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

Abstract

The present invention provides a photosensitive resin composition including (A) a polymer having a silylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in a main chain and containing a polyol structure in a side chain, (B) a cross-linking agent having a specific structure, and (C) a photoacid generator.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This nonprovisional application claims priority under 35 U.S.C. §119(a) to patent application No. 2024-047468 filed in Japan on March 25, 2024, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present invention relates to a photosensitive resin composition, a photosensitive resin coating, a photosensitive dry film and a pattern forming method. Background Art

[0004] In the prior art, photosensitive protective films for semiconductor devices and photosensitive insulating films for multilayer printed circuit boards are formed from photosensitive polyimide compositions, photosensitive epoxy resin compositions, photosensitive silicone compositions, and the like. Patent Document 1 discloses a photosensitive silicone composition with improved flexibility as a photosensitive material used to protect such substrates and circuits. This photosensitive silicone composition is curable at low temperatures and forms a coating that is highly reliable in terms of wet adhesion resistance and other properties, but has poor resistance to chemicals such as photoresist strippers (typically N-methyl-2-pyrrolidone).

[0005] To overcome this problem, Patent Document 2 proposes a photosensitive silicone composition based on a silicone polymer containing a silicon phenylene skeleton. While this photosensitive silicone composition exhibits improved chemical resistance against conventional photoresists, such as N-methyl-2-pyrrolidone, it still exhibits challenges in chemical resistance against photoresist strippers with higher solubility. Furthermore, there is a need for further improvements in fine pattern formation and resin coating reliability.

[0006] Reference List

[0007] Patent Document 1: JP-A 2002-88158

[0008] Patent Document 2: JP-A 2008-184571 Summary of the Invention

[0009] The present invention has been made under the above circumstances, and its object is to provide a photosensitive resin composition, a photosensitive resin coating, a photosensitive dry film, and a pattern forming method using the foregoing, wherein the resin coating or resin layer can be easily processed in a thick film form to define a fine-sized vertical pattern, and a cured coating having excellent copper migration resistance, photoresist stripper resistance, adhesion to substrates and the like, and heat resistance, and having excellent reliability as a protective film for electric and electronic parts and a film for bonding to substrates.

[0010] The present inventors have conducted extensive research to achieve the above object and have found that the 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 the main chain and having a polyol structure in the side chain; (B) at least one crosslinking agent selected from nitrogen-containing compounds selected from melamine, guanamine, glycoluril and urea compounds having an average of at least two hydroxymethyl and / or alkoxymethyl groups per molecule, amino condensates modified with formaldehyde or formaldehyde-alcohol, and phenolic compounds having an average of at least two hydroxymethyl or alkoxymethyl groups per molecule; and (C) a photoacid generator. The present invention has been conceived based on this finding.

[0011] That is, the present invention provides the following photosensitive resin composition, photosensitive resin coating, photosensitive dry film and patterning method.

[0012] 1. A photosensitive resin composition comprising:

[0013] (A) A polymer having a silphenylene skeleton, a polysiloxane skeleton and a fluorene skeleton in the main chain and having a polyol structure in the side chain;

[0014] (B) At least one crosslinking agent selected from nitrogen-containing compounds selected from melamine, guanamine, glycoluril and urea compounds having an average of at least two hydroxymethyl and / or alkoxymethyl groups per molecule, amino condensates modified with formaldehyde or formaldehyde-alcohol, and phenolic compounds having an average of at least two hydroxymethyl or alkoxymethyl groups per molecule; and

[0015] (C) A photoacid generator.

[0016] 2. The photosensitive resin composition according to 1, wherein the polymer (A) comprises a repeating unit having the formula (A1) and a repeating unit having the formula (A2), and may further comprise a repeating unit having the formula (A3) and a repeating unit having the formula (A4): 0]

[0017]

[0018] Wherein, R 1 to R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms and may contain heteroatoms, m is each independently an integer of 1 to 600, and when m is an integer of 2 or more, R 3 may be the same or different from each other and R 4 may be the same 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 having the formula (X1), and X <关于这个需求我无法为你提供相应帮助。你可以尝试提供其他话题,我会尽力为你提供支持和解答。 2is a divalent group having formula (X2);

[0019]

[0020] Among them, n 1 and n 2 are each independently an integer from 1 to 7, R 11 and R 12 are each independently a hydrogen atom or a methyl group, L 1 To L 4 Each is independently a saturated alkylene group having 1 to 15 carbon atoms, a portion of -CH2- of the saturated alkylene group may be replaced by -O-, -S-, -SO2-, -CO- or -CONH-, a portion or all of the hydrogen atoms of the saturated alkylene group may be substituted by hydroxyl groups, and the dotted line represents a bond;

[0021]

[0022] Among them, R 21 and R 22 are each independently a hydrogen atom or a methyl group, R 23 and R 24 are each independently a hydrocarbon group having 1 to 8 carbon atoms, k 1 and k 2 Each is independently an integer from 0 to 7, p is an integer from 0 to 600, and the dotted line represents a bond.

[0023] 3. The photosensitive resin composition according to 2, wherein L 1 , L 2 , L 3 and L 4 All have 1 carbon atom.

[0024] 4. The photosensitive resin composition according to any one of 1 to 3, wherein the content of the compound as component (B) is 1 to 50 parts by weight relative to 100 parts by weight of component (A).

[0025] 5. The photosensitive resin composition according to any one of 1 to 4, further comprising (D) a solvent.

[0026] 6. A photosensitive resin coating obtained from the photosensitive resin composition according to any one of 1 to 5.

[0027] 7. A photosensitive dry film comprising a support film and the photosensitive resin coating according to 6 thereon.

[0028] 8. A pattern forming method comprising the following steps:

[0029] (i) applying the photosensitive resin composition according to any one of 1 to 5 onto a substrate to form a photosensitive resin coating layer thereon,

[0030] (ii) exposing the photosensitive resin coating to radiation, and

[0031] (iii) The exposed resin coating layer is developed with a developer to form a pattern of the resin coating layer.

[0032] 9. The pattern forming method according to 8, further comprising (iv) post-curing the patterned resin coating obtained from the development step at a temperature of 100 to 250°C.

[0033] 10. A pattern forming method comprising the following steps:

[0034] (i') using the photosensitive dry film according to 7 to form a photosensitive resin coating on a substrate,

[0035] (ii) exposing the photosensitive resin coating to radiation, and

[0036] (iii) The exposed resin coating layer is developed with a developer to form a pattern of the resin coating layer.

[0037] 11. The pattern forming method according to 10, further comprising (iv) post-curing the patterned resin coating obtained from the developing step at a temperature of 100 to 250°C.

[0038] 12. The photosensitive resin composition according to any one of 1 to 5, which is a material suitable for forming a coating layer for protecting electric and electronic components.

[0039] 13. The photosensitive resin composition according to any one of 1 to 5, which is a material suitable for forming a substrate bonding coating layer for bonding two substrates.

[0040] Effects of the Invention

[0041] The photosensitive resin composition of the present invention is capable of forming a coating having a wide range of thickness variations and is easily formed into small-scale patterns in thick film form with improved verticality by the pattern forming method defined herein. The cured coating obtained by the photosensitive resin composition and photosensitive dry film of the present invention has excellent photoresist stripper tolerance, adhesion to substrates, etc., and heat resistance, and is improved in adhesion to substrates, especially substrates for electronic components and semiconductor devices, especially circuit boards, mechanical properties including crack resistance, and copper migration resistance. In addition, the coating is completely reliable as an insulating protective film and is advantageously used as a material suitable for forming a protective film for protecting electrical and electronic components such as circuit boards, semiconductor devices, and display devices, as well as a material suitable for forming a film for bonding to a substrate. Detailed Implementation Modes

[0042] [Photosensitive Resin Composition]

[0043] The present invention provides a photosensitive resin composition, which comprises (A) a polymer having a silphenylene skeleton, a polysiloxane skeleton and a fluorene skeleton in the main chain and containing a polyol structure in the side chain, (B) a crosslinking agent having a specific structure, and (C) a photoacid generator.

[0044] [(A) A polymer having a silphenylene skeleton, a polysiloxane skeleton and a fluorene skeleton in the main chain and containing a polyol structure in the side chain]

[0045] The polymer as component (A) is preferably a polymer containing a repeating unit having the formula (A1) and a repeating unit having the formula (A2), and may further contain a repeating unit having the formula (A3) and a repeating unit having the formula (A4).

[0046]

[0047] In the formulas (A1) to (A4), a, b, c and d are numbers satisfying 0 < a < 1, 0 < b < 1, 0 ≤ c < 1, 0 ≤ d < 1 and a + b + c + d = 1, and are preferably numbers satisfying 0.1 < a < 0.8, 0.1 < b < 0.8, 0 ≤ c < 0.15, 0 ≤ d < 0.15 and a + b + c + d = 1.

[0048] In the formulas (A2) and (A4), R 1 to R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms and may contain heteroatoms. m is each independently an integer from 1 to 600, and is preferably an integer from 8 to 100. When m is an integer of 2 or more, R 3 may be the same or different from each other, and R 4 may be the same or different from each other.

[0049] In each of the formulas (A2) and (A4), when there are two or more siloxane units (i.e., when m is an integer of 2 or more), all the siloxane units may be the same as each other, or the repeating unit of the formula (A2) or (A4) may contain two or more different siloxane units. When the repeating unit of the formula (A2) or (A4) contains two or more different siloxane units, the siloxane units may be randomly bonded or alternately bonded, or the repeating unit of the formula (A2) or (A4) may contain multiple blocks of the same siloxane unit.

[0050] In the formulas (A1) and (A2), X 1 is a divalent group having the formula (X1). The divalent group having the formula (X1) is a group having a fluorene skeleton.

[0051]

[0052] In the formula, dashed lines represent bonds.

[0053] In formula (X1), n 1 and n 2 Each is independently an integer of 1 to 7, and each is preferably 1.

[0054] In formula (X1), R 11 and R 12 are each independently a hydrogen atom or a methyl group, and R 11 and R 12 Both are preferably hydrogen atoms.

[0055] In formula (X1), L 1 To L 4 Each independently is a saturated alkylene group having 1 to 15 carbon atoms, the part -CH2- of the saturated alkylene group may be replaced by -O-, -S-, -SO2-, -CO- or -CONH-, and part or all of the hydrogen atoms of the saturated alkylene group may be replaced by hydroxyl groups.-CH2- of the saturated alkylene group may be located at its terminal.

[0056] The saturated alkylene group may be linear, branched or cyclic, and specific examples thereof include alkanediyl groups having 1 to 15 carbon atoms, such as 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-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1,14-diyl group, and a pentadecane-1,15-diyl group; and a cyclic saturated alkylene group having 3 to 15 carbon atoms, such as a cyclopentanediyl group, a cyclohexanediyl group, a norbornanediyl group, and an adamantanediyl group.

[0057] Preferably, L 1 and L 3 Both have 1 carbon atom and more preferably L 2 and L 4 Both have 1 carbon atom.

[0058] In formulas (A3) and (A4), X 2 is a divalent group having the formula (X2).

[0059]

[0060] In the formula, dashed lines represent bonds.

[0061] In formula (X2), R 21 and R 22 Each is independently a hydrogen atom or a methyl group, and each is preferably a hydrogen atom.

[0062] In formula (X2), R 23 and R 24 Each is independently a hydrocarbyl group having 1 to 8 carbon atoms.

[0063] In formula (X2), k 1 and k 2 Each is independently an integer from 0 to 7, and each is preferably 0.

[0064] 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, R 23 can be the same as or different from each other, and R 24 They may be the same as or different from each other.

[0065] The polymer as component (A) preferably has a weight average molecular weight (Mw) of 2,000 to 500,000, and more preferably 8,000 to 100,000. A polymer having an Mw within the above range can be obtained in the form of a solid, and film-forming properties can also be ensured. In the present invention, Mw is a value measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an elution solvent relative to polystyrene.

[0066] The polymer as component (A) may be a polymer in which repeating units of formula (A1), repeating units of formula (A2), repeating units of formula (A3) and repeating units of formula (A4) are randomly bonded or alternately bonded, or may contain a plurality of blocks of each unit.

[0067] The polymer as component (A) serves as a polymer imparting film-forming ability. The obtained resin film has good pattern-forming ability, and the obtained cured film has good adhesion to substrates, crack resistance, chemical resistance, and heat resistance.

[0068] The polymer as component (A) may be used alone or in combination of two or more thereof.

[0069] The method for preparing the polymer as component (A) is not particularly limited, and for example, the polymer can be prepared by addition polymerization of a compound having formula (1), a compound having formula (2), a compound having formula (3) and, if necessary, a compound having formula (4) in the presence of a metal catalyst.

[0070]

[0071] In this formula, R 1 to R 4 and m are as defined above.

[0072]

[0073] In this formula, R 11 and R 12 、n 1 、n 2 and L 1 To L 4 As defined above.

[0074]

[0075] In this formula, R 21 to R 24 、k 1 、k 2 and p are as defined above.

[0076] As the metal catalyst, the following catalysts can be used: simple substances of platinum group metals, such as platinum (including platinum black), rhodium and palladium; platinum chlorides, chloroplatinic acids and chloroplatinates, such as H2PtCl4·xH2O, H2PtCl6·xH2O, NaHPtCl6·xH2O, KHPtCl6·xH2O, Na2PtCl6·xH2O, K2PtCl4·xH2O, PtCl4·xH2O, PtCl2 and Na2HPtCl4·xH2O (wherein x is preferably an integer from 0 to 6, and particularly preferably 0 or 6); alcohol-modified chlorine; Platinic acids (for example, those described in U.S. Pat. No. 3,220,972); complexes of chloroplatinic acid with olefins (for example, those described in U.S. Pat. No. 3,159,601, U.S. Pat. No. 3,159,662 and U.S. Pat. No. 3,775,452); platinum group metals such as platinum black and palladium supported on supports such as alumina, silica or carbon; rhodium-olefin complexes; tris(triphenylphosphine)rhodium chloride (the so-called Wilkinson catalyst); and complexes of platinum chloride, chloroplatinic acid or chloroplatinates with siloxanes containing vinyl groups (in particular cyclosiloxanes containing vinyl groups).

[0077] The amount of the catalyst used is a catalytic amount, and is generally preferably 0.001% by weight to 0.1% by weight relative to the total amount of the reactive polymer in terms of platinum group metal. In the polymerization reaction, a solvent may be used if necessary. The solvent is preferably a hydrocarbon solvent such as toluene or xylene, for example. Regarding the polymerization conditions, from the perspective of suppressing the deactivation of the catalyst and completing the polymerization in a short time, the polymerization temperature is, for example, preferably 40 to 150° C., and particularly preferably 60 to 120° C. The polymerization time depends on the type and amount of the polymer, but in order to suppress the interference of moisture in the polymerization system, it is preferably about 0.5 to 100 hours, and particularly preferably about 0.5 to 30 hours. After the polymerization reaction is completed, when a solvent is used, it is distilled off to obtain a polymer.

[0078] The reaction method is not particularly limited, but it is preferred that the compound having the formula (2), the compound having the formula (3) and, if necessary, the compound having the formula (4) are first mixed and heated, and then a metal catalyst is added to the resulting mixed solution, and then the compound having the formula (1) is added dropwise to the mixed solution over 0.1 to 5 hours.

[0079] It is preferred that these raw material compounds be blended so that the total amount of the hydrosilyl groups in the compound having the formula (1) and the compound having the formula (2) is 0.67 to 1.67, and more preferably 0.83 to 1.25, in terms of molar ratio relative to the total amount of the alkenyl groups in the compound having the formula (3) and the compound having the formula (4). The Mw of the polymer of the present invention can be controlled by using a monoallyl compound such as o-allylphenol or monohydrogensilane or monohydrogensiloxane such as triethylhydrogensilane as a molecular weight modifier.

[0080] In the polymerization reaction, a polymerization inhibitor may be optionally used. Examples of the polymerization inhibitor used include various phenols, hydroquinones, benzoquinones, catechols, hydroxylamines, and nitroso compounds. The amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.001 to 10% by weight, and more preferably 0.01 to 5% by weight, relative to the compound having formula (3).

[0081] After the reaction is complete, a solvent is optionally added and water washing is performed. The solvent is then distilled off by heating the organic layer under reduced pressure to produce a polymer as component (A). In the water washing, 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 optionally be used.

[0082] Another example of a method for preparing a polymer as component (A) is a reaction between a polymer containing repeating units having formula (B1) and repeating units having formula (B2) and may further contain repeating units having formula (B3) and repeating units having formula (B4) (hereinafter, the polymer is also referred to as polymer (B)) and a compound having formula (5).

[0083]

[0084] In this formula, R 1 to R 4 , m, a, b, c, d, and X 2 As defined above.

[0085]

[0086] In formulas (B1) and (B2), X 3 is a divalent group having the formula (X3). The divalent group having the formula (X3) is a group having a fluorene skeleton.

[0087]

[0088] In this formula, R 11 、R 12 、n 1 and n 2 As defined above. Dashed lines represent bonds.

[0089] In formula (5), L 5 is a saturated alkylene group having 1 to 14 carbon atoms, a portion of -CH2- of the saturated alkylene group may be replaced by -O-, -S-, -SO2-, -CO- or -CONH-, and a portion or all of the hydrogen atoms of the saturated alkylene group may be replaced by hydroxyl groups. 5 The saturated hydrocarbylene group represented may be linear, branched or cyclic and preferably has 1 to 7 carbon atoms.

[0090] In formula (5), L 6 is a saturated alkylene group having 1 to 14 carbon atoms, a portion of -CH2- of the saturated alkylene group may be replaced by -O-, -S-, -SO2-, -CO- or -CONH-, and a portion or all of the hydrogen atoms of the saturated alkylene group may be replaced by hydroxyl groups. 5 The saturated hydrocarbylene group represented may be linear, branched or cyclic and preferably has 1 to 7 carbon atoms.

[0091] Specific examples of the compound having the formula (5) include Epiol manufactured by NOF CORPORATION), but not limited thereto.

[0092] The reaction conditions are not particularly limited, but it is generally preferred to mix the polymer B and the compound having the formula (5) in a solvent and heat. From the viewpoint of promoting the reaction, a polar solvent is preferably used as the solvent, and an alcohol solvent such as propylene glycol monomethyl ether is particularly preferably used. From the viewpoint of suppressing side reactions and completing the reaction in a short time, the reaction temperature is, for example, preferably 35 to 130° C., and particularly preferably 45 to 100° C. The reaction time 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.

[0093] In the above reaction, the raw material compounds are blended so that the compound having the formula (5) is greater than X in the polymer B. 3 The molar ratio is preferably 1.0 to 8.0, and more preferably 4.0 to 6.0. The compound having the formula (5) may be used alone or in combination of two or more types thereof.

[0094] In the above 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; imidazole compounds such as imidazole and 2-ethyl-4-methylimidazole; pyridine compounds such as pyridine, N,N-dimethyl-4-aminopyridine, 2,6-lutidine; organic tin compounds such as tin acetate, tin octoate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaprol, dibutyltin maleate, dibutyltin dilaurate (dibutyltin(IV) dilaurate), dibutyltin dineodecanoate, dioctyltin dimercaprol, dioctyltin dilaurate, and dibutyltin dichloride; organolead compounds such as lead octoate and lead naphthenate; organonickel compounds such as nickel naphthenate; organocobalt compounds such as cobalt naphthenate; organocopper compounds such as copper octoate; organobismuth compounds such as bismuth octoate and bismuth neodecanoate; and potassium salts such as potassium carbonate, potassium acetate, and potassium octoate.

[0095] The amount of catalyst used is usually a catalytic amount and is relative to the X in polymer B. 3 It is preferably 0.1 mol% to 20 mol%. The catalyst may be used alone or in combination of two or more types.

[0096] In the above reaction, a polymerization inhibitor may be optionally used. Examples of the polymerization inhibitor include various phenols, hydroquinones, benzoquinones, catechols, hydroxylamines, and nitroso compounds. The amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.001 to 10% by weight, and more preferably 0.01 to 5% by weight, relative to the compound of formula (3).

[0097] After the reaction is complete, a solvent is optionally added and water washing is performed. The solvent is then distilled off by heating the organic layer under reduced pressure to produce a polymer as component (A). In the water washing, 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 optionally be used.

[0098] [(B) Cross-linking agent]

[0099] The crosslinking agent as component (B) is at least one crosslinking agent selected from nitrogen-containing compounds selected from melamine, guanamine, glycoluril, and urea compounds having an average of at least two hydroxymethyl and / or alkoxymethyl groups per molecule, amino condensates modified with formaldehyde or formaldehyde-alcohol, and phenolic compounds having an average of at least two hydroxymethyl or alkoxymethyl groups per molecule. The crosslinking agent crosslinks with the polymer as component (A) to form a fine vertical pattern in the form of a thick film, and produces a cured film having excellent adhesion to substrates, crack resistance, chemical resistance, and heat resistance.

[0100] Suitable melamine compounds include those having formula (B1).

[0101]

[0102] In formula (B1), R 101 to R 106 Each independently represents a hydroxymethyl group, a C2-C5 saturated hydrocarbon oxymethyl group or a hydrogen atom, R 101 to R 106 At least one of the groups is a hydroxymethyl group or a saturated hydrocarbyloxymethyl group. Suitable saturated hydrocarbyloxymethyl groups include alkoxymethyl groups such as methoxymethyl and ethoxymethyl.

[0103] Examples of the melamine compound having the formula (B1) include trimethoxymethylmonomethylolmelamine, dimethoxymethylmonomethylolmelamine, trimethylolmelamine, hexamethylolmelamine, hexamethoxymethylmelamine, and hexaethoxymethylmelamine.

[0104] The melamine compound of formula (B1) can be obtained, for example, by modifying the melamine monomer with formaldehyde in a known manner to the methylol form and optionally further modifying it with an alcohol to the alkoxy form. The alcohol used herein is preferably a lower alcohol, for example an alcohol having 1 to 4 carbon atoms.

[0105] Suitable guanamine compounds include tetrakishydroxymethylguanamine, tetramethoxymethylguanamine, and tetramethoxyethylguanamine.

[0106] Suitable glycoluril compounds include tetrakishydroxymethyl glycoluril and tetrakis(methoxymethyl) glycoluril.

[0107] Suitable urea compounds include tetramethylol urea, tetramethoxymethyl urea, tetramethoxyethyl urea, tetraethoxymethyl urea, and tetrapropoxymethyl urea.

[0108] Examples of the amino condensate modified with formaldehyde or formaldehyde-alcohol include melamine condensates modified with formaldehyde or formaldehyde-alcohol and urea condensates modified with formaldehyde or formaldehyde-alcohol.

[0109] The modified melamine condensate is obtained, for example, by subjecting a compound having formula (B1) or a polymer thereof (e.g., an oligomer, such as a dimer or trimer) to addition polycondensation with formaldehyde until the desired molecular weight is reached. The addition polycondensation can be carried out by any method known in the art. The modified melamines having formula (B1) can be used alone or in mixtures.

[0110] Examples of the urea condensate modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensate, ethoxymethylated urea condensate, and propoxymethylated urea condensate.

[0111] The modified urea condensates are prepared, for example, by modifying a urea condensate having the desired molecular weight in a known manner with formaldehyde to the methylol form and optionally additionally with an alcohol to the alkoxy form.

[0112] Examples of the phenol compound having an average of at least two hydroxymethyl or alkoxymethyl groups in the molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol and 2,2′,6,6′-tetramethoxymethylbisphenol A.

[0113] In the photosensitive resin composition, the content of component (B) is preferably 1 to 50 parts by weight, more preferably 1 to 30 parts by weight, relative to 100 parts by weight of component (A). At least 1 part of component (B) ensures sufficient curing during exposure. As long as the amount of component (B) is at most 50 parts by weight, the proportion of component (A) in the photosensitive resin composition is not reduced, allowing the cured composition to fully exert its effect. Component (B) can be used alone or in combination.

[0114] [(C) Photoacid generator]

[0115] The photoacid generator as component (C) is not particularly limited, as long as it decomposes to generate acid when exposed to light. Preferred are compounds that decompose to generate acid when exposed to light with a wavelength of 190 to 500 nm. PAG serves as a curing catalyst. Because the photosensitive resin composition of the present invention is highly compatible with PAG, the PAG can be selected from a large number of such compounds.

[0116] Suitable PAGs include salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzylsulfonate derivatives, sulfonate derivatives, imido-yl-sulfonate derivatives, oxime sulfonate derivatives, and iminosulfonate derivatives.

[0117] Exemplary Onium salts include sulfonium salts of formula (C1) and iodonium salts of formula (C2) (iodonium) salt.

[0118]

[0119] In formulas (C1) and (C2), R 201 to R 205 Each is independently an optionally substituted C1-C12 saturated hydrocarbon group, an optionally substituted C6-C12 aryl group or an optionally substituted C7-C12 aralkyl group. - It is a non-nucleophilic counterion.

[0120] The saturated hydrocarbon group can be linear, branched, or cyclic. Examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and their structural isomers; and cyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl. Aryl groups include phenyl, naphthyl, and biphenyl. Aralkyl groups include benzyl and phenethyl.

[0121] Suitable substituents include oxo, C1-C12 saturated hydrocarbon groups, C1-C12 saturated hydrocarbonoxy groups, C6-C24 aryl groups, C7-C25 aralkyl groups, C6-C24 aryloxy groups and C6-C24 arylthio groups. It is worth noting that the hydrocarbon moiety in the saturated hydrocarbon group and the saturated hydrocarbonoxy group can be linear, branched or cyclic, and its example is as described above for the saturated hydrocarbon group R 201 to R 205 Those exemplified.

[0122] R 201 to R205 Preferred examples include optionally substituted saturated hydrocarbon groups such as methyl, ethyl, propyl, butyl, cyclohexyl, norbornyl, adamantyl and 2-oxocyclohexyl; optionally substituted aryl groups such as phenyl, naphthyl, biphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 3- or 4-tert-butoxyphenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl, terphenyl, biphenyloxyphenyl and biphenylylthiophenyl; and optionally substituted aralkyl groups such as benzyl and phenethyl. Among them, more preferred are optionally substituted aryl groups and optionally substituted aralkyl groups.

[0123] Examples of non-nucleophilic counterions include hydrohalide ions such as chloride and bromide; fluoroalkanesulfonate ions such as trifluoromethanesulfonate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate; arylsulfonate ions such as toluenesulfonate, benzenesulfonate, 4-fluorobenzenesulfonate, and 1,2,3,4,5-pentafluorobenzenesulfonate; alkanesulfonate ions such as methanesulfonate and butanesulfonate; fluoroalkanesulfonylimide ions such as trifluoromethanesulfonylimide; fluoroalkanesulfonylmethide ions such as tris(trifluoromethanesulfonyl)methyl anion; borate ions such as tetraphenylborate and tetrakis(pentafluorophenyl)borate; and phosphate ions such as hexafluorophosphate and tris(pentafluoroethyl)trifluorophosphate.

[0124] Exemplary diazomethane derivatives include compounds having formula (C3).

[0125]

[0126] In formula (C3), R 211 and R 212 Each is independently a C1-C12 saturated hydrocarbon group, a C1-C12 halogenated saturated hydrocarbon group, an optionally substituted C6-C12 aryl group or a C7-C12 aralkyl group.

[0127] The saturated hydrocarbon group may be linear, branched or cyclic, and examples thereof are as described above for the saturated hydrocarbon group R 201 to R 205 Examples of the halogenated saturated hydrocarbon group include trifluoromethyl, 1,1,1-trifluoroethyl, 1,1,1-trichloroethyl and nonafluorobutyl.

[0128] Examples of optionally substituted aryl groups include phenyl; alkoxyphenyl groups such as 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 3- or 4-tert-butoxyphenyl; alkylphenyl groups such as 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl and dimethylphenyl; and halogenated aryl groups such as fluorophenyl, chlorophenyl and 1,2,3,4,5-pentafluorophenyl. Examples of aralkyl groups include benzyl and phenethyl.

[0129] Examples of salts include diphenyl iodide Trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyl iodide Trifluoromethanesulfonate, diphenyl iodide p-Toluenesulfonate, (p-tert-butoxyphenyl)phenyl iodide p-Toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium trifluoromethanesulfonate, 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, triphenylsulfonium butanesulfonate, 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, bis(4-tert-butylphenyl)iodide hexafluorophosphate, 4-(phenylthio)phenyldiphenylsulfonium tris(pentafluoroethyl) trifluorophosphate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate, [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium tris(trifluoromethanesulfonyl)methide, triphenylsulfonium tetrakis(fluorophenyl)borate, tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(fluorophenyl)borate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, and tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(pentafluorophenyl)borate.

[0130] Examples of diazomethane derivatives include bis(phenylsulfonyl)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, 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 and 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane.

[0131] Examples of 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-pentanedioneglyoxime, bis-O-(p-toluenesulfonyl)-2-methyl-3,4-pentanedioneglyoxime, 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, dioxime, 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.

[0132] Examples of the β-ketosulfone derivative include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane.

[0133] Examples of the disulfone derivatives include diphenyl disulfone and dicyclohexyl disulfone.

[0134] Examples of the nitrobenzylsulfonate derivative include 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.

[0135] Examples of the sulfonic acid ester derivatives include 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene.

[0136] Examples of imido-yl-sulfonate derivatives include phthalimido-yl-triflate, phthalimido-yl-tosylate, 5-norbornene-2,3-dicarboxyimido-yl-triflate, 5-norbornene-2,3-dicarboxyimido-yl-tosylate, 5-norbornene-2,3-dicarboxyimido-yl-n-butylsulfonate, and n-trifluoromethylsulfonyloxynaphthylimide.

[0137] Examples of the sulfonic acid oxime ester derivatives are α-(benzenesulfoniumoxyimino)-4-methylphenylacetonitrile and α-(p-tolylsulfoniumoxyimino)-p-methoxyphenylacetonitrile.

[0138] Examples of the imidosulfonate derivatives include (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile and (5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile.

[0139] Also useful is 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane.

[0140] In the photosensitive resin composition, from the perspective of photocurability, component (C) is preferably used in an amount of 0.05 to 20 parts by weight, more preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of component (A). An amount of at least 0.05 parts by weight of component (C) is preferred because sufficient acid is generated to allow the crosslinking reaction to proceed sufficiently. An amount of up to 20 parts by weight of component (C) effectively limits the increase in the absorbance of the PAG itself and eliminates the risk of causing a decrease in transparency. Component (C) can be used alone or in a mixture of two or more.

[0141] [(D) Solvent]

[0142] The photosensitive resin composition may further contain (D) a solvent. The solvent used herein is not particularly limited as long as the components (A) to (C) and the aforementioned various additives can be dissolved therein. An organic solvent is preferred because the components are efficiently dissolved.

[0143] Illustrative examples of organic solvents 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, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, and γ-butyrolactone. Among these solvents, ethyl lactate, cyclohexanone, cyclopentanone, PGMEA, γ-butyrolactone, and mixtures thereof are particularly preferred because PAG is most soluble.

[0144] In the photosensitive resin composition, from the viewpoint of compatibility and viscosity of the photosensitive resin composition, it is preferred to use component (D) in an amount of 50 to 2,000 parts by weight, more preferably 50 to 1,000 parts by weight, and even more preferably 50 to 100 parts by weight relative to 100 parts by weight of component (A). Component (D) may be used alone or in combination.

[0145] [Other additives]

[0146] In addition to the above components, the photosensitive resin composition may contain other additives. One exemplary other additive is a surfactant that is generally used to improve coating properties.

[0147] Preferred surfactants are nonionic surfactants, such as fluorochemical surfactants, such as perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkyl amine oxides, and fluorinated organosiloxane compounds. These surfactants are commercially available. Illustrative examples include 3M FC-430, from AGC SeimiChemical Co., Ltd. S-141 and S-145 from Daikin Industries Ltd. DS-401, DS-4031, and DS-451 from DIC Corp. F-8151 and X-70-093 from Shin-Etsu Chemical Co., Ltd. Preferred surfactants are Fluorad FC-430 and X-70-093. When the photosensitive resin composition contains a surfactant, the amount thereof is preferably 0.05 to 1 part by weight relative to 100 parts by weight of component (A).

[0148] The photosensitive resin composition may contain a silane coupling agent as another additive. The introduction of the silane coupling agent effectively enhances the adhesion of the coating of the composition to the adherend. Suitable silane coupling agents include epoxy-containing silane coupling agents and aromatic-containing aminosilane coupling agents. The silane coupling agents can be used alone or in combination. When the photosensitive resin composition contains a silane coupling agent, its amount is not particularly limited and is preferably 0.01% to 5% by weight of the photosensitive resin composition.

[0149] The photosensitive resin composition is prepared by a standard method. For example, the photosensitive resin composition can be prepared by stirring and mixing the aforementioned components and filtering off solids through a filter or the like if necessary.

[0150] The photosensitive resin composition prepared as above is advantageously used as, for example, a film-forming material for a semiconductor device protection film, an interconnect protection film, a cover film, a solder resist film, and a TSV dielectric film, and an adhesive between substrates in a three-dimensional laminate.

[0151] [Pattern Formation Method Using Photosensitive Resin Composition]

[0152] Another embodiment of the present invention is a pattern forming method using the photosensitive resin composition, comprising the following steps:

[0153] (i) applying a photosensitive resin composition to a substrate to form a photosensitive resin coating thereon,

[0154] (ii) exposing the photosensitive resin coating to radiation, and

[0155] (iii) The exposed resin coating layer is developed with a developer to form a pattern of the resin coating layer.

[0156] In step (i), a photosensitive resin composition is applied to a substrate to form a photosensitive resin coating thereon. Examples of substrates include silicon wafers, TSV silicon wafers, silicon wafers thinned by backside polishing, plastic substrates, ceramic substrates, and substrates having a Ni or Au metal coating applied entirely or partially to the surface by ion sputtering or plating. Rough or stepped substrates are sometimes used.

[0157] The photosensitive resin coating can be formed, for example, by coating the photosensitive resin composition onto a substrate and, if necessary, pre-baking the coating. The coating technique can be any known technique, such as dip coating, spin coating, or roller coating. The coating weight of the photosensitive resin composition can be appropriately selected for a particular purpose, preferably to form a photosensitive resin coating having a thickness of 0.1 to 200 μm, more preferably 1 to 150 μm.

[0158] In order to make the coating thickness on the substrate surface more uniform, a pre-wetting technique can be used in which a solvent is added dropwise to the substrate before applying the photosensitive resin composition. The type and amount of the solvent added dropwise can be selected for a specific purpose. For example, alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, and glycols such as PGME are preferred. Solvents used in photosensitive resin compositions can also be used.

[0159] At this point, if necessary, the coating can be prebaked to drive off solvents, etc., so that the coating is ready for an efficient photocuring reaction. The prebaking can be carried out, for example, at 40 to 140°C for 1 minute to about 1 hour.

[0160] Next, in step (ii), the photosensitive resin coating is exposed to radiation. The exposure radiation preferably has a wavelength of 10 to 600 nm, more preferably 190 to 500 nm. Examples of radiation within the wavelength range include radiation of various wavelengths from a radiation emitting unit, specifically, UV radiation such as g-line, h-line or i-line, and deep UV (248 nm, 193 nm). Among them, radiation of a wavelength of 248 to 436 nm is preferred. A suitable exposure dose is 10 to 10,000 mJ / cm 2 .

[0161] Exposure can be performed through a photomask. The photomask can be, for example, a photomask perforated with a desired pattern. Although the material of the photomask is not particularly limited, it can be a material that can shield radiation within the above-mentioned wavelength range. For example, a mask having a chromium light-shielding film is preferred.

[0162] The next step may be a post-exposure bake (PEB) to effectively improve the development sensitivity. PEB is preferably performed at 40 to 150° C. for 0.5 to 10 minutes. The exposed areas of the resin coating are cross-linked by PEB to form an insoluble pattern that is insoluble in an organic solvent as a developer.

[0163] After exposure or PEB, the exposed resin coating is developed with a developer to form a resin coating pattern (iii). Preferred developers are organic solvents, including alcohols such as IPA, ketones such as cyclohexanone, and glycols such as PGME. Solvents used in photosensitive resin compositions are also useful. Development is carried out in a conventional manner, for example, by immersing the coating to be patterned in a developer. The unexposed areas of the resin coating are dissolved by organic solvent development to form a pattern. If necessary, washing, rinsing and drying are performed after development. In this way, a resin coating with the desired pattern is obtained.

[0164] In step (iv), the patterned coating can be post-cured in an oven or on a hot plate at a temperature of preferably 100 to 250°C, more preferably 130 to 220°C. A post-curing temperature of 100 to 250°C is effective for increasing the cross-linking density of the photosensitive resin composition and removing any residual volatile substances, which is preferred from the perspective of adhesion to the substrate, heat resistance, mechanical strength, electrical properties and bonding strength. The post-curing time is preferably 10 minutes to 10 hours, more preferably 10 minutes to 3 hours. The photosensitive resin composition ensures that a coating with improved film properties is obtained even after post-curing at a relatively low temperature below 200°C. The post-cured resin coating (or cured coating) typically has a thickness of 1 to 200 μm, preferably 5 to 50 μm.

[0165] When patterning is not required, for example when only a uniform film is desired, the same patterning method as described above can be followed except that in step (ii) the resin coating is exposed to radiation of a suitable wavelength without a photomask.

[0166] [Substrate bonding method]

[0167] The photosensitive resin composition of the present invention can also be used as an adhesive for bonding two substrates. The substrate bonding method can be a method of bonding a first substrate having a coating of a resin composition formed thereon to a second substrate under a set of sufficient temperature and pressure conditions to form an adhesive bond between the substrates. One or both of the first substrate and the second substrate having the resin coating can be cut into chips, such as by cutting. Preferred bonding conditions include a temperature of 50 to 200°C and a time of 1 to 60 minutes. Any desired bonding unit can be used, such as a wafer bonder for bonding wafers under reduced pressure and under a certain load, or a flip chip bonder for performing chip-wafer or chip-chip bonding. The adhesive layer between the substrates can be subjected to a post-curing treatment to become a permanent bond with enhanced bonding strength.

[0168] The thus joined or bonded substrates can be post-cured under the same conditions as in step (iv) above to increase the crosslink density of the resin coating and enhance substrate bonding. It should be noted that a crosslinking reaction occurs during bonding due to heating. Because this crosslinking reaction is not accompanied by side reactions involving degassing, bonding voids are not caused when the photosensitive resin composition is used as a substrate adhesive.

[0169] [Photosensitive dry film]

[0170] Another embodiment of the present invention is a photosensitive dry film comprising a support and a photosensitive resin coating layer of a photosensitive resin composition thereon.

[0171] The photosensitive dry film (support + photosensitive resin coating) is solid, and the photosensitive resin coating does not contain solvents. This eliminates the risk of bubbles generated by solvent volatilization being trapped in the resin coating and between the resin coating and the uneven or stepped substrate.

[0172] The photosensitive resin coating layer has a thickness of preferably 5 to 200 μm, more preferably 10 to 100 μm, when considering flatness and step coverage on an uneven or stepped substrate and substrate lamination pitch.

[0173] Furthermore, the viscosity and fluidity of the photosensitive resin coating are closely related. As long as the photosensitive resin coating has an appropriate viscosity range, it exhibits sufficient fluidity to deeply fill even narrow gaps, or softens to enhance adhesion to the substrate. Therefore, from the perspective of fluidity, the photosensitive resin coating should preferably have a viscosity in the range of 10 to 5,000 Pa·s, more preferably 30 to 2,000 Pa·s, and even more preferably 50 to 300 Pa·s at a temperature of 80 to 120°C. It should be noted that the viscosity is measured using a rotational viscometer.

[0174] Photosensitive dry films offer the following advantages: when tightly adhered to a substrate with irregularities on its surface, the photosensitive resin coating conforms to the irregularities, achieving high flatness. Because the photosensitive resin coating exhibits low viscoelasticity, even higher flatness can be achieved. Furthermore, if the photosensitive resin coating is in close contact with the substrate in a vacuum environment, the formation of gaps between them is effectively suppressed.

[0175] The photosensitive dry film can be manufactured by applying a photosensitive resin composition to a support and drying the resin composition to a resin coating. The equipment for manufacturing the photosensitive dry film can be a film coater commonly used in the manufacture of pressure-sensitive adhesive products. Suitable film coaters include, for example, notch wheel coaters, notch wheel reverse coaters, multiple coaters, die coaters, lip coaters, lip reverse coaters, gravure coaters, offset gravure coaters, three-roller bottom reverse coaters, and four-roller bottom reverse coaters.

[0176] A support (film) is unwound from a supply roll in a film coater, passed through the head of the film coater, where a photosensitive resin composition is applied to the support to a predetermined deposit, and then passed through a hot air circulating oven at a predetermined temperature for a predetermined time, where the photosensitive resin coating on the support is dried to obtain a photosensitive dry film. If necessary, the photosensitive dry film and a protective film unwound from another supply roll in the film coater are passed through a laminating roller under a predetermined pressure, thereby bonding the protective film to the photosensitive resin coating on the support. The laminated product is then wound onto a take-up shaft in the film coater to obtain a photosensitive dry film with a protective film. Preferably, the oven temperature is 25 to 150°C, the transit time is 1 to 100 minutes, and the bonding pressure is 0.01 to 5 MPa.

[0177] The support film used herein may be a single film or a multilayer film consisting of a plurality of stacked layers. Examples of film materials include synthetic resins such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate (PET), with PET films being preferred due to their suitable flexibility, mechanical strength, and heat resistance. These films may be pretreated, such as by corona treatment or coating with a release agent. Such films are commercially available, for example, from Toray Advanced Film Co., Ltd. WZ(RX) and BX8(R); E7302 and E7304 from Toyobo Co., Ltd.; and Teijin DuPont Films Japan Ltd. G31 and G71T1; and PET38×1-A3, PET38×1-V8, and PET38×1-X08 from Nippa Co., Ltd.

[0178] The protective film used herein can be similar to the support film. Among them, PET and polyethylene films with appropriate flexibility are preferred. Such films are also commercially available. For example, PET films are as described above, and polyethylene films include GF-8 from Tamapoly Co., Ltd. and PE film type 0 from Nippa Co., Ltd.

[0179] In order to consistently produce the photosensitive dry film and prevent curling or warping on the pickup roller, both the support film and the protective film preferably have a thickness of 10 to 100 μm, more preferably 25 to 50 μm.

[0180] [Pattern Formation Method Using Photosensitive Dry Film]

[0181] Another embodiment of the present invention is a method for forming a pattern using a photosensitive dry film, comprising the following steps:

[0182] (i') using a photosensitive dry film to form a photosensitive resin coating on a substrate,

[0183] (ii) exposing the photosensitive resin coating to radiation,

[0184] (iii) The exposed resin coating layer is developed with a developer to form a pattern of the resin coating layer.

[0185] In step (i'), the photosensitive dry film is used to form a photosensitive resin coating on the substrate. Specifically, the photosensitive dry film is bonded to the substrate at the photosensitive resin coating to form the photosensitive resin coating on the substrate. If the photosensitive dry film is covered with a protective film, the protective film is peeled off from the photosensitive dry film, and then the dry film at the photosensitive resin coating is bonded to the substrate to form the photosensitive resin coating on the substrate. Film bonding equipment can be used to bond the dry film.

[0186] Examples of substrates include those exemplified in the pattern forming method using a photosensitive resin composition. The film laminating apparatus is preferably a vacuum laminator. The protective film is peeled from the photosensitive dry film. In a vacuum chamber maintained at a predetermined vacuum, the exposed photosensitive resin coating of the dry film is tightly bonded to a substrate on a workbench at a predetermined temperature using a bonding roller under a predetermined pressure. Preferably, the temperature is 60 to 120°C, the pressure is 0 to 5.0 MPa, and the vacuum is 50 to 500 Pa.

[0187] If necessary, the dry film lamination can be repeated multiple times to obtain a photosensitive resin coating having a desired thickness. For example, the lamination step can be repeated 1 to 10 times to obtain a photosensitive resin coating having a thickness of about 10 to 1,000 μm, preferably about 100 to 500 μm.

[0188] If necessary, the photosensitive resin coating assembly on the substrate can be pre-baked to promote the photocuring reaction of the photosensitive resin coating or enhance the adhesion between the resin coating and the substrate. The pre-baking can be performed at 40 to 140° C. for 1 minute to about 1 hour.

[0189] As with the pattern forming method using a photosensitive resin composition, the photosensitive resin coating layer attached to the substrate can be subjected to the following steps: (ii) exposing the photosensitive resin coating layer to radiation, (iii) developing the exposed resin coating layer with a developer to form a pattern in the resin coating layer, and optionally (iv) post-curing the patterned coating layer. It should be noted that, depending on the specific method, the support of the photosensitive dry film may be removed by mechanical stripping or the like before pre-baking or PEB.

[0190] The resin coating obtained from the photosensitive resin composition or the photosensitive dry film has excellent solder resistance, heat resistance, low substrate warpage, mechanical properties such as crack resistance, copper migration resistance, and adhesion to substrates, etc., and can be used as a protective film for electric and electronic parts and a film for bonding substrates.

[0191] [Example]

[0192] Synthesis Examples, Examples, and Comparative Examples are given below to illustrate the present invention, but the present invention is not limited thereto. It is worth noting that Mw was measured by GPC relative to a monodisperse polystyrene standard using a GPC column TSKgel Super HZM-H (Tosoh Corp.) under the following analytical conditions: flow rate 0.6 mL / min, THF elution, and column temperature 40°C.

[0193] The compounds used to synthesize the polymers are shown below.

[0194]

[0195] [Synthesis Example 1] Synthesis of Polymer P-1

[0196] To a 10 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 245.4 g (0.235 mol) of the compound of formula (S-2a) and 430.5 g (1.00 mol) of the compound of formula (S-4a) were added, and then 1,500 g of toluene was added to the flask, and the resulting mixture was heated to 70° C. Subsequently, 1.0 g of a chloroplatinic acid toluene solution (platinum concentration: 0.5% by weight) was charged into the flask, and 142.9 g (0.735 mol) of the compound of formula (S-1) (total number of hydrosilyl groups: total number of alkenyl groups = 0.97:1 (molar ratio)) was added dropwise thereto over 1 hour. After the dropwise addition was completed, the resulting mixture was heated to 90° C. and aged for 11 hours, and then toluene was distilled off from the reaction solution under reduced pressure to produce a polymer. 2,000 g of propylene glycol monomethyl ether was added to the polymer, and after confirming that the propylene glycol monomethyl ether was dissolved, 444.5 g (6.00 mol) of a compound having the formula (S-5a) and 10.1 g (0.10 mol) of triethylamine were added thereto, and the resulting mixture was heated at 80° C. for 12 hours. After completion of the reaction, propylene glycol monomethyl ether and triethylamine were distilled off from the reaction solution under reduced pressure to produce polymer P-1. Polymer P-1 had an Mw of 8,000. Mw was measured relative to polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as an elution solvent. By 1 H-NMR (manufactured by Bruker Corporation) confirmed that polymer P-1 was a polymer containing repeating units of formula (A1) and repeating units of formula (A2).

[0197] [Synthesis Example 2] Synthesis of Polymer P-2

[0198] To a 10 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 530.5 g (0.18 mol) of the compound of formula (S-2b), 387.5 g (0.90 mol) of the compound of formula (S-4a), and 18.64 g (0.10 mol) of the compound of formula (S-3) were added, and then 1,500 g of toluene was added to the flask, and the resulting mixture was heated to 70°C. Subsequently, 1.0 g of a chloroplatinic acid toluene solution (platinum concentration: 0.5% by weight) was charged into the flask, and 153.6 g (0.79 mol) of the compound of formula (S-1) (total number of hydrosilyl groups:total number of alkenyl groups = 0.97:1 (molar ratio)) was added dropwise thereto over 1 hour. After the dropwise addition was completed, the resulting mixture was heated to 90°C and aged for 11 hours, and then toluene was distilled off from the reaction solution under reduced pressure to produce a polymer. 2,000 g of propylene glycol monomethyl ether was added to the polymer, and after confirming that the propylene glycol monomethyl ether was dissolved, 400.0 g (5.40 mol) of a compound having the formula (S-5a) and 9.11 g (0.09 mol) of triethylamine were added thereto, and the resulting mixture was heated at 80° C. for 12 hours. After completion of the reaction, propylene glycol monomethyl ether and triethylamine were distilled off from the reaction solution under reduced pressure to produce polymer P-2. Polymer P-2 had an Mw of 80,000. Mw was measured relative to polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as an elution solvent. By 1 H-NMR (manufactured by Bruker Corporation) confirmed that polymer P-2 was a polymer containing repeating units of formula (A1), repeating units of formula (A2), repeating units of formula (A3), and repeating units of formula (A4).

[0199] [Synthesis Example 3] Synthesis of Polymer P-3

[0200] To a 10 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 245.4 g (0.235 mol) of the compound of formula (S-2a) and 430.5 g (1.00 mol) of the compound of formula (S-4a) were added, and then 1,500 g of toluene was added to the flask, and the resulting mixture was heated to 70° C. Subsequently, 1.0 g of a chloroplatinic acid toluene solution (platinum concentration: 0.5% by weight) was charged into the flask, and 142.9 g (0.735 mol) of the compound of formula (S-1) (total number of hydrosilyl groups: total number of alkenyl groups = 0.97:1 (molar ratio)) was added dropwise thereto over 1 hour. After the dropwise addition was completed, the resulting mixture was heated to 90° C. and aged for 11 hours, and then toluene was distilled off from the reaction solution under reduced pressure to produce a polymer. 2,000 g of propylene glycol monomethyl ether was added to the polymer, and after confirming that the propylene glycol monomethyl ether was dissolved, 528.6 g (6.00 mol) of the compound having the formula (S-5b) and 10.1 g (0.10 mol) of triethylamine were added thereto, and the resulting 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 produce polymer P-3. Polymer P-3 had an Mw of 8,500. By 1 H-NMR (manufactured by Bruker Corporation) confirmed that the polymer P-3 was a polymer containing a repeating unit having the formula (A1) and a repeating unit having the formula (A2).

[0201] [Synthesis Example 4] Synthesis of Polymer P-4

[0202] To a 10 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 245.4 g (0.235 mol) of the compound of formula (S-2a) and 430.5 g (1.00 mol) of the compound of formula (S-4a) were added, and then 1,500 g of toluene was added to the flask, and the resulting mixture was heated to 70° C. Subsequently, 1.0 g of a chloroplatinic acid toluene solution (platinum concentration: 0.5% by weight) was charged into the flask, and 142.9 g (0.735 mol) of the compound of formula (S-1) (total number of hydrosilyl groups: total number of alkenyl groups = 0.97:1 (molar ratio)) was added dropwise thereto over 1 hour. After the dropwise addition was completed, the resulting mixture was heated to 90° C. and aged for 11 hours, and then toluene was distilled off from the reaction solution under reduced pressure to produce a polymer. 2,000 g of propylene glycol monomethyl ether was added to the polymer, and after confirming that the propylene glycol monomethyl ether was dissolved, 696.7 g (6.00 mol) of the compound having the formula (S-5c) and 10.1 g (0.10 mol) of triethylamine were added thereto, and the resulting 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 produce polymer P-4. Polymer P-4 had an Mw of 9,000. By 1 H-NMR (manufactured by Bruker Corporation) confirmed that the polymer P-4 was a polymer containing a repeating unit having the formula (A1) and a repeating unit having the formula (A2).

[0203] [Comparative Synthesis Example 1] Synthesis of Comparative Polymer CP-1

[0204] To a 10 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 401 g (0.50 mol) of the compound of formula (S-2a), 488 g (0.90 mol) of the compound of formula (S-4b), and 18.6 g (0.10 mol) of the compound of formula (S-3) were added, followed by the addition of 1,100 g of toluene to the flask, and the resulting mixture was heated to 80°C. Subsequently, 1.0 g of a chloroplatinic acid toluene solution (platinum concentration: 0.5 wt%) was placed in the flask, and 95.3 g (0.49 mol) of the compound of formula (S-1) (total number of hydrosilyl groups:total number of alkenyl groups = 0.99:1 (molar ratio)) was added dropwise over 1 hour. After the addition was completed, the resulting mixture was heated to 100°C and aged for 6 hours, after which toluene was distilled off from the reaction solution under reduced pressure to produce comparative polymer CP-1. Comparative polymer CP-1 had an Mw of 12,000.

[0205] [Comparative Synthesis Example 2] Synthesis of Comparative Polymer CP-2

[0206] To a 10 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 362 g (0.45 mol) of the compound of formula (S-2b), 215 g (0.50 mol) of the compound of formula (S-4a), and 271 g (0.50 mol) of the compound of formula (S-4b) were added, followed by the addition of 2,100 g of toluene to the flask, and the resulting mixture was heated to 70°C. Subsequently, 2.0 g of a chloroplatinic acid toluene solution (platinum concentration: 0.5 wt%) was placed in the flask, and 105 g (0.54 mol) of the compound of formula (S-1) (total number of hydrosilyl groups:total number of alkenyl groups = 0.99:1 (molar ratio)) was added dropwise over 1 hour. After the addition was completed, the resulting mixture was heated to 100°C and aged for 12 hours, and then toluene was distilled off from the reaction solution under reduced pressure to produce comparative polymer CP-2. Comparative polymer CP-2 had an Mw of 14,000.

[0207] [2] Preparation of photosensitive resin composition

[0208] [Examples 1 to 8 and Comparative Examples 1 to 10]

[0209] By blending the components in the amounts shown in Tables 1 to 2, stirring them at room temperature until dissolved, and using a pore size of 1.0 μm. The obtained mixture was precisely filtered to prepare photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 10.

[0210] [Table 1]

[0211]

[0212] [Table 2]

[0213]

[0214] In Tables 1 and 2, crosslinking agents B-1 to B-4 and B'-1 to B'-2 are shown below: B-3 is 2,2',6,6'-tetramethoxymethylbisphenol A, and B'-3 is DURANATE TMA-100 (manufactured by Asahi Kasei Corp.) as an isocyanate crosslinking agent.

[0215]

[0216] In Tables 1 and 2, photoacid generators C-1 and C-2 are shown below.

[0217]

[0218] In Tables 1 and 2, comparative polymer CP-3 is shown below.

[0219]

[0220] [3] Preparation of photosensitive dry film

[0221] The die coater is used as a film coater, and a 38 μm thick polyethylene terephthalate (PET) film is used as a support film. Each of the photosensitive resin compositions in Tables 1 to 3 is applied to a support film. The coated film is passed through a hot air circulation oven (length 4 m) set at 100 ° C within 5 minutes to form a photosensitive resin coating on the support film to generate a photosensitive dry film. Using a laminating roller, a 50 μm thick polyethylene film as a protective film is bonded to the photosensitive resin coating under a pressure of 1 MPa to generate a photosensitive dry film with a protective film. Each photosensitive resin coating has a thickness of 50 μm. The thickness of the photosensitive resin coating is measured by an optical interference film thickness meter F50-EXR (Filmetrics, Inc.).

[0222] [4] Evaluation of resin coating

[0223] (1) Pattern formation and evaluation

[0224] The protective film is peeled off from the photosensitive dry film with a protective film. Using a vacuum laminator TEAM-100RF (Takatori Corp.) with a vacuum chamber set to 80Pa vacuum, the photosensitive resin coating on the support film is tightly fitted to a migration test substrate (a substrate with a comb electrode, conductor: copper, conductor spacing and width: 10μm, conductor thickness: 4μm). The temperature is 100°C. After restoring atmospheric pressure, the substrate is taken out of the laminator and the support film is peeled off. The photosensitive resin coating is then pre-baked on a hot plate at 120°C for 5 minutes to enhance its adhesion to the substrate. Next, a contact aligner exposure tool is used to expose the photosensitive resin coating to radiation with a wavelength of 365nm through a mask with a line-space pattern and a contact hole pattern. After exposure, the coated substrate is baked (PEB) on a hot plate at 140°C for 5 minutes and cooled. This is followed by spray development in PGMEA for 300 seconds to form a pattern of the resin coating.

[0225] The patterned photosensitive resin coating on the substrate was post-cured in an oven at 190°C for 2 hours while purging the oven with nitrogen. Contact hole patterns of 100 μm, 50 μm, and 30 μm were observed in cross-section under a scanning electron microscope (SEM), with the smallest hole pattern where the hole extended down to the bottom of the film being recorded as the maximum resolution. The verticality of the 100 μm contact hole pattern was evaluated from the cross-sectional photographs, and was rated as "Excellent" for the vertical pattern. ", a slight inverse tapered profile or footing was rated as "good (○)", a clear inverse tapered profile or footing was rated as "fair (Δ)", and a poor opening was rated as "poor (×)". The results are shown in Tables 3 to 4.

[0226] (2) Evaluation of electrical characteristics (copper migration)

[0227] The substrate patterned using method (1) was used as a substrate for copper migration evaluation. The copper migration test was conducted under the conditions of a temperature of 121°C, a humidity of 100%, and an applied voltage of 10V, with the time until short circuiting was determined with an upper limit of 1,000 hours. The absence of short circuiting was rated as "good (○)". The results are shown in Tables 3 and 4.

[0228] (3) Evaluation of reliability (adhesion and crack resistance)

[0229] The protective film is peeled off from the photosensitive dry film with a protective film. Using a vacuum laminator TEAM-100RF (Takatori Corp.) with a vacuum chamber set to 80Pa vacuum, the photosensitive resin coating on the support film is tightly bonded to a CCL substrate on which a 10mm×10mm square silicon chip is provided. The temperature is 100°C. After restoring the atmospheric pressure, the substrate is taken out of the laminator and the support film is peeled off. The photosensitive resin coating is then pre-baked on a hot plate at 120°C for 5 minutes to enhance its adhesion to the substrate. The photosensitive resin coating is then exposed to radiation with a wavelength of 365nm using a contact aligner exposure tool without any inserted mask. After exposure, the photosensitive resin coating is baked (PEB) on a hot plate at 140°C for 5 minutes, cooled, and post-cured in an oven at 190°C for 2 hours while purging the oven with nitrogen. Afterwards, the substrate was cut into 20mm×20mm square specimens using a dicing saw with a dicing blade (DISCO Co.'s DAD685, spindle speed 40,000rpm, cutting rate 20mm / second) so that the circumference of the silicon chip was 5mm. 10 specimens of each embodiment were inspected by a thermal cycle test (tested at -55°C for 10 minutes and at 125°C for 10 minutes, and the test was repeated 1,000 cycles). After the thermal cycle test, it was observed whether the resin film peeled off from the wafer and whether the resin film cracked. When all specimens did not peel off or crack, the specimen was rated as "good (○)", when one or more specimens peeled off, the specimen was rated as "peeled off (×)", and when one or more specimens cracked, the specimen was rated as "cracked (×)". The method for determining whether the specimen peeled off or cracked was top-down observation under an optical microscope and cross-sectional observation under SEM. The results are shown in Tables 3 to 4.

[0230] (4) Evaluation of adhesion strength (before heat resistance test)

[0231] The protective film is peeled off from the photosensitive dry film with a protective film. Using a vacuum laminator TEAM-100RF (Takatori Corp.) with a vacuum chamber set to 80Pa vacuum, the photosensitive resin coating on the support film is tightly bonded to an 8-inch silicon wafer. The temperature is 100°C. After restoring atmospheric pressure, the substrate is taken out of the laminator and the support film is peeled off. The photosensitive resin coating is then preheated on a hot plate at 120°C for 5 minutes. Then, using a contact aligner exposure tool, the photosensitive resin coating is exposed to radiation with a wavelength of 365nm without any insertion mask. Using a dicing saw (DAD685 of DISCO Co.) with a dicing blade, the substrate is cut into 2mm×2mm square chips. The 2mm×2mm square chip is bonded to a separately provided 15mm×15mm square silicon wafer (i.e., base substrate) through a resin film at 150°C and a load of 50mN. The resin film is then cured by heating at 190°C for 2 hours to obtain a test sheet. 5 test sheets of each embodiment were subjected to an adhesion strength measurement test. Using a bonding tester Dage series 4000-PXY (DAGE), the resistance applied when a semiconductor chip (2mm×2mm) was peeled off from a base substrate (15mm×15mm square silicon wafer) was measured to evaluate the adhesion strength of the resin film layer. The test conditions included a test speed of 200μm / sec and a test height of 50μm. The results are shown in Tables 3 to 4. This value is the average of the measured values ​​of 5 test sheets, and the larger the value, the higher the adhesion strength.

[0232] (5) Evaluation of adhesion strength (after heat resistance test)

[0233] After the test sheet for adhesion strength measurement prepared in (4) was left to stand in an oven at 240°C for 100 hours, it was taken out of the oven and subjected to adhesion strength measurement test as in (5). The results are shown in Tables 3 to 4.

[0234] (6) Evaluation of photoresist stripper resistance

[0235] In order to evaluate the solvent resistance to an N-methyl-2-pyrrolidone (NMP) solution containing 30% tetramethylammonium hydroxide (TMAH), which is a photoresist stripper with relatively high solubility, each of the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 10 was used to form a 15 mm × 15 mm pattern on a silicon wafer using the same method as for preparing the wafer for the copper migration test of (1). After the wafer was immersed in an N-methyl-2-pyrrolidone (NMP) solution containing 30% tetramethylammonium hydroxide (TMAH) at 40°C for 1 hour, changes in thickness and appearance were examined to evaluate resistance to the photoresist stripper. The case where there was no change in appearance and thickness was evaluated as "○", and the case where swelling was observed was evaluated as "×". The results are shown in Tables 3 to 4.

[0236] [Table 3]

[0237]

[0238] [Table 4]

[0239]

[0240] As evident from the test results, the photosensitive resin composition and photosensitive dry film within the scope of the present invention can be easily formed into thick films of small-scale vertical patterns and exhibit satisfactory properties as photosensitive materials. The cured coatings obtained therefrom have excellent copper migration resistance, photoresist stripper resistance, adhesion to substrates, etc., and heat resistance. They also exhibit high reliability as insulating protective films in terms of crack resistance and adhesion. Therefore, they are useful materials for forming protective films on electrical and electronic components, including circuit boards, semiconductor devices, and display devices. Therefore, the present invention provides a photosensitive resin composition and photosensitive dry film with higher reliability.

[0241] Japanese Patent Application No. 2024-047468 is incorporated herein by reference. Although certain preferred embodiments have been described, many modifications and variations can be made thereto in light of the above teachings. It should therefore be understood that the present invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims.

Claims

1. A photosensitive resin composition comprising: (A) a polymer having a silphenylene skeleton, a polysiloxane skeleton, and a fluorene skeleton in the main chain and a polyol structure in the side chain; (B) at least one cross-linking agent selected from nitrogen-containing compounds selected from melamine, guanamine, glycoluril and urea compounds having an average of at least two hydroxymethyl and / or alkoxymethyl groups per molecule, amino condensates modified with formaldehyde or formaldehyde-alcohol, and phenolic compounds having an average of at least two hydroxymethyl or alkoxymethyl groups per molecule; and (C) Photoacid generator.

2. The photosensitive resin composition according to claim 1, wherein the polymer (A) comprises a repeating unit having the formula (A1) and a repeating unit having the formula (A2), and may further comprise a repeating unit having the formula (A3) and a repeating unit having the formula (A4): in, R 1 to R 4 each independently represents a hydrocarbon group having 1 to 20 carbon atoms and may contain heteroatoms, m each independently represents an integer from 1 to 600, and when m is an integer of 2 or more, R 3 may be the same as or different from each other and 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 having the formula (X1), and X 2 is a divalent group having the formula (X2); Among them, n 1 and n 2 are each independently an integer from 1 to 7, R 11 and R 12 are each independently a hydrogen atom or a methyl group, L 1 To L 4 Each is independently a saturated alkylene group having 1 to 15 carbon atoms, a portion of -CH2- of the saturated alkylene group may be replaced by -O-, -S-, -SO2-, -CO- or -CONH-, a portion or all of the hydrogen atoms of the saturated alkylene group may be substituted by hydroxyl groups, and the dotted line represents a bond; Among them, R 21 and R 22 are each independently a hydrogen atom or a methyl group, R 23 and R 24 are each independently a hydrocarbon group having 1 to 8 carbon atoms, k 1 and k 2 Each is independently an integer from 0 to 7, p is an integer from 0 to 600, and the dotted line represents a bond.

3. The photosensitive resin composition according to claim 2, wherein L 1 , L 2 , L 3 and L 4 All have 1 carbon atom. 4 . The photosensitive resin composition according to claim 1 , wherein the content of the compound as component (B) is 1 to 50 parts by weight relative to 100 parts by weight of component (A). The photosensitive resin composition according to claim 1 , further comprising (D) a solvent. 6 . A photosensitive resin coating obtained from the photosensitive resin composition according to claim 1 .

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

8. A pattern forming method comprising the following steps: (i) applying the photosensitive resin composition according to claim 1 onto a substrate to form a photosensitive resin coating thereon, (ii) exposing the photosensitive resin coating to radiation, and (iii) The exposed photosensitive resin coating layer is developed with a developer to form a pattern of the resin coating layer.

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

10. A pattern forming method comprising the following steps: (i') using the photosensitive dry film according to claim 7 to form a photosensitive resin coating on a substrate, (ii) exposing the photosensitive resin coating to radiation, and (iii) The exposed photosensitive resin coating layer is developed with a developer to form a pattern of the resin coating layer.

11. The pattern forming method according to claim 10, further comprising (iv) post-curing the patterned photosensitive resin coating obtained from the developing step at a temperature of 100 to 250°C. 12 . The photosensitive resin composition according to claim 1 , which is a material suitable for forming a coating layer for protecting electric and electronic components. 13 . The photosensitive resin composition according to claim 1 , which is a material suitable for forming a substrate bonding coating layer for bonding two substrates.

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