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

Abstract

To provide a photosensitive resin composition which facilitates formation of a vertical pattern that is thick and fine, yields a cured film having excellent copper migration resistance, photoresist peeling liquid resistance, adhesion to a substrate and heat resistance, and enables formation of a resin film having excellent reliability as a film for electric / electronic component protection and a film for substrate adhesion, and also to provide a photosensitive resin film, a photosensitive dry film, and a pattern formation method using them.SOLUTION: A photosensitive resin composition contains (A) a polymer having a silphenylene skeleton, a polysiloxane skeleton and a fluorene skeleton in its main chain, and a polyhydric alcohol structure in its side chain, (B) a predetermined crosslinking agent, and (C) a photoacid generator.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Conventionally, photosensitive polyimide compositions, photosensitive epoxy resin compositions, photosensitive silicone compositions, and the like have been used as photosensitive protective films for semiconductor devices and insulating films for multilayer printed circuit boards. A photosensitive silicone composition with particularly excellent flexibility has been proposed as a photosensitive material used to protect such substrates and circuits (Patent Document 1). This photosensitive silicone composition can be cured at low temperatures and can form a film with excellent reliability, such as moisture-resistant adhesion. However, it suffers from the problem of poor chemical resistance to photoresist stripping solutions such as N-methyl-2-pyrrolidone.

[0003] In response to this, a photosensitive silicone composition has been proposed that primarily contains a silphenylene skeleton-containing silicone polymer (Patent Document 2). While this photosensitive silicone composition has improved chemical resistance to conventional photoresist stripping solutions such as N-methyl-2-pyrrolidone, there remains the problem of poor chemical resistance to photoresist stripping solutions with even stronger dissolving power. In addition, further improvements are desired in terms of the level of fineness in pattern formation and the reliability of resin coatings. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-88158 [Patent Document 2] Japanese Patent Application Laid-Open No. 2008-184571 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, a photosensitive resin film, a photosensitive dry film, and a pattern formation method using the same, which are capable of forming a resin film (resin layer) that can be easily formed into a thick, fine, vertical pattern and that has excellent copper migration resistance, photoresist stripping solution resistance, adhesion to substrates, etc., and heat resistance, and is therefore highly reliable as a film for protecting electric and electronic components, a film for bonding substrates, etc. [Means for solving the problem]

[0006] As a result of intensive research into achieving the above-mentioned object, the present inventors have found that the above-mentioned object can be achieved by a photosensitive resin composition comprising: (A) a polymer having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in its main chain and containing a polyhydric alcohol structure in its side chain; (B) at least one crosslinking agent selected from a melamine compound, a guanamine compound, a glycoluril compound, and a urea compound, each containing an average of two or more methylol groups and / or alkoxymethyl groups per molecule; an amino condensate modified with formaldehyde or formaldehyde-alcohol; and a phenol compound having an average of two or more methylol groups or alkoxymethyl groups per molecule; and (C) a photoacid generator, thereby completing the present invention.

[0007] That is, the present invention provides the following photosensitive resin composition, photosensitive resin film, photosensitive dry film, and pattern forming method. 1. (A) A polymer having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in the main chain and containing a polyhydric alcohol structure in the side chain; (B) at least one crosslinking agent selected from nitrogen-containing compounds selected from melamine compounds, guanamine compounds, glycoluril compounds, and urea compounds, each containing an average of two or more methylol groups and / or alkoxymethyl groups per molecule; amino condensates modified with formaldehyde or formaldehyde-alcohol; and phenol compounds having an average of two or more methylol groups or alkoxymethyl groups per molecule; and (C) Photoacid generator A photosensitive resin composition containing the same. 2. The photosensitive resin composition of 1, wherein the (A) polymer contains a repeating unit represented by the following formula (A1) and a repeating unit represented by the following formula (A2), and may further contain a repeating unit represented by the following formula (A3) and a repeating unit represented by the following formula (A4). [Chemical formula] (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).) [Chemical formula] (In the formula, n 1 and n 2 are each independently an integer of 1 to 7. R 11 and R 12 are each independently a hydrogen atom or a methyl group. L 1 ~L 4 are each independently a saturated hydrocarbylene group having 1 to 15 carbon atoms, and a part of -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 dashed line is a bond.) [Chemical formula] (In the formula, R 21 and R22 are 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.L 1 , L 2 , L 3 and L 4 2. A photosensitive resin composition in which the number of carbon atoms in each of the above is 1. 4. The photosensitive resin composition of any one of 1 to 3, wherein the content of the compound of component (B) is 1 to 50 parts by mass per 100 parts by mass of component (A). 5. The photosensitive resin composition according to any one of 1 to 4, further comprising (D) a solvent. 6. A photosensitive resin film obtained from the photosensitive resin composition of any one of 1 to 5. 7. A photosensitive dry film comprising a support film and a photosensitive resin coating 6 on the support film. 8. (i) forming a photosensitive resin film on a substrate using the photosensitive resin composition according to any one of 1 to 5; (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. A pattern forming method comprising: 9. The pattern forming method according to 8, further comprising the step of (iv) post-curing the photosensitive resin film patterned by development at a temperature of 100 to 250°C. 10. (i') A step of forming a photosensitive resin film on a substrate using the photosensitive dry film of 7; (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. A pattern forming method comprising: 11. The pattern forming method of 10, further comprising the step of (iv) post-curing the photosensitive resin film patterned by development at a temperature of 100 to 250°C. 12. A photosensitive resin composition according to any one of 1 to 5, which is a material for a protective coating for electrical and electronic parts. 13. A photosensitive resin composition according to any one of 1 to 5, which is a material for a substrate bonding film for bonding two substrates. [Effects of the Invention]

[0008] The photosensitive resin composition of the present invention can form films over a wide range of thicknesses, and furthermore, by the pattern formation method described below, it is possible to easily form thick, fine, and perpendicular patterns. Cured films obtained using the photosensitive resin composition and photosensitive dry film of the present invention have excellent resistance to photoresist stripping solutions, adhesion to substrates, etc., and heat resistance. They also have excellent adhesion to substrates used in substrates, electronic components, semiconductor elements, etc., particularly circuit boards, mechanical properties such as crack resistance, and copper migration resistance. Furthermore, the films have high reliability as insulating protective films and can be suitably used as film-forming materials for protecting various electric and electronic components, such as circuit boards, semiconductor elements, and display elements, and as film-forming materials for bonding substrates. DETAILED DESCRIPTION OF THE INVENTION

[0009] [Photosensitive resin composition] The photosensitive resin composition of the present invention comprises (A) a polymer having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in its main chain and containing a polyhydric alcohol structure in its side chain, (B) a crosslinking agent having a specific structure, and (C) a photoacid generator.

[0010] [(A) A polymer having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in the main chain and a polyhydric alcohol structure in the side chain]

[0011] The polymer of component (A) is preferably 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 a repeating unit represented by the following formula (A3) and a repeating unit represented by the following formula (A4). [ka]

[0012] In formulas (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, and preferably 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.

[0013] In formulas (A2) and (A4), R 1 ~R 4 are each independently a hydrocarbyl group having 1 to 20 carbon atoms, which may contain heteroatoms. m is each independently an integer of 1 to 600, and 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.

[0014] In formulas (A2) and (A4), when there are two or more siloxane units (that is, when m is an integer of 2 or more), all the siloxane units may 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 units.

[0015] [[ID=! 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.

Chemical formula

[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), R 11 and R 12 are each independently a hydrogen atom or a methyl group, but R 11 and R 12 and are preferably both hydrogen atoms.

[0018] In formula (X1), L 1 ~L 4 are each independently a saturated hydrocarbylene group having 1 to 15 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. The -CH2- groups of the saturated hydrocarbylene group may be located at its terminal.

[0019] The saturated hydrocarbylene group may be linear, branched, or cyclic, and 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-1,1 alkanediyl groups having 1 to 15 carbon atoms, such as 0-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, and pentadecane-1,15-diyl group; and cyclic saturated hydrocarbylene groups having 3 to 15 carbon atoms, such as cyclopentanediyl group, cyclohexanediyl group, norbornanediyl group, and adamantanediyl group.

[0020] L 1 and L 3 Preferably, each of L 2 and L 4 However, it is more preferable that both of them have one carbon atom.

[0021] In formulas (A3) and (A4), X 2is a divalent group represented by the following formula (X2). [ka] (In the formula, the dashed lines represent bonds.)

[0022] In formula (X2), R 21 and R 22 are each independently a hydrogen atom or a methyl group, and preferably a hydrogen atom.

[0023] In formula (X2), R 23 and R 24 are each independently a hydrocarbyl group having 1 to 8 carbon atoms.

[0024] In formula (X2), k 1 and k 2 are each independently an integer of 0 to 7, preferably 0.

[0025] 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 may be the same or different from each other.

[0026] The polymer of component (A) preferably has a weight-average molecular weight (Mw) of 2,000 to 500,000, more preferably 8,000 to 100,000. When Mw is within the above range, the polymer can be obtained in a solid form, and film-forming properties can be ensured. In the present invention, Mw is a value measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an elution solvent.

[0027] The polymer of component (A) may be a polymer in which the repeating unit represented by formula (A1), the repeating unit represented by formula (A2), the repeating unit represented by formula (A3), and the repeating unit represented by formula (A4) are randomly or alternately bonded, or may contain multiple blocks of each unit.

[0028] The polymer of component (A) functions to provide film-forming ability, and the resulting resin film has good pattern-forming ability, and the resulting cured film has good adhesion to substrates and other surfaces, as well as crack resistance, chemical resistance, and heat resistance.

[0029] The polymer of component (A) may be used alone or in combination of two or more.

[0030] The method for producing the polymer of component (A) is not particularly limited, but it 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), 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.

[0031] [ka] (In the formula, R 11 and R 12 , n 1 , n 2 , L 1 ~L 4 is the same as above.)

[0032] [ka] (In the formula, R 21 ~R 24 , k 1 , k 2and p is the same as above.

[0033] Examples of the metal catalyst include platinum group metals such as platinum (including platinum black), rhodium, and palladium; platinum chlorides, chloroplatinic acids, and chloroplatinic salts such as HPtCl·xH2O, HPtCl·xH2O, NaHPtCl·xH2O, KHPtCl·xH2O, NaPtCl·xH2O, KPtCl·xH2O, PtCl·xH2O, PtCl, and NaHPtCl·xH2O (where x is preferably an integer of 0 to 6, particularly preferably 0 or 6); alcohol-modified chloroplatinic acid (for example, as 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 a support such as alumina, silica, or carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (the so-called Wilkinson 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.

[0034] The amount of catalyst used is a catalytic amount, and typically, as a platinum group metal, it is preferably 0.001 to 0.1 mass% relative to the total amount of the reaction polymer. In the polymerization reaction, a solvent may be used as needed. Examples of the solvent include hydrocarbon solvents such as toluene and xylene. Regarding 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, for example, 40 to 150°C, and particularly preferably 60 to 120°C. The polymerization time varies depending on the type and amount of polymer, but is preferably approximately 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 complete, if a solvent was used, it can be distilled off to obtain the polymer.

[0035] The reaction method is not particularly limited, but it is preferable to first mix and heat the compound represented by formula (2), the compound represented by formula (3), and, if necessary, the compound represented by formula (4), and then add a metal catalyst to the mixed solution, and then add the compound represented by formula (1) dropwise over 0.1 to 5 hours.

[0036] The raw material compounds are preferably blended so that the molar ratio of the total hydrosilyl groups in the compound represented by formula (1) and the compound represented by formula (2) to the total 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 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.

[0037] In the polymerization reaction, a polymerization inhibitor may be optionally used. 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).

[0038] After the reaction is complete, optionally additional solvent may be added, the mixture may be washed with water, and the organic layer may then be heated under reduced pressure to remove the solvent, yielding the polymer (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 hydrogencarbonate such as sodium carbonate, sodium hydrogencarbonate, or potassium carbonate may be used.

[0039] Another method for producing the polymer of component (A) is to react a polymer (hereinafter also referred to as polymer B) containing a repeating unit represented by the following formula (B1) and a repeating unit represented by the following formula (B2), and which may further contain a repeating unit represented by the following formula (B3) and a repeating unit represented by the following formula (B4), with 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.)

[0040] [ka]

[0041] 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 , R 12 , n 1 and n 2 is the same as above. The dashed lines represent bonds.)

[0042] In formula (5), L 5 is a saturated hydrocarbylene group having 1 to 14 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 The saturated hydrocarbylene group represented by the formula (I) may be linear, branched or cyclic, but preferably has 1 to 7 carbon atoms.

[0043] In formula (5), L 6is a saturated hydrocarbylene group having 1 to 14 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 The saturated hydrocarbylene group represented by the formula (I) may be linear, branched or cyclic, but preferably has 1 to 7 carbon atoms.

[0044] Specific examples of the compound represented by formula (5) include, but are not limited to, glycidol (Epiol OH (registered trademark) manufactured by NOF Corporation).

[0045] The reaction conditions are not particularly limited, but typically involve mixing polymer B and the compound represented by formula (5) in a solvent and heating the mixture. From the viewpoint of accelerating the reaction, it is preferable to use a polar solvent as the 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 45 to 100°C. The reaction time, which varies depending 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.

[0046] In the reaction, each raw material compound is X in polymer B. 3 The compound represented by formula (5) is preferably blended in such a way that the molar ratio relative to the total amount of the compound represented by formula (5) is 1.0 to 8.0, more preferably 4.0 to 6.0. Only one type of compound represented by formula (5) may be used, or two or more types of compounds may be used in combination.

[0047] In the reaction, a catalyst may be optionally used. 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 octoate, tin oleate, tin laurate, dibutyltin diacetate, and dimethyltin. 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 octenate; organic bismuth compounds such as bismuth octylate and bismuth neodecanoate; and potassium salts such as potassium carbonate, potassium acetate, and potassium octylate.

[0048] 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 of the catalyst. The catalysts may be used singly or in combination of two or more.

[0049] In the reaction, a polymerization inhibitor may be optionally used. 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).

[0050] After the reaction is complete, optionally additional solvent may be added, the mixture may be washed with water, and the organic layer may then be heated under reduced pressure to remove the solvent, yielding the polymer (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 hydrogencarbonate such as sodium carbonate, sodium hydrogencarbonate, or potassium carbonate may be used.

[0051] [(B) Crosslinking agent] The crosslinking agent (B) is at least one selected from the group consisting of nitrogen-containing compounds containing an average of two or more methylol groups and / or alkoxymethyl groups per molecule, such as melamine compounds, guanamine compounds, glycoluril compounds, and urea compounds, amino condensates modified with formaldehyde or formaldehyde-alcohol, and phenol compounds containing an average of two or more methylol groups or alkoxymethyl groups per molecule. The crosslinking agent crosslinks with the polymer (A) to form a thick, fine, vertical pattern, resulting in a cured film with excellent adhesion to substrates and other surfaces, crack resistance, chemical resistance, and heat resistance.

[0052] The melamine compound may be one represented by the following formula (B1). [ka]

[0053] In formula (B1), R 101 ~R 106 are each independently a methylol group, a saturated hydrocarbyloxymethyl group having 2 to 5 carbon atoms, or a hydrogen atom, and at least one is a methylol group or a saturated hydrocarbyloxymethyl group. Examples of the saturated hydrocarbyloxymethyl group include alkoxymethyl groups such as a methoxymethyl group and an ethoxymethyl group.

[0054] Examples of the melamine compound represented by formula (B1) include trimethoxymethyl monomethylol melamine, dimethoxymethyl monomethylol melamine, trimethylol melamine, hexamethylol melamine, hexamethoxymethyl melamine, and hexaethoxymethyl melamine.

[0055] The melamine compound represented by formula (B1) can be obtained, for example, by first modifying a melamine monomer by methylolation with formaldehyde according to a known method, or by further modifying the melamine monomer by alkoxylation with an alcohol, preferably a lower alcohol, for example, an alcohol having 1 to 4 carbon atoms.

[0056] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, and tetramethoxyethylguanamine.

[0057] Examples of the glycoluril compound include tetramethylol glycoluril and tetrakis(methoxymethyl) glycoluril.

[0058] Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, tetramethoxyethyl urea, tetraethoxymethyl urea, and tetrapropoxymethyl urea.

[0059] Examples of the amino condensate modified with formaldehyde or formaldehyde-alcohol include a melamine condensate modified with formaldehyde or formaldehyde-alcohol, and a urea condensate modified with formaldehyde or formaldehyde-alcohol.

[0060] The modified melamine condensate may be obtained by addition-condensation polymerization of a compound represented by formula (B1) or a multimer thereof (e.g., an oligomer such as a dimer or trimer) with formaldehyde until a desired molecular weight is reached. The addition-condensation polymerization method may be a conventionally known method. The modified melamine represented by formula (B1) may be used singly or in combination of two or more.

[0061] Examples of urea condensates modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensates, ethoxymethylated urea condensates, and propoxymethylated urea condensates.

[0062] The modified urea condensate can be obtained, for example, by modifying a urea condensate of a desired molecular weight by methylolating it with formaldehyde according to a known method, or by further modifying it by alkoxylating it with an alcohol.

[0063] Examples of the phenol compound having two or more methylol groups or alkoxymethyl groups on average per molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol and 2,2',6,6'-tetramethoxymethylbisphenol A.

[0064] In the photosensitive resin composition of the present invention, the content of component (B) is preferably 1 to 50 parts by mass, and more preferably 1 to 30 parts by mass, per 100 parts by mass of component (A). When the content of component (B) is 1 part by mass or more, sufficient curing properties are obtained upon light irradiation, while when the content is 50 parts by mass or less, the proportion of component (A) in the photosensitive resin composition does not decrease, allowing the cured product to exhibit sufficient effects. The component (B) may be used alone or in combination of two or more types.

[0065] [(C) Photoacid generator] The photoacid generator (C) is not particularly limited as long as it is decomposed by light irradiation to generate an acid, but it is preferably one that is decomposed by light with a wavelength of 190 to 500 nm to generate an acid. The photoacid generator serves as a curing catalyst. The photosensitive resin composition of the present invention has excellent compatibility with photoacid generators, allowing the use of a wide range of photoacid generators.

[0066] Examples of the photoacid generator include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzylsulfonate derivatives, sulfonate ester derivatives, imido-yl-sulfonate derivatives, oxime sulfonate derivatives, and iminosulfonate derivatives.

[0067] Examples of the onium salt include a sulfonium salt represented by the following formula (C1) and an iodonium salt represented by the following formula (C2). [ka]

[0068] In formulas (C1) and (C2), R 201 ~R 205 are each independently a saturated hydrocarbyl group having 1 to 12 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms which may have a substituent. - is a non-nucleophilic counterion.

[0069] The saturated hydrocarbyl group may be linear, branched, or cyclic, and specific examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and structural isomers thereof; and cyclic saturated hydrocarbyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl. Examples of the aryl group include phenyl, naphthyl, and biphenylyl. Examples of the aralkyl group include benzyl and phenethyl.

[0070] Examples of the substituent include an oxo group, a saturated hydrocarbyl group having 1 to 12 carbon atoms, a saturated hydrocarbyloxy group having 1 to 12 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aralkyl group having 7 to 25 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, and an arylthio group having 6 to 24 carbon atoms. The saturated hydrocarbyl group and the hydrocarbyl moiety of the saturated hydrocarbyloxy group may be linear, branched, or cyclic, and specific examples thereof include R 201 ~R 205 Examples of the saturated hydrocarbyl group represented by the formula (I) include the same as those exemplified above.

[0071] R 201 ~R 205 Preferred examples of the alkyl group include saturated hydrocarbyl groups which may have a substituent such as a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, or a 2-oxocyclohexyl group; aryl groups which may have a substituent such as a phenyl group, a naphthyl group, a biphenylyl group, a 2-, 3-, or 4-methoxyphenyl group, a 2-, 3-, or 4-ethoxyphenyl group, a 3- or 4-tert-butoxyphenyl group, a 2-, 3-, or 4-methylphenyl group, a 2-, 3-, or 4-ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, a dimethylphenyl group, a terphenylyl group, a biphenylyloxyphenyl group, or a biphenylylthiophenyl group; and aralkyl groups which may have a substituent such as a benzyl group or a phenethyl group. Of these, aryl groups which may have a substituent and aralkyl groups which may have a substituent are more preferred.

[0072] Examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; fluoroalkanesulfonate ions such as triflate ion, 1,1,1-trifluoroethanesulfonate ion and nonafluorobutanesulfonate ion; arylsulfonate ions such as tosylate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion and 1,2,3,4,5-pentafluorobenzenesulfonate ion; alkanesulfonate ions such as mesylate ion and butanesulfonate ion; fluoroalkanesulfonimide ions such as trifluoromethanesulfonimide ion; fluoroalkanesulfonylmethide ions such as tris(trifluoromethanesulfonyl)methide ion; borate ions such as tetrakisphenylborate ion and tetrakis(pentafluorophenyl)borate ion; and phosphate ions such as hexafluorophosphate ion and tris(pentafluoroethyl)trifluorophosphate ion.

[0073] The diazomethane derivatives include compounds represented by the following formula (C3). [ka]

[0074] In formula (C3), R 211 and R 212 are each independently a saturated hydrocarbyl group having 1 to 12 carbon atoms, a halogenated saturated hydrocarbyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms which may have a substituent.

[0075] The saturated hydrocarbyl group may be linear, branched, or cyclic, and specific examples thereof include R 201 ~R 205 Examples of the halogenated saturated hydrocarbyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, and a nonafluorobutyl group.

[0076] Examples of the aryl group which may have a substituent include a phenyl group; an alkoxyphenyl group such as a 2-, 3-, or 4-methoxyphenyl group, a 2-, 3-, or 4-ethoxyphenyl group, or a 3- or 4-tert-butoxyphenyl group; an alkylphenyl group such as a 2-, 3-, or 4-methylphenyl group, a 2-, 3-, or 4-ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, or a dimethylphenyl group; and a halogenated aryl group such as a fluorophenyl group, a chlorophenyl group, or a 1,2,3,4,5-pentafluorophenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0077] Specific examples of the onium salt include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyliodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenylsulfonium, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenyl butanesulfonate Sulfonium, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate Cyclohexylphenylsulfonium, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, 4-(phenylthio)phenyldiphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tris(trifluoromethanesulfonyl)methide, triphenylsulfonium tetrakis(fluorophenyl)borate,Examples include tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(fluorophenyl)borate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, and tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(pentafluorophenyl)borate.

[0078] Specific examples of the diazomethane derivatives include bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis( tert-butylsulfonyl)diazomethane, bis(n-pentylsulfonyl)diazomethane, bis(isopentylsulfonyl)diazomethane, bis(sec-pentylsulfonyl)diazomethane, bis(tert-pentylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-pentylsulfonyl)diazomethane, 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane, and the like.

[0079] Specific examples of the glyoxime derivatives include bis-o-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-o-(p-toluenesulfonyl)-α-diphenylglyoxime, bis-o-(p-toluenesulfonyl)-α-dicyclohexylglyoxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedione glyoxime, bis-o-(p-toluenesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis-o-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis Examples of suitable dimethylglyoxime include bis-o-(methanesulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-o-(tert-butanesulfonyl)-α-dimethylglyoxime, bis-o-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-o-(cyclohexanesulfonyl)-α-dimethylglyoxime, bis-o-(benzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime, and bis-o-(camphorsulfonyl)-α-dimethylglyoxime.

[0080] Specific examples of the β-ketosulfone derivative include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane, 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane, and the like.

[0081] Specific examples of the disulfone derivatives include diphenyl disulfone and dicyclohexyl disulfone.

[0082] Specific examples of the nitrobenzyl sulfonate derivative include 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.

[0083] Specific examples of the sulfonate derivatives include 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene.

[0084] Specific examples of the imide-yl sulfonate derivatives include phthalimide-yl triflate, phthalimide-yl tosylate, 5-norbornene-2,3-dicarboximide-yl triflate, 5-norbornene-2,3-dicarboximide-yl tosylate, 5-norbornene-2,3-dicarboximide-yl-n-butylsulfonate, and n-trifluoromethylsulfonyloxynaphthylimide.

[0085] Specific examples of the oxime sulfonate derivatives include α-(benzenesulfonium oxyimino)-4-methylphenylacetonitrile, α-(p-tolylsulfonium oxyimino)-p-methoxyphenylacetonitrile, and the like.

[0086] Specific examples of the iminosulfonate derivatives include (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophen-2-ylidene)-(2-methylphenyl)-acetonitrile, and the like.

[0087] Also suitable for use are 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane and the like.

[0088] In the photosensitive resin composition of the present invention, the content of component (C) is preferably 0.05 to 20 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of component (A) from the viewpoint of photocurability. A content of component (C) of 0.05 parts by mass or more allows sufficient acid to be generated and the crosslinking reaction to proceed sufficiently, while a content of 20 parts by mass or less is preferred because it can prevent an increase in the absorbance of the photoacid generator itself and therefore does not cause problems such as a decrease in transparency. The component (C) may be used alone or in combination of two or more types.

[0089] [(D) Solvent] The photosensitive resin composition of the present invention may further contain a solvent as component (D). The solvent is not particularly limited as long as it is a solvent that can dissolve components (A) to (C) and the various additives described below, but organic solvents are preferred because they have excellent solubility for these components.

[0090] Examples of the organic solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, and γ-butyrolactone. In particular, ethyl lactate, cyclohexanone, cyclopentanone, PGMEA, γ-butyrolactone, and mixed solvents thereof, which have the best solubility for the photoacid generator, are preferred.

[0091] In the photosensitive resin composition of the present invention, the content of component (D) is preferably 50 to 2000 parts by mass, more preferably 50 to 1000 parts by mass, and particularly preferably 50 to 100 parts by mass, per 100 parts by mass of component (A), from the viewpoints of compatibility and viscosity of the photosensitive resin composition. Component (D) may be used singly or in combination of two or more types.

[0092] [Other additives] The photosensitive resin composition of the present invention may contain other additives in addition to the above-mentioned components, such as surfactants commonly used to improve coatability.

[0093] The surfactant is preferably a nonionic surfactant, such as a fluorine-containing surfactant, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, or fluorine-containing organosiloxane compound. Commercially available surfactants may be used, such as Fluorad (registered trademark) FC-430 (manufactured by 3M), Surflon (registered trademark) S-141, S-145 (manufactured by AGC Seimi Chemical Co., Ltd.), Unidyne (registered trademark) DS-401, DS-4031, DS-451 (manufactured by Daikin Industries, Ltd.), Megafac (registered trademark) F-8151 (manufactured by DIC Corporation), and X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.). Of these, Fluorad FC-430 and X-70-093 are preferred. When the photosensitive resin composition of the present invention contains the surfactant, the content thereof is preferably 0.05 to 1 part by mass per 100 parts by mass of component (A).

[0094] The photosensitive resin composition of the present invention may contain a silane coupling agent as another additive. The inclusion of a silane coupling agent can further enhance the adhesion of the coating obtained from the composition to the substrate. Examples of silane coupling agents include epoxy group-containing silane coupling agents and aromatic group-containing aminosilane coupling agents. These can be used alone or in combination of two or more. When the photosensitive resin composition of the present invention contains the silane coupling agent, its content is not particularly limited, but is preferably 0.01 to 5% by mass in the photosensitive resin composition of the present invention.

[0095] The photosensitive resin composition of the present invention can be prepared by a conventional method, for example, by mixing the above-mentioned components with stirring, and then filtering the mixture using a filter or the like, if necessary, to remove solids.

[0096] The photosensitive resin composition of the present invention prepared in this manner is suitable for use as, for example, a protective film for semiconductor elements, a protective film for wiring, a coverlay film, a solder mask, a material for insulating films for through-hole electrodes (TSV), and further as an adhesive between laminated substrates in three-dimensional lamination.

[0097] [Pattern Forming Method Using Photosensitive Resin Composition] 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:

[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-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.

[0099] A method for forming a photosensitive resin film includes, for example, 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 dipping, spin coating, or roll coating. The amount of the photosensitive resin composition applied can 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.

[0100] To improve the film thickness uniformity on the substrate surface, a solvent may be dripped onto the substrate before applying the photosensitive resin composition (pre-wetting method). The solvent to be dripped and its amount 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 preferred, but it is also possible to use the solvent used in the photosensitive resin composition.

[0101] 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.

[0102] Next, (ii) the photosensitive resin film is exposed to light. At this time, the exposure is preferably carried out with light having a wavelength of 10 to 600 nm, more preferably with light having a wavelength of 190 to 500 nm. Examples of light having such 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 is preferred.

[0103] The exposure may be performed through a photomask. The photomask may be, for example, a photomask having a desired pattern cut out therein. The material of the photomask is not particularly limited, but is preferably one that blocks light of the wavelengths described above. For example, a photomask having a light-shielding film made of chromium or the like is preferably used.

[0104] Furthermore, to enhance development sensitivity, post-exposure bake (PEB) may be performed. PEB is preferably performed at 40 to 150°C for 0.5 to 10 minutes. PEB crosslinks the exposed areas, forming an insolubilized pattern that is insoluble in the organic solvent used as the developer.

[0105] After exposure or PEB, (iii) the photosensitive resin film is developed using a developer to form a pattern. As the developer, organic solvents such as alcohols such as IPA, ketones such as cyclohexanone, and glycols such as PGME are preferred, but solvents used in photosensitive resin compositions can also be used. Examples of development methods include conventional methods, such as immersing a patterned substrate in the developer. The unexposed areas are dissolved and removed by organic solvent development, forming a pattern. Thereafter, washing, rinsing, drying, etc. are performed as necessary to obtain a resin film having the desired pattern.

[0106] Furthermore, (iv) the patterned film may be post-cured using an oven or hot plate, preferably at 100 to 250°C, more preferably 130 to 220°C. A post-curing temperature of 100 to 250°C increases the crosslink density of the photosensitive resin composition and removes residual volatile components, which is preferable from the viewpoints of adhesion to the substrate, heat resistance and strength, electrical properties, and adhesive strength. The post-curing time is preferably 10 minutes to 10 hours, more preferably 10 minutes to 3 hours. By using the photosensitive resin composition of the present invention, a film with excellent film properties can be obtained even when post-cured at a relatively low temperature of 200°C or less. The film thickness of the post-cured film (cured film) is usually 1 to 200 μm, preferably 5 to 50 μm.

[0107] When it is not necessary to form a pattern, for example, when it is desired to simply form a uniform film, the film can be formed by exposing the film to light of an appropriate wavelength without using the photomask in step (ii) of the pattern formation method.

[0108] [Board bonding method] The photosensitive resin composition of the present invention can also be used as an adhesive for bonding two substrates. Examples of methods for bonding substrates include bonding a substrate on which a film is formed using the photosensitive resin composition of the present invention to a second substrate under suitable conditions of heat and pressure so that an adhesive bond is formed between the two substrates. Either or both of the substrate on which the film is formed and the second substrate may be chipped by dicing or other processes. Preferred bonding conditions include a heating temperature of 50 to 200°C and a time of 1 to 60 minutes. A wafer bonder can be used as the bonding device to bond wafers together under reduced pressure while applying a load, or a flip-chip bonder can be used to perform chip-wafer or chip-chip bonding. The adhesive layer formed between the substrates can be strengthened by a post-curing treatment, described below, to form a permanent bond.

[0109] By post-curing the attached (bonded) substrates under the same conditions as in step (iv), the crosslink density of the film increases, thereby enhancing the substrate adhesive strength. Note that a crosslinking reaction occurs due to heating during bonding, but this crosslinking reaction does not cause side reactions involving degassing, so it does not induce bonding defects (voids), especially when used as a substrate adhesive.

[0110] [Photosensitive dry film] The photosensitive dry film of the present invention comprises a support film and a photosensitive resin film obtained from the photosensitive resin composition on the support film.

[0111] The photosensitive dry film (support film and photosensitive resin film) is solid, and since the photosensitive resin film does not contain a solvent, there is no risk of bubbles caused by the evaporation remaining inside the photosensitive resin film or between it and the uneven substrate.

[0112] The thickness of the photosensitive resin film is preferably 5 to 200 μm, more preferably 10 to 100 μm, from the viewpoints of flatness on an uneven substrate, step coverage, and the spacing between substrates.

[0113] Furthermore, the viscosity and fluidity of the photosensitive resin film are closely related, and the photosensitive resin film can exhibit appropriate fluidity within an appropriate viscosity range, allowing it to penetrate deep into narrow gaps and strengthen adhesion to the substrate by softening the resin. Therefore, from the perspective of fluidity, the viscosity of the photosensitive resin film is preferably 10 to 5000 Pa·s, more preferably 30 to 2000 Pa·s, and even more preferably 50 to 300 Pa·s, at 80 to 120°C. In the present invention, viscosity is measured using a rotational viscometer.

[0114] When the photosensitive dry film of the present invention is adhered to a substrate having irregularities, the photosensitive resin film conforms to the irregularities and covers the substrate, achieving high flatness. In particular, the photosensitive resin film is characterized by low viscoelasticity, which allows for even higher flatness. Furthermore, when the photosensitive resin film is adhered to the substrate in a vacuum environment, the occurrence of gaps can be more effectively prevented.

[0115] The photosensitive dry film of the present invention can be produced by applying the photosensitive resin composition to a support film and drying it to form a photosensitive resin film. A film coater typically used for producing adhesive products can be used as the photosensitive dry film production equipment. Examples of the film coater include a comma coater, a comma reverse coater, a multicoater, a die coater, a lip coater, a lip reverse coater, a direct gravure coater, an offset gravure coater, a three-roll bottom reverse coater, and a four-roll bottom reverse coater.

[0116] A photosensitive dry film can be produced by applying the photosensitive resin composition to a predetermined thickness onto a support film as it is unwound from the unwinding shaft of the film coater and passed through the coater head of the film coater. The film is then passed through a hot air circulating oven at a predetermined temperature and time, and dried on the support film to form a photosensitive resin film. If necessary, the photosensitive dry film can be passed through a laminating roll at a predetermined pressure together with a protective film unwound from another unwinding shaft of the film coater to bond the photosensitive resin film on the support film to the protective film. The photosensitive dry film with a protective film can then be produced by winding the film onto the winding shaft of the film coater. In this case, the temperature is preferably 25 to 150°C, the time is preferably 1 to 100 minutes, and the pressure is preferably 0.01 to 5 MPa.

[0117] The support film may be a single-layer film made of a single film, or a multilayer film made of a laminate of multiple films. Examples of materials for the film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Among these, polyethylene terephthalate is preferred because it has appropriate flexibility, mechanical strength, and heat resistance. These films may be subjected to various treatments such as corona treatment or release agent coating. Commercially available products may be used, such as Cerapeel WZ (RX) and Cerapeel BX8 (R) (manufactured by Toray Advanced Film Co., Ltd.), E7302 and E7304 (manufactured by Toyobo Co., Ltd.), Purex G31 and Purex G71T1 (manufactured by Teijin DuPont Films Co., Ltd.), PET38x1-A3, PET38x1-V8, and PET38x1-X08 (manufactured by Nippa Corporation).

[0118] The protective film may be the same as the support film described above, but polyethylene terephthalate and polyethylene are preferred because they have appropriate flexibility. Commercially available products can be used for these, and examples of polyethylene terephthalate include those already exemplified, and examples of polyethylene include GF-8 (manufactured by Tamapoly Corporation) and PE Film 0 Type (manufactured by Nippa Corporation).

[0119] The thickness of each of the support film and the protective film is preferably 10 to 100 μm, more preferably 25 to 50 μm, from the viewpoints of stability in the production of the photosensitive dry film and prevention of curling around the core.

[0120] [Pattern formation method using photosensitive dry film] The pattern forming method using the photosensitive dry film of the present invention comprises the steps of: (i') forming a photosensitive resin film on a substrate using the photosensitive dry film 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:

[0121] First, in step (i'), a photosensitive resin film is formed on a substrate using a photosensitive dry film. Specifically, the photosensitive resin film of the photosensitive dry film is attached to the substrate to form the photosensitive resin film on the substrate. If the photosensitive dry film has a protective film, the protective film is peeled off from the photosensitive dry film, and then the photosensitive resin film of the photosensitive dry film is attached to the substrate. The attachment can be performed, for example, using a film attachment device.

[0122] Examples of the substrate include those described in the pattern formation method using a photosensitive resin composition. A vacuum laminator is preferred as the film laminating device. For example, the protective film of the photosensitive dry film is peeled off, and the exposed photosensitive resin film is adhered to the substrate on a table at a predetermined temperature using a laminating roll at a predetermined pressure in a vacuum chamber at a predetermined vacuum level. The temperature is preferably 60 to 120°C, the pressure is preferably 0 to 5.0 MPa, and the vacuum level is preferably 50 to 500 Pa.

[0123] To obtain a photosensitive resin film of the required thickness, the film may be applied multiple times as necessary. For example, the number of times of application is about 1 to 10, which can obtain a photosensitive resin film of a thickness of 10 to 1000 μm, particularly about 100 to 500 μm.

[0124] In order to efficiently carry out the photocuring reaction of the photosensitive resin film and to improve the adhesion between the photosensitive resin film and the substrate, pre-baking may be performed as necessary, for example, at 40 to 140°C for about 1 minute to 1 hour.

[0125] As in the case of the pattern formation method using the photosensitive resin composition, the photosensitive resin film attached to the substrate can be patterned by (ii) exposing the photosensitive resin film to light, (iii) developing the exposed photosensitive resin film with a developer to form a pattern, and (iv) performing a post-curing treatment as needed. Note that the support film of the photosensitive dry film is peeled off before pre-baking or PEB, or removed by other methods depending on the process.

[0126] Films obtained from the photosensitive resin composition and photosensitive dry film have excellent mechanical properties such as solder resistance, heat resistance, low substrate warpage and crack resistance, copper migration resistance and adhesion to substrates, etc., and are suitable for use as protective films for electric and electronic components such as semiconductor elements and as films for bonding substrates. [Example]

[0127] 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 a TSKGEL Super HZM-H (manufactured by Tosoh Corporation) as a GPC column under analytical 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.

[0128] The compounds used in the synthesis of the polymer are shown below. [ka]

[0129] [ka]

[0130] [ka]

[0131] [ka]

[0132] [ka]

[0133] [Synthesis Example 1] Synthesis of Polymer P-1 A 10L flask equipped with a stirrer, thermometer, nitrogen purge device, and reflux condenser was charged with 245.4g (0.235 mol) of the compound represented by formula (S-2a) and 430.5g (1.00 mol) of the compound represented by formula (S-4a), followed by 1500g of toluene and heating to 70°C. Then, 1.0g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 142.9g (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 completion of the dropwise addition, the mixture was heated to 90°C and aged for 11 hours. The toluene was then removed from the reaction solution by distillation under reduced pressure to obtain a polymer. 2000 g of propylene glycol monomethyl ether was added to this polymer, and after confirming that it had dissolved, 444.5 g (6.00 mol) of the compound represented by formula (S-5a) 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 completed, propylene glycol monomethyl ether and triethylamine were distilled off under reduced pressure from the reaction solution to obtain polymer P-1. The Mw of polymer P-1 was 8000. The Mw was measured by gel permeation chromatography (GPC) using tetrahydrofuran as an elution solvent, using a polystyrene equivalent value. Polymer P-1 was 1 It was confirmed by 1 H-NMR (manufactured by Bruker) that the polymer contained repeating units represented by formula (A1) and repeating units represented by formula (A2).

[0134] [Synthesis Example 2] Synthesis of Polymer P-2 A 10L flask equipped with a stirrer, thermometer, nitrogen purge device, and reflux condenser was charged with 530.5g (0.18 mol) of the compound represented by formula (S-2b), 387.5g (0.90 mol) of the compound represented by formula (S-4a), and 18.64g (0.10 mol) of the compound represented by formula (S-3). Then, 1500g of toluene was added and heated to 70°C. Then, 1.0g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 153.6g (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, the mixture was heated to 90°C and aged for 11 hours. The toluene was then removed from the reaction solution by vacuum distillation to obtain a polymer. 2000 g of propylene glycol monomethyl ether was added to this polymer, and after confirming that it had dissolved, 400.0 g (5.40 mol) of the compound represented by formula (S-5a) 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 completed, propylene glycol monomethyl ether and triethylamine were distilled off from the reaction solution under reduced pressure to obtain polymer P-2. The Mw of polymer P-2 was 80,000. Polymer P-2 was also obtained by 1 H-NMR (Bruker) confirmed that the polymer contained 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).

[0135] [Synthesis Example 3] Synthesis of Polymer P-3 A 10L flask equipped with a stirrer, thermometer, nitrogen purge device, and reflux condenser was charged with 245.4g (0.235 mol) of the compound represented by formula (S-2a) and 430.5g (1.00 mol) of the compound represented by formula (S-4a), followed by 1500g of toluene and heating to 70°C. Then, 1.0g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 142.9g (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 completion of the dropwise addition, the mixture was heated to 90°C and aged for 11 hours. The toluene was then removed from the reaction solution by distillation under reduced pressure to obtain a polymer. 2000 g of propylene glycol monomethyl ether was added to this polymer, and after confirming that it had dissolved, 528.6 g (6.00 mol) of the compound represented by formula (S-5b) 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 completed, propylene glycol monomethyl ether and triethylamine were distilled off from the reaction solution under reduced pressure to obtain polymer P-3. The Mw of polymer P-3 was 8500. Polymer P-3 was 1 It was confirmed by 1 H-NMR (manufactured by Bruker) that the polymer contained repeating units represented by formula (A1) and repeating units represented by formula (A2).

[0136] [Synthesis Example 4] Synthesis of Polymer P-4 A 10L flask equipped with a stirrer, thermometer, nitrogen purge device, and reflux condenser was charged with 245.4g (0.235 mol) of the compound represented by formula (S-2a) and 430.5g (1.00 mol) of the compound represented by formula (S-4a), followed by 1500g of toluene and heating to 70°C. Then, 1.0g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 142.9g (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 completion of the dropwise addition, the mixture was heated to 90°C and aged for 11 hours. The toluene was then removed from the reaction solution by distillation under reduced pressure to obtain a polymer. 2000 g of propylene glycol monomethyl ether was added to this polymer, and after confirming that it had dissolved, 696.7 g (6.00 mol) of the compound represented by formula (S-5c) 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 completed, propylene glycol monomethyl ether and triethylamine were distilled off from the reaction solution under reduced pressure to obtain polymer P-4. The Mw of polymer P-4 was 9000. Polymer P-4 was 1 It was confirmed by 1 H-NMR (manufactured by Bruker) that the polymer contained repeating units represented by formula (A1) and repeating units represented by formula (A2).

[0137] [Comparative Synthesis Example 1] Synthesis of Comparative Polymer CP-1 A 10-L flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser was charged with 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-4b), and 18.6 g (0.10 mol) of the compound represented by formula (S-3). Then, 1100 g of toluene was added and the mixture was heated to 80 °C. Next, 1.0 g of a toluene solution of chloroplatinic acid (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, the mixture was heated to 100 °C and aged for 6 hours. The toluene was then removed from the reaction solution by distillation under reduced pressure to obtain comparative polymer CP-1. The Mw of comparative polymer CP-1 was 12,000.

[0138] [Comparative Synthesis Example 2] Synthesis of Comparative Polymer CP-2 A 10-L flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser was charged with 362 g (0.45 mol) of the compound represented by formula (S-2b), 215 g (0.50 mol) of the compound represented by formula (S-4a), and 271 g (0.50 mol) of the compound represented by formula (S-4b). Then, 2100 g of toluene was added and the mixture was heated to 70 °C. Then, 2.0 g of a toluene solution of chloroplatinic acid (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, the mixture was heated to 100 °C and aged for 12 hours. The toluene was then removed from the reaction solution by distillation under reduced pressure to obtain comparative polymer CP-2. The Mw of comparative polymer CP-2 was 14,000.

[0139] [2] Preparation of photosensitive resin composition [Examples 1 to 8 and Comparative Examples 1 to 10] The components were mixed according to the amounts shown in Tables 1 and 2, then stirred at room temperature to dissolve, and then microfiltered through a 1.0 μm Teflon (registered trademark) filter to prepare the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 10.

[0140] [Table 1]

[0141] [Table 2]

[0142] In Tables 1 and 2, crosslinking agents B-1 to B-4 and B'-1 to B'-2 are as follows: B-3 is 2,2',6,6'-tetramethoxymethylbisphenol A, and B'-3 is the isocyanate crosslinking agent Duranate TMA-100 (manufactured by Asahi Kasei Corporation). [ka]

[0143] In Tables 1 and 2, the photoacid generators C-1 and C-2 are as follows. [ka]

[0144] In Tables 1 and 2, the comparative polymer CP-3 is as follows: [ka]

[0145] [3] Preparation of photosensitive dry film Using a die coater as the film coater and a polyethylene terephthalate film (38 μm thick) as the support film, each of the photosensitive resin compositions listed in Tables 1 to 3 was applied onto the support film. The film was then dried by passing it through a hot air circulating oven (4 m long) set at 100°C for 5 minutes, forming a photosensitive resin film on the support film, thereby obtaining a photosensitive dry film. A polyethylene film (50 μm thick) was attached as a protective film to the photosensitive resin film using a laminating roll at a pressure of 1 MPa, producing a photosensitive dry film with a protective film. The thickness of each photosensitive resin film was 50 μm. The thickness of the photosensitive resin film was measured using an optical interference film thickness measuring instrument (F50-EXR, manufactured by Filmetrics Inc.).

[0146] [4] Evaluation of resin film (1) Pattern formation and its evaluation The protective film was peeled off from the photosensitive dry film with the protective film attached, and the photosensitive resin film on the support film was adhered to a migration test substrate (a comb-shaped electrode substrate with copper conductive material, conductive portion spacing and width of 10 μm, and conductive portion thickness of 4 μm) using a vacuum laminator TEAM-100RF (manufactured by Takatori Corporation) with the vacuum level set to 80 Pa. The temperature condition was 100°C. After returning to normal pressure, the substrate was removed from the vacuum laminator and the support film was peeled off. Next, to improve adhesion to the substrate, the substrate was preheated at 120°C for 5 minutes using a hot plate. To form a line-and-space pattern and a contact hole pattern in the resulting photosensitive resin film, the photosensitive resin film was exposed through a mask using a contact aligner-type exposure device at a wavelength of 365 nm. After exposure, the film was subjected to PEB for 5 minutes using a hot plate at 140°C, cooled, and then spray-developed with PGMEA for 300 seconds to form a pattern.

[0147] The photosensitive resin film on the substrate, patterned using the above method, was post-cured in an oven at 190°C for 2 hours with a nitrogen purge. The cross sections of the resulting 100 μm, 50 μm, and 30 μm contact hole patterns were then observed using a scanning electron microscope (SEM). The smallest hole pattern, with holes penetrating all the way to the bottom of the film, was defined as the limiting resolution. The verticality of the 100 μm contact hole pattern was evaluated using the resulting cross-sectional photographs. A perfectly vertical pattern was rated as ◎, slight inverted tapering or footing was rated as ○, severe inverted tapering or footing was rated as △, and poor opening was rated as ×. The results are shown in Tables 3 and 4.

[0148] (2) Evaluation of electrical properties (copper migration) A test was conducted using a substrate on which a pattern was formed by method (1) as a substrate for copper migration evaluation. The copper migration test was conducted under conditions of a temperature of 121°C, humidity of 100%, and an applied voltage of 10V, and the time until a short circuit occurred was counted up to 1000 hours. A mark of "O" was given if no short circuit occurred. The results are shown in Tables 3 and 4.

[0149] (3) Evaluation of reliability (adhesion, crack resistance) The protective film was peeled off from the photosensitive dry film with the protective film. Using a vacuum laminator TEAM-100RF (manufactured by Takatori Corporation), the vacuum level in the vacuum chamber was set to 80 Pa. The photosensitive resin film on the support film was adhered to a CCL substrate with a 10 mm x 10 mm silicon chip laminated thereon. The temperature was 100°C. After returning to normal pressure, the substrate was removed from the vacuum laminator and the support film was peeled off. Next, to enhance adhesion to the substrate, the substrate was preheated at 120°C for 5 minutes using a hot plate. The resulting photosensitive resin film was exposed to light at a wavelength of 365 nm without a mask using a contact aligner exposure device. After exposure, the film was subjected to PEB on a hot plate at 140°C for 5 minutes, cooled, and then post-cured in an oven at 190°C for 2 hours while purging with nitrogen. Then, using a dicing saw equipped with a dicing blade (DAD685, manufactured by DISCO, spindle rotation speed 40,000 rpm, cutting speed 20 mm / sec), 20 mm × 20 mm square test pieces were obtained so that the silicon chip circumference was 5 mm. The obtained test pieces (10 pieces each) were subjected to a heat cycle test (1000 cycles of holding at -55°C for 10 minutes and at 125°C for 10 minutes). After the heat cycle test, the state of peeling of the resin film from the wafer and the presence or absence of cracks were confirmed. A circle was marked for no peeling or cracking, a cross-sectional SEM was marked for at least one peeling, and a cross-sectional SEM was marked for at least one crack. The presence or absence of peeling and cracking was confirmed by top-down observation using an optical microscope and cross-sectional SEM observation. The results are shown in Tables 3 and 4.

[0150] (4) Evaluation of adhesive strength (before heat resistance test) The protective film was peeled off from the photosensitive dry film with protective film described above. Using a vacuum laminator TEAM-100RF (manufactured by Takatori Corporation), the vacuum level in the vacuum chamber was set to 80 Pa, and the photosensitive resin film on the support film was adhered to an 8-inch silicon wafer. The temperature condition was 100°C. After returning to normal pressure, the substrate was removed from the vacuum laminator, and the support film was peeled off. The substrate was then preheated at 120°C for 5 minutes using a hot plate. It was then exposed to light at a wavelength of 365 nm without a mask using a contact aligner-type exposure device. The substrate was cut into 2 mm x 2 mm square pieces using a dicing saw (DAD685, manufactured by DISCO Corporation) equipped with a dicing blade. A 2 mm x 2 mm square chip was then bonded to a separately prepared 15 mm x 15 mm square silicon wafer (base substrate) via the resin film at 150°C and a load of 50 mN. The resin film was then cured by heating at 190°C for 2 hours to obtain test specimens. Five test specimens were produced for each test and subjected to an adhesion strength measurement test. Adhesion strength measurements were performed using a bond tester (Dage Corporation, Dage series 4000-PXY) to measure the resistance force required to peel a semiconductor chip (2 mm x 2 mm) from a base substrate (a 15 mm x 15 mm square silicon wafer), and the adhesion strength of the resin film layer was evaluated. The test was performed at a test speed of 200 μm / sec and a test height of 50 μm. The results are shown in Tables 3 and 4. The values ​​are the average of the measurements for five test specimens, with higher values ​​indicating higher adhesion strength.

[0151] (5) Evaluation of adhesive strength (after heat resistance test) The test pieces for adhesive strength measurement prepared in (4) above were left in an oven heated to 240°C for 100 hours, and then the test pieces were removed from the oven and subjected to the adhesive strength measurement test in the same manner as in (5). The results are shown in Tables 3 and 4.

[0152] (6) Evaluation of photoresist stripper resistance To evaluate the solvent resistance to N-methyl-2-pyrrolidone (NMP) solution containing 30% tetramethylammonium hydroxide (TMAH), a photoresist stripper with relatively strong dissolving power, 15 mm × 15 mm patterns were formed on silicon wafers using the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 10 in the same manner as in (1) for preparing wafers for copper migration testing. The wafers were immersed in N-methyl-2-pyrrolidone (NMP) solution containing 30% tetramethylammonium hydroxide (TMAH) at 40°C for 1 hour, and then the change in film thickness and appearance were examined to evaluate the photoresist stripper resistance. Those that showed no change in appearance or film thickness were marked with an ◯, and those that showed swelling or other abnormalities were marked with an ×. The results are shown in Tables 3 and 4.

[0153] [Table 3]

[0154] [Table 4]

[0155] From the above results, the photosensitive resin composition and photosensitive dry film of the present invention can easily form a thick, fine, vertical pattern, demonstrating sufficient properties as a photosensitive material. Furthermore, the cured film obtained from them exhibits excellent copper migration resistance, photoresist stripping solution resistance, adhesion to substrates, and heat resistance, and is highly reliable as an insulating protective film in terms of crack resistance, adhesion, etc., making it suitable for use as a material for forming protective films for various electrical and electronic components, such as circuit boards, semiconductor elements, and display elements. The present invention makes it possible to provide a more reliable photosensitive resin composition and photosensitive dry film.

Claims

1. (A) a polymer having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in its main chain and containing a polyhydric alcohol structure in its side chain; (B) at least one crosslinking agent selected from a nitrogen-containing compound selected from a melamine compound, a guanamine compound, a glycoluril compound, and a urea compound, each containing an average of two or more methylol groups and / or alkoxymethyl groups per molecule, an amino condensate modified with formaldehyde or formaldehyde-alcohol, and a phenol compound having an average of two or more methylol groups or alkoxymethyl groups per molecule, and (C) Photoacid generator A photosensitive resin composition comprising:

2. 2. The photosensitive resin composition according to claim 1, wherein the polymer (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 a repeating unit represented by the following formula (A3) and a repeating unit represented by the following formula (A4): 【Chemical 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 from each other. a, b, c, and d are numbers that satisfy the following conditions: 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, n 1 and n 2 are each independently an integer of 1 to 7. 11 and R 12 are each independently a hydrogen atom or a methyl group. 1 ~L 4 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 are 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. L 1 , L 2 , L 3 and L 4 3. The photosensitive resin composition according to claim 2, wherein each of the carbon atoms of is 1.

4. 2. The photosensitive resin composition according to claim 1, wherein the content of the compound of component (B) is 1 to 50 parts by mass per 100 parts by mass of component (A).

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

6. A photosensitive resin film obtained from the photosensitive resin composition according to any one of claims 1 to 5.

7. A photosensitive dry film comprising a support film and the photosensitive resin film according to claim 6 on the support film.

8. (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 developer to form a pattern. A pattern forming method comprising:

9. The pattern forming method according to claim 8, further comprising the step of (iv) post-curing the photosensitive resin film patterned by development at a temperature of 100 to 250°C.

10. (i') forming a photosensitive resin film on a substrate using the photosensitive dry film according to claim 7; (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. A pattern forming method comprising:

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

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

13. The photosensitive resin composition according to any one of claims 1 to 5, which is a material for a substrate bonding film for bonding two substrates together.

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