Photosensitive resin composition and pattern formation method

Abstract

Provided is a photosensitive resin composition containing: (A) a silicone resin having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in the main chain and a urethane bond, a carboxy group, and an acryloyl group or methacryloyl group in the side chain; and (B) a photoinitiator.

Description

Photosensitive resin composition and pattern forming method

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

[0002] Conventionally, photosensitive polyimide compositions, photosensitive epoxy resin compositions, and photosensitive silicone compositions have been used as photosensitive protective films for semiconductor devices and insulating films for multilayer printed circuit boards. As a photosensitive material applicable to the protection of such substrates and circuits, a photosensitive silicone composition 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 the 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.

[0004] Japanese Patent Publication No. 2023-001980

[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.

[0006] As a result of repeated studies to achieve the above object, the present inventors have found that the above object can be achieved by 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, and a photosensitive resin composition containing a photo radical generator, and have completed the present invention.

[0007] That is, the present invention provides the following photosensitive resin composition and pattern forming method. 1. A photosensitive resin composition comprising (A) a silicone resin having a silphenylene skeleton, a polysiloxane skeleton and a fluorene skeleton in the main chain and a urethane bond, a carboxy group and an acryloyl group or a methacryloyl group in the side chain, and (B) a photo radical generator. 2. The photosensitive resin composition of 1, wherein the (A) silicone resin 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 selected from a repeating unit represented by the following formula (A3) and a repeating unit represented by the following formula (A4). [In the formula, 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. 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. 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 is a divalent group represented by the following formula (X1). X 2 is a divalent group represented by the following formula (X2). (In the formula, 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 ~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 also be located at their terminal ends. 13 ~R 16 Each of these is 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 in the polymer 13 ~R 16 Of these, at least 10% R 13 ~R 16 However, the group is represented by the following formula (Y), and at least 10% R 13 ~R 16 This is the base represented by the following formula (Z). The dashed lines represent bonds. (In the formula, L 5 This is a hydrocarbylene group having 2 to 14 carbon atoms, and some of the -CH2- atoms of the hydrocarbylene group may be substituted with -O-, -S-, -SO2-, or -CO-. The -CH2- atoms of the hydrocarbylene group may also be located at its terminal end. 17 L is a hydrogen atom or a methyl group. 6 This is a hydrocarbylene group having 2 to 14 carbon atoms, and some of the -CH2- atoms of the hydrocarbylene group may be substituted with -O-, -S-, -SO2-, or -CO-. The -CH2- atoms of the hydrocarbylene group may also be located at its terminal ends. The dashed lines represent bonds. (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 2Each of the following is an integer from 0 to 7. p is an integer from 0 to 600. The dashed line is a coupling. 3. A photosensitive resin composition 1 or 2 further comprising (C) a crosslinking agent having two or more (meth)acryloyl groups. 4. A photosensitive resin composition 1 to 3 further comprising (D) a silane coupling agent. 5. A photosensitive resin composition 1 to 4 further comprising (E) a solvent. 6. A pattern forming method comprising the steps of (i) forming a photosensitive resin film on a substrate using a photosensitive resin composition 1 to 5, (ii) exposing the photosensitive resin film, and (iii) forming a pattern by developing the exposed photosensitive resin film with a developer to remove unexposed areas. 7. A pattern forming method 6 further comprising the step of (iv) post-curing the photosensitive resin film patterned by development at a temperature of 40 to 190°C. 8. A photosensitive resin composition, one of 1 to 5, which is a material for a protective coating for electrical and electronic components.

[0008] The photosensitive resin composition of the present invention can form fine patterns that could not be achieved with conventional silicone resins containing epoxy or phenolic groups in their side chains, and with photosensitive resin compositions containing photoacid generators, and exhibits sufficient solubility in alkaline aqueous solutions.

[0009] [Photosensitive resin composition] The photosensitive resin composition of the present invention comprises (A) a silicone resin having a silphenylene skeleton, a polysiloxane skeleton and a fluorene skeleton in its main chain and a urethane bond in its side chain, and (B) a photoradical generator.

[0010] [(A) Silicone Resin] The silicone resin of component (A) is a polymer 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. While there are no particular limitations on such a silicone resin, a polymer is preferred that includes repeating units represented by the following formula (A1) and repeating units represented by the following formula (A2), and may further include at least one selected from repeating units represented by the following formula (A3) and repeating units represented by the following formula (A4).

[0011] In equations (A1) to (A4), 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, but it is preferable that they are numbers that satisfy 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 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, 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. (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). (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- atoms of the hydrocarbylene group may be substituted with -O-, -S-, -SO2-, or -CO-. The -CH2- atoms of the hydrocarbylene group may be located at its terminal end.

[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; cyclic saturated hydrocarbylene groups with 3 to 14 carbon atoms, such as cyclopentanediyl, cyclohexanediyl, norbornanediyl, and adamantanediyl; ethene-1,1-diyl, ethene-1,2-diyl, and 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 C2-14 alkenediyl groups such as 1-dodecene-1,2-diyl, 1-tridecene-1,2-diyl, and 1-tetradecene-1,2-diyl; C3-14 cyclic unsaturated carbylene groups such as cyclohexenediyl and norbornenediyl; and C6-14 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- atoms of the hydrocarbylene group may be substituted with -O-, -S-, -SO2-, or -CO-. The -CH2- atoms of the hydrocarbylene group may be located at its terminal end.

[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; cyclic saturated hydrocarbylene groups with 3 to 14 carbon atoms, such as cyclopentanediyl, cyclohexanediyl, norbornanediyl, and adamantanediyl; ethene-1,1-diyl, ethene-1,2-diyl, and 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 C2-14 alkenediyl groups such as 1-dodecene-1,2-diyl, 1-tridecene-1,2-diyl, and 1-tetradecene-1,2-diyl; C3-14 cyclic unsaturated carbylene groups such as cyclohexenediyl and norbornenediyl; and C6-14 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 R is present in an amount of 25 mol% or more. 13 ~R16 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). (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 producing 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). (In the formula, R 1 ~R 4 , m, a, b, c, d and X 2 (This is the same as above.)

[0037] (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. (In the formula, R 11 and R 12 , L 1 ~L 4 , n 1and 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 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 the 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 contrast, the compound represented by formula (1) is preferably blended 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 used as an option. 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 above reaction, a polymerization inhibitor may optionally be used. As the polymerization inhibitor, various phenols, hydroquinones, benzoquinones, catechols, hydroxyamines, nitroso compounds, etc. can be used. The amount of the 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 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 solvent, and particularly preferably 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 viewpoints of preventing side reactions and enabling completion of the reaction 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, particularly preferably 3 to 24 hours.

[0049] In the above 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 mixed so as to have a molar ratio of 0.80 to 8.00, and more preferably 1.60 to 6.40. The compound represented by formula (2) may be used alone or in combination of two or more kinds of compounds.

[0050] In the above reaction, a catalyst may be used as an option. 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. 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 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 the compound represented by formula (3), the compound represented by formula (4), and the compound represented by formula (5), and optionally the compound represented by formula (6), in the presence of a metal catalyst. (In the formula, R 1 ~R 4 (And m are the same as above.)

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

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

[0057] As the metal catalyst, a simple platinum group metal such as platinum (including platinum black), rhodium, 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 of 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); those obtained by supporting a platinum group metal such as platinum black or palladium on a carrier such as alumina, silica, carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (so-called Wilkinson catalyst); complexes of chloroplatinic acid, chloroplatinic acid or chloroplatinate with a vinyl group-containing siloxane (particularly, a 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 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] Each raw material compound is preferably blended such that the total number of hydrosilyl groups from the compound represented by formula (3) and the compound represented by 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 compound represented by formula (5) and the compound represented by 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 involves the reaction of a polymer (hereinafter also referred to as polymer C) containing repeating units represented by the following formula (C1) and repeating units represented by the following formula (C2), and which may further contain repeating units represented by the following formula (C3) and repeating units represented by the following formula (C4), with a compound represented by the following formula (7). (In the formula, R 1 ~R 4 , m, a, b, c, d and X 2 (This is the same as above.)

[0064]

[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. (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, and 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 8This is a saturated hydrocarbylene group having 1 to 14 carbon atoms, and 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 used as an option. The catalyst may be an amine such as triethylamine, triethylenediamine, bis-(2-dimethylaminoethyl) ether, or N-methylmorpholine; a phosphine such as triphenylphosphine or tri(o-tolyl)phosphine; a quaternary ammonium salt such as tetrabutylammonium chloride, benzyltriethylammonium chloride, or tetraethylhydroxylammonium; an imidazole such as imidazole or 2-ethyl-4-methylimidazole; a pyridine such as pyridine, N,N-dimethyl-4-aminopyridine, or 2,6-lutidine; or tin acetate, tin octylate, tin oleate, tin laurylate, dibutyltin diacetate, or 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. As the polymerization inhibitor, various phenols, hydroquinones, benzoquinones, catechols, hydroxyamines, nitroso compounds, etc., can be used. The amount of polymerization inhibitor used is not particularly limited, but it 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, and oxime compounds are more preferred.

[0076] Specific examples of the acetophenone compounds mentioned above include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyltrichloroacetophenone, p-t-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 benzophenone compounds mentioned above 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 oxime compounds mentioned above 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]ethaneone, and O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-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, 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 components (A) to (D) described above and other various additives.

[0092] (E) As the solvent, 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 excellent 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 Forming Method] A pattern forming method using the photosensitive resin composition of the present invention includes 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) forming a pattern by developing the exposed photosensitive resin film with a developer to remove unexposed areas.

[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 with thin films formed 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 necessary. 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 the photosensitive resin composition 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 with 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 the creation of finer patterns. 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, (iv) the film with the pattern formed can be post-cured at 40 to 190°C using an oven or hot plate. If the post-curing temperature is 40 to 190°C, the crosslinking density of the photosensitive resin composition can be increased 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. By 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 to 190°C. The film thickness of the cured film after post-curing is usually 1 to 200 μm, preferably 5 to 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.

[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.

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[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 polystyrene equivalent values ​​using gel permeation chromatography (GPC) with tetrahydrofuran as the eluent. 1 ¹H-NMR (manufactured by 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, followed by the addition of 1500 g of toluene and heating to 70°C. Then, 1.0 g of toluene chlorplatinate 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. 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, 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 polystyrene equivalent values ​​using gel permeation chromatography (GPC) with tetrahydrofuran as the eluent. 1 ¹H-NMR (manufactured by 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 800 g of polymer b1 was added to a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device and reflux condenser, 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 vacuum distillation to obtain polymer A1. The Mw of polymer A1 was 9000. 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 800 g of polymer b1 was added to a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device and reflux condenser, and dissolved in 2200 g of cyclopentanone. 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. 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 vacuum distillation to obtain polymer A2. The Mw of polymer A2 was 9000. 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 800 g of polymer b1 was added to a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device and reflux condenser, and dissolved in 2200 g of cyclopentanone. 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. 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 vacuum distillation to obtain polymer A3. The Mw of polymer A3 was 9000. Note that 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 800 g of polymer b1 was added to a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device and reflux condenser, and dissolved in 2200 g of cyclopentanone. 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. 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 vacuum distillation to obtain polymer A4. The Mw of polymer A4 was 10000. 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 800 g of polymer b1 was added to a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device and reflux condenser, and dissolved in 2200 g of cyclopentanone. 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. 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 vacuum distillation 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 800 g of polymer b2 was added to a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device and reflux condenser, and dissolved in 2200 g of cyclopentanone. 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. 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 vacuum distillation to obtain polymer A6. The Mw of polymer A6 was 82,000. 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 800 g of polymer b2 was added to a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device and reflux condenser, and dissolved in 2200 g of cyclopentanone. 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. 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 vacuum distillation to obtain polymer A7. The Mw of polymer A7 was 82000. 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 800 g of polymer b2 was added to a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device and reflux condenser, 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 vacuum distillation 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: 400 g of dimethyl carbonate was added to a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, and heated to 70°C. 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. The mixture was then dissolved in 800 g of cyclopentanone. To this, 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 comparative polymer A'1. The Mw of comparative polymer A'1 was 15000.

[0128] [Comparative Synthesis Example 2] Synthesis of Comparative Polymer A'2 400 g of dimethyl carbonate was added to a 10 L flask equipped with a stirrer, thermometer, nitrogen purging device and reflux condenser, and heated to 70°C. 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, after which dimethyl carbonate was removed from the reaction solution under reduced pressure. It was then dissolved in 800 g of cyclopentanone. 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 vacuum distillation to obtain comparative polymer A'2. The Mw of comparative polymer A'2 was 16,000.

[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, followed by the addition of 1100 g of toluene and heating to 80°C. Then, 1.0 g of toluene chlorplatinate 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 chlorplatinate 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 compositions [Examples 1-23 and Comparative Examples 1-12] Each component was mixed according to the amounts shown in Tables 1-3, then stirred and dissolved at room temperature, and then microfiltration was performed using a 1.0 μm Teflon® filter to prepare the photosensitive resin compositions of Examples 1-23 and Comparative Examples 1-12.

[0132]

[0133]

[0134]

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

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

[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 the resin film (1) Pattern formation and evaluation thereof Each photosensitive resin composition was coated to a thickness of 20 μm on a substrate for migration testing (a comb-shaped electrode substrate with conductive material being copper, conductive part spacing and conductive part width of 20 μm, and conductive part thickness of 4 μm) using a spin coater. 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. Light with a wavelength of 365 nm was shone at 500 mJ / cm² through a quartz mask having sets of lines and spaces of equal width with line widths 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 the TMAH aqueous solution, spray development was performed in 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 using a 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 characteristics (copper migration) A substrate with a pattern formed by the method in (1) was used as a substrate for evaluating copper migration and tested. 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 the photosensitive resin film obtained from the photosensitive resin composition, each photosensitive resin composition listed in Tables 1 to 3 was applied to a 13 cm x 15 cm, 0.7 mm thick iron plate using a bar coater. The plate was exposed using a contact aligner type exposure apparatus at a wavelength of 405 nm 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 thickness of the resulting film was 0.2 μm. Using this photosensitive resin film, a dielectric breakdown tester TM-5031AM (manufactured by Tama Densoku Co., Ltd.) was used to apply voltage starting at a voltage increase rate of 5 V / sec, and the voltage at which the test specimen broke was measured to determine 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 15 mm x 15 mm pattern was formed on a silicon wafer using each of the photosensitive resin compositions listed in Tables 1 to 3, in the same manner as for wafer preparation for the copper migration test in (1), and then post-cured at 180°C for 2 hours while purging with nitrogen. After immersing 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. ○ was used for those with no change in appearance or film thickness, and × was used for those in which swelling or film loss was observed.

[0142] (5) Evaluation of Adhesion Each photosensitive resin composition described in Tables 1 to 3 was applied to a silicon wafer by spin coating, and a film (30 μm thick) was prepared by pre-baking at 120°C for 2 minutes. A silicon wafer diced into 4 mm squares was thermocompressed onto each obtained 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 ​​when each composition was measured 10 times are shown in Table 1.

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

[0144]

[0145]

[0146]

[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 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.

2. The photosensitive resin composition according to claim 1, wherein the silicone resin 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 selected from a repeating unit represented by the following formula (A3) and a repeating unit represented by the following formula (A4). [In the formula, R 1 ~R 4 are each independently a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. m is each independently an integer of 1 to 600. 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. 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 is a divalent group represented by the following formula (X1). X 2 is a divalent group represented by the following formula (X2). (In the formula, 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 ~L 4 are each independently a saturated hydrocarbylene group having 1 to 8 carbon atoms, and a part of -CH2- of the saturated hydrocarbylene group may be substituted with -O-, -S-, -SO2-, or -CO-. In addition, -CH2- of the saturated hydrocarbylene group may be located at its terminal. R 13 ~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 at least 10% of all R 13 ~R 16 in the polymer are R 13 ~R 16 represented by the following formula (Y), and at least 10% of R 13 ~R 16 are groups represented by the following formula (Z). The dashed line is a bond. (In the formula, L 5 This is a hydrocarbylene group having 2 to 14 carbon atoms, and some of the -CH2- atoms of the hydrocarbylene group may be substituted with -O-, -S-, -SO2-, or -CO-. The -CH2- atoms of the hydrocarbylene group may also be located at its terminal end. 17 L is a hydrogen atom or a methyl group. 6 This is a hydrocarbylene group having 2 to 14 carbon atoms, and some of the -CH2- atoms of the hydrocarbylene group may be substituted with -O-, -S-, -SO2-, or -CO-. The -CH2- atoms of the hydrocarbylene group may also be located at its terminal ends. The dashed lines represent bonds. (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. The photosensitive resin composition according to claim 1, further comprising a crosslinking agent having two or more (C)(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. A pattern forming method comprising: (i) forming a photosensitive resin film on a substrate using a photosensitive resin composition according to any one of claims 1 to 5; (ii) exposing the photosensitive resin film; and (iii) forming a pattern by developing the exposed photosensitive resin film with a developer to remove unexposed areas.

7. The pattern forming method according to claim 6, further comprising (iv) a step of 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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