but it is also possible to use a solvent used in the photosensitive resin composition. As a development method, a normal method, for example, a method of immersing a substrate on which a pattern has been formed in the developer, can be mentioned. The non-exposed portion is dissolved and removed by organic solvent development to form a pattern. Thereafter, washing, rinsing, drying, etc. are performed as necessary to obtain a resin film having a desired pattern.

[0096] Furthermore, (iv) the film on which the pattern is formed can be post-cured at a low temperature of 40 to 140°C using an oven or a hot plate. If the post-curing temperature is 40 to 140°C, the crosslinking density of the photosensitive resin composition can be increased without damaging the laminated semiconductor element, and the cured film can have high chemical resistance, copper migration resistance, and reliability. The post-curing time is preferably 10 minutes to 12 hours, more preferably 1 hour to 6 hours. If the photosensitive resin composition of the present invention is used, a film having excellent various cured film properties can be obtained even if the post-curing is performed at a low temperature of about 40 to 140°C. The thickness of the cured film after post-curing is usually 1 to 200 μm, preferably 5 to 50 μm.

[0097] When it is not necessary to form a pattern, for example when it is desired to simply form a uniform film, in step (ii) of the pattern formation method, the film can be formed by exposing the film to light of an appropriate wavelength without using the photomask.

[0098] The film obtained from the photosensitive resin composition can ensure high chemical resistance, copper migration resistance, and reliability despite being cured at a low temperature, and can be suitably used as a film-forming material for protecting various electric and electronic parts such as circuit boards, semiconductor elements, and display elements. EXAMPLES

[0099] The present invention will be described in more detail below with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples. Note that Mw was measured by GPC using a TSKgel Super HZM-H (manufactured by Tosoh Corporation) column under analysis conditions of a flow rate of 0.6 mL / min, an elution solvent of THF, and a column temperature of 40° C., with monodisperse polystyrene as the standard.

[0100] The compounds used in the synthesis of the polymer are shown below. [ka]

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] [ka]

[0105] [ka]

[0106] [ka]

[0107] [1] Synthesis of silicone resin [Synthesis Example 1] Synthesis of Silicone Resin A1 In a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 361g (0.45 mol) of the compound represented by formula (S-2a) and 715g (1.00 mol) of the compound represented by formula (S-3a) were added, followed by adding 1800g of toluene and heating to 70°C. Then, 1.5g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 105g (0.54 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total of hydrosilyl groups: total of alkenyl groups = 0.99: 1 (molar ratio)). After the dropwise addition, the mixture was heated to 100°C and aged for 7 hours, after which toluene was distilled off from the reaction solution under reduced pressure to obtain silicone resin A1. The Mw of silicone resin A1 was 12000. The silicone resin A1 was 1 It was confirmed by 1 H-NMR (Bruker) that the polymer contained a repeating unit represented by formula (A1) and a repeating unit represented by formula (A2).

[0108] [Synthesis Example 2] Synthesis of Silicone Resin A2 In a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 1513g (0.50 mol) of the compound represented by formula (S-2b), 606g (0.85 mol) of the compound represented by formula (S-3b), and 28.0g (0.15 mol) of the compound represented by formula (S-4) were added, and then 3000g of toluene was added and heated to 80°C. Then, 2.5g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 95.3g (0.49 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total of hydrosilyl groups: total of alkenyl groups = 0.99: 1 (molar ratio)). After the dropwise addition, the mixture was heated to 105°C and aged for 10 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain silicone resin A2. The Mw of silicone resin A2 was 18000. The silicone resin A2 was 1 H-NMR (Bruker) confirmed that the polymer contained repeating units represented by formula (A1), repeating units represented by formula (A2), repeating units represented by formula (A3) and repeating units represented by formula (A4).

[0109] [Synthesis Example 3] Synthesis of Silicone Resin A3 In a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 908g (0.30 mol) of the compound represented by formula (S-2b), 387g (0.90 mol) of the compound represented by formula (S-5a) and 18.6g (0.10 mol) of the compound represented by formula (S-4) were added, and then 2100g of toluene was added and heated to 70°C. Then, 1.0g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 134g (0.69 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total of hydrosilyl groups: total of alkenyl groups = 0.99: 1 (molar ratio)). After the dropwise addition, the mixture was heated to 90°C and aged for 11 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain a polymer. 2500g of propylene glycol monomethyl ether acetate was added to this polymer, and after confirming that it was dissolved, 279g (1.80mol) of the compound represented by formula (S-6a) and 5.06g (0.05mol) of triethylamine were added and heated at 50°C for 12 hours. After the reaction was completed, propylene glycol monomethyl ether acetate and triethylamine were distilled off from the reaction solution under reduced pressure to obtain silicone resin A3. Mw of silicone resin A3 was 14000. Silicone resin A3 was, 1 H-NMR (Bruker) confirmed that the polymer contained repeating units represented by formula (A1), repeating units represented by formula (A2), repeating units represented by formula (A3) and repeating units represented by formula (A4).

[0110] [Synthesis Example 4] Synthesis of Silicone Resin A4 A 10L flask equipped with a stirrer, a thermometer, a nitrogen purge device and a reflux condenser was charged with 401g (0.50 mol) of the compound represented by formula (S-2a) and 431g (1.00 mol) of the compound represented by formula (S-5a), followed by 1900g of toluene and heating to 80°C. Then, 1.4g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was charged, and 95.3g (0.49 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total of hydrosilyl groups: total of alkenyl groups = 0.99: 1 (molar ratio)). After the dropwise addition was completed, the mixture was heated to 100°C and aged for 12 hours, after which toluene was distilled off under reduced pressure from the reaction solution to obtain a polymer. After adding 1800 g of propylene glycol monomethyl ether acetate to this polymer and confirming that it was dissolved, 312 g (2.00 mol) of the compound represented by formula (S-6b) and 10.1 g (0.10 mol) of triethylamine were added and heated at 70°C for 10 hours. After the reaction was completed, the propylene glycol monomethyl ether acetate and triethylamine were distilled off from the reaction solution under reduced pressure to obtain silicone resin A4. The Mw of silicone resin A4 was 13,000. Silicone resin A4 was, 1 H-NMR (Bruker) confirmed that the polymer contained repeating units represented by formula (A1), repeating units represented by formula (A2), repeating units represented by formula (A3) and repeating units represented by formula (A4).

[0111] [Synthesis Example 5] Synthesis of Silicone Resin A5 In a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 321g (0.40 mol) of the compound represented by formula (S-2a), 499g (0.92 mol) of the compound represented by formula (S-5b) and 14.9g (0.08 mol) of the compound represented by formula (S-4) were added, followed by adding 700g of toluene and heating to 90°C. Then, 1.3g of a chloroplatinic acid toluene solution (platinum concentration 0.5% by mass) was added, and 115g (0.59 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total of hydrosilyl groups: total of alkenyl groups = 0.99: 1 (molar ratio)). After the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, after which toluene was distilled off under reduced pressure from the reaction solution to obtain a polymer. 1000g of propylene glycol monomethyl ether was added to this polymer, and after confirming that it was dissolved, 475g (5.52mol) of methacrylic acid and 24.1g (0.092mol) of triphenylphosphine were added and heated at 110°C for 12 hours. After the reaction was completed, propylene glycol monomethyl ether and methacrylic acid were distilled off from the reaction solution under reduced pressure to obtain silicone resin A5. Mw of silicone resin A5 was 15000. Silicone resin A5 was, 1 H-NMR (Bruker) confirmed that the polymer contained repeating units represented by formula (A1), repeating units represented by formula (A2), repeating units represented by formula (A3) and repeating units represented by formula (A4).

[0112] [Comparative Synthesis Example 1] Synthesis of Comparative Silicone Resin A'1 A 3L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser was charged with 215.0g (0.5 mol) of the compound represented by formula (S-5a), followed by 2000g of toluene, and heated to 70°C. Then, 1.0g of a chloroplatinic acid toluene solution (platinum concentration 0.5% by mass) was charged, and 67.9g (0.35 mol) of the compound represented by formula (S-1) and 453.0g (0.15 mol) of the compound represented by formula (S-2b) were dropped over 1 hour (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, after which toluene was distilled off under reduced pressure from the reaction solution to obtain a comparative silicone resin A'1. The Mw of the comparative silicone resin A'1 was 62000.

[0113] [Comparative Synthesis Example 2] Synthesis of Comparative Silicone Resin A'2 A 3L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser was charged with 53.00g (0.20 mol) of the compound represented by formula (S-7) and 162.6g (0.30 mol) of the compound represented by formula (S-5b), then 2000g of toluene was added and heated to 70°C. Then, 1.0g of a chloroplatinic acid toluene solution (platinum concentration 0.5% by mass) was charged, and 48.5g (0.25 mol) of the compound represented by formula (S-1) and 755.0g (0.25 mol) of the compound represented by formula (S-2b) were dropped over 1 hour (total of hydrosilyl groups / total of alkenyl groups = 1 / 1 (molar ratio)). After the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, after which toluene was distilled off under reduced pressure from the reaction solution to obtain a comparative silicone resin A'2. The Mw of the comparative silicone resin A'2 was 83,000.

[0114] [Comparative Synthesis Example 3] Synthesis of Comparative Silicone Resin A'3 A 3L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser was charged with 27.9g (0.15 mol) of the compound represented by formula (S-4), 27.1g (0.05 mol) of the compound represented by formula (S-5b) and 129.0g (0.30 mol) of the compound represented by formula (S-5a), then 2,000g of toluene was added and heated to 70°C. Then, 1.0g of a chloroplatinic acid toluene solution (platinum concentration 0.5% by mass) was added, and 87.3g (0.45 mol) of the compound represented by formula (S-1) and 79.3g (0.05 mol) of the compound represented by formula (S-2a) were added dropwise over 1 hour (total of hydrosilyl groups / total of alkenyl groups = 1 / 1 (molar ratio)). After the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, after which toluene was distilled off under reduced pressure from the reaction solution to obtain a comparative silicone resin A'3. The Mw of the comparative silicone resin A'3 was 24,000.

[0115] [2] Preparation of photosensitive resin composition [Examples 1 to 14 and Comparative Examples 1 to 12] The components were mixed according to the amounts shown in Tables 1 and 2, then dissolved by stirring at room temperature, and then microfiltered through a 1.0 μm Teflon (registered trademark) filter to prepare the photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 12.

[0116] [Table 1]

[0117] [Table 2]

[0118] In Tables 1 and 2, B1 to B4 and B'1 to B'2 are as follows. [ka]

[0119] In Tables 1 and 2, C1 to C2 and C'1 to C'2 are as follows. [ka]

[0120] In Tables 1 and 2, D1 is manufactured by Shin-Etsu Chemical Co., Ltd. under the trade name "KBM-503" (3-methacryloxypropyltrimethoxysilane), and D2 is manufactured by Shin-Etsu Chemical Co., Ltd. under the trade name "KBM-403" (3-glycidoxypropyltrimethoxysilane).

[0121] [5] Evaluation of resin coating (1) Pattern formation and its evaluation Each photosensitive resin composition was coated to a thickness of 20 μm using a spin coater on a migration test substrate (a comb-shaped electrode substrate with copper conductive material, conductive part spacing and width of 20 μm, and conductive part thickness of 4 μm). In order to remove the solvent from the composition, the substrate was heated and dried at 100° C. for 5 minutes using a hot plate to obtain a photosensitive resin film. The obtained photosensitive resin film was irradiated with light of 365 nm wavelength at 500 mJ / cm through a quartz mask having a set of equal-width lines and spaces with line widths ranging from 1 μm to 50 μm. 2 The exposure was performed using a stepper type exposure device NSR-1755i7A manufactured by Nikon Corporation. The exposed photosensitive resin film was then spray-developed with PGMEA for 180 seconds to form a pattern. At this time, in Comparative Examples 1 to 12, since the exposed parts were all developed, a post-exposure bake (PEB) was performed. The PEB process was performed under optimized conditions of 140°C and 5 minutes, and development was performed in the same manner. Finally, the photosensitive resin film on the substrate on which the pattern was formed was post-cured using an oven at 120°C for 2 hours while purging with nitrogen, and then observed. The cross section of the pattern was observed by SEM, and the minimum pattern size resolved was taken as the limiting resolution. Furthermore, the perpendicularity was evaluated from the obtained cross-sectional photograph, and a perpendicular pattern was marked with ◎, a tapered shape or footing was slightly observed with ○, a tapered shape or footing was strongly observed with △, and an opening defect was marked with ×.

[0122] (2) Evaluation of electrical properties (copper migration) The substrate on which the pattern was formed by the method in (1) was used as the substrate for copper migration evaluation, and the test was carried out under the conditions of a temperature of 130°C, humidity of 85%, and an applied voltage of 15 V. The time until a short circuit occurred was confirmed up to an upper limit of 1000 hours.

[0123] (3) Evaluation of electrical properties (dielectric breakdown strength) In order to evaluate the dielectric breakdown strength of the photosensitive resin film obtained from the photosensitive resin composition, each photosensitive resin composition described in Tables 1 and 2 was applied to a 13 cm x 15 cm, 0.7 mm thick iron plate using a bar coater, exposed to light using a contact aligner type exposure device without a mask under exposure conditions of a wavelength of 405 nm, and then heated at 100 ° C. for 2 hours using an oven to obtain a photosensitive resin film. The photosensitive resin composition was applied so that the film thickness obtained was 0.2 μm. Using this photosensitive resin film, a voltage was applied at a voltage rise rate of 5 V / sec using a dielectric breakdown tester TM-5031AM (manufactured by Tama Densoku Co., Ltd.), and the voltage at which the test specimen broke was measured and used as the dielectric breakdown strength of the film.

[0124] (4) Evaluation of solvent resistance In order to evaluate the solvent resistance to N-methyl-2-pyrrolidone (NMP), which is often used when forming semiconductor elements, etc., a 15 mm x 15 mm pattern was formed on a silicon wafer using each photosensitive resin composition listed in Tables 1 and 2 in the same manner as in the wafer preparation for the copper migration test in (1), and post-cured at 110°C for 2 hours while purging with nitrogen. The wafer was immersed in NMP at 40°C for 1 hour, after which the change in film thickness and appearance were investigated to evaluate the solvent resistance. Those that showed no change in appearance or film thickness were marked with ○, and those that showed swelling, film loss, etc. were marked with ×.

[0125] The results are shown in Tables 3 and 4.

[0126] [Table 3]

[0127] [Table 4]

[0128] From the above results, the photosensitive resin composition of the present invention can form fine patterns that could not be achieved with conventional silicone resins containing epoxy or phenol groups in the side chains and photosensitive resin compositions containing a photoacid generator, and the cured film exhibits high chemical resistance and copper migration resistance even when cured at low temperatures of less than 150° C. In addition, since the cured film has the above-mentioned properties, it can be suitably used as a film-forming material for protecting various electric and electronic parts such as circuit boards, semiconductor elements, and display elements.

Claims

1. (A) a silicone resin having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in its main chain and an acryloyl group or a methacryloyl group in its side chain; and (B) Photoradical generator A photosensitive resin composition comprising:

2. 2. The photosensitive resin composition according to claim 1, wherein the silicone resin (A) is a polymer that 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 repeating unit selected from the group consisting of a repeating unit represented by the following formula (A3) and a repeating unit represented by the following formula (A4): 【Chemistry 1】 (In the formula, R 1 ~R 4 are each independently a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. Each m is independently an integer of 1 to 600. When m is an integer of 2 or more, each R 3 may be the same or different, and each R 4 may be the same or different. 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 is a divalent group represented by the following formula (X1): 2 is a divalent group represented by the following formula (X2): 【Chemistry 2】 (In the formula, R 11 ~R 14 are each independently a hydrogen atom or a methyl group. 1 and n 2 are each independently an integer from 1 to 7. 1 and L 2 are each independently a saturated hydrocarbylene group having 1 to 15 carbon atoms, and the —CH 2 Part of - is -O-, -S-, -SO 2 The saturated hydrocarbylene group may be substituted with --, --CO-- or --CONH--, and some or all of the hydrogen atoms of the saturated hydrocarbylene group may be substituted with hydroxy groups. The dashed lines represent bonds. 【Chemistry 3】 (In the formula, R 21 and R 22 R is each independently a hydrogen atom or a methyl group. 23 and R 24 are each independently a hydrocarbyl group having 1 to 8 carbon atoms. 1 and k 2 are each independently an integer of 0 to 7. p is an integer of 0 to 600. The dashed lines represent bonds.

3. 2. The photosensitive resin composition according to claim 1, further comprising (C) a crosslinking agent having two or more (meth)acryloyl groups.

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

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

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

7. The method for forming a pattern according to claim 6, further comprising the step of (iv) post-curing the photosensitive resin film patterned by development at a temperature of 40 to 150°C.

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

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