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

Abstract

This invention provides a photosensitive resin composition, a photosensitive resin film, a photosensitive dry film, and a pattern forming method using the above. The photosensitive resin composition can easily form fine vertical patterns in a thick film, and can form a resin film (resin layer) with excellent heat resistance, crack resistance, adhesion to substrates, electronic components, semiconductor devices, and especially for circuit boards, as well as low warpage. It also exhibits excellent reliability as a protective film for electrical and electronic components and a film for bonding substrates. The photosensitive resin composition of this invention comprises (A) a polysiloxane resin containing an acid crosslinking group, (B) an epoxy compound represented by the following formula (B), and (C) a photoacid generator. (In the formula, R 51 to R 55 are each independently a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms).

Description

Technical Field

[0001] This invention relates to photosensitive resin compositions, photosensitive resin films, photosensitive dry films, and methods for forming patterns. Prior Technology

[0002] Typically, photosensitive polyimide compositions, photosensitive epoxy resin compositions, and photosensitive polysiloxane compositions are used as protective films for photosensitive semiconductor devices or insulating films for multilayer printed circuit boards. As a photosensitive material suitable for protecting such substrates or circuits, a photosensitive polysiloxane composition with particularly excellent flexibility is proposed (Patent Document 1). This photosensitive polysiloxane composition can be cured at low temperatures and can form a film with excellent reliability, such as good wet adhesion. However, it has the problem of poor resistance to chemical release solutions with strong dissolving power, such as N-methyl-2-pyrrolidone.

[0003] In contrast, a photosensitive polysiloxane composition containing a polysiloxane-based polymer with a silylphenyl backbone as the main component has been proposed (Patent Document 2). While this photosensitive polysiloxane composition improves resistance to photoresist stripping solutions, it suffers from problems such as the hardened material peeling off from the substrate after heat resistance testing, or reduced adhesion to the substrate. Further improvements in reliability are desired. Furthermore, with advancements in semiconductor technology, the requirements for pattern formation are becoming increasingly refined. [Previous Patent Documents] [Patent Literature]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2002-88158 [Patent Document 2] Japanese Patent Application Publication No. 2008-184571 Summary of the Invention

[0005] [The problem the invention aims to solve]

[0006] The present invention was made in view of the foregoing circumstances, and its object is to provide a photosensitive resin composition, a photosensitive resin film, a photosensitive dry film, and a pattern forming method using the above. The photosensitive resin composition can easily form fine vertical patterns in a thick film, and can form a resin film (resin layer) with excellent heat resistance, crack resistance, adhesion to substrates, electronic components, semiconductor elements, especially to substrates used in circuit boards, and low warpage of the substrate, etc. It is also a resin film (resin layer) with excellent reliability as a protective film for electrical and electronic components and a film for bonding substrates. [Methods used to solve problems]

[0007] As a result of the inventors' active research to achieve the above object, it was found that the above object can be achieved by a photosensitive resin composition containing (A) a silicone resin having an acid crosslinking group, (B) an epoxy compound having a specific structure, and (C) a photoacid generator, and thus the present invention was completed.

[0008] Therefore, the present invention provides the following photosensitive resin composition, photosensitive resin film, photosensitive dry film, and patterning method. 1. A photosensitive resin composition comprising: (A) A silicone resin having an acid crosslinking group, (B) an epoxy compound represented by the following formula (B), and (C) a photoacid generator, (In the formula, R51 to R55 are each independently a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms). 2. The photosensitive resin composition according to 1, wherein the (A) silicone resin is represented by the following formula (A), (In the formula, R1 to R4 are each independently a hydrocarbon group having 1 to 8 carbon atoms, k is an integer of 1 to 600, a and b represent the composition ratio (mole ratio) of each repeating unit, and satisfy 0 < a < 1, 0 < b < 1, and a + b = 1, and X is a divalent organic group containing an epoxy group and / or a phenolic hydroxyl group). 3. The photosensitive resin composition according to 2, wherein the (A) silicone resin contains repeating units represented by the following formulas (a1) to (a4) and (b1) to (b4), [[ID=;28]] [In the formula, R1 to R4 are each independently a hydrocarbon group having 1 to 8 carbon atoms, k is an integer of 1 to 600, a1 to a4 and b1 to b4 represent the composition ratio (mole ratio) of each repeating unit, and satisfy 0 ≤ a1 < 1, 0 ≤ a2 < 1, 0 ≤ a3 < 1, 0 ≤ a4 < ;1, 0 ≤ b1 < 1, 0 ≤ b2 < 1, 0 ≤ b3 < 1, 0 ≤ b4 < 1, 0 < a1 + a2 + a3 < 1, 0 < b1 + b2 + b3 < 1, and a1 + a2 + a3 + a4 + b1 + b2 + b3 + b4 = 1, X1 is a divalent group represented by the following formula (X1), X2 is a divalent group represented by the following formula (X2), X3 is a divalent group represented by the following formula (X3), X4 is a divalent group represented by the following formula (X4), (In the formula, Y1 represents a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl; R11 and R12 are each independently a hydrogen atom or a methyl group; R13 and R14 are each independently a saturated hydrocarbon group with 1 to 4 carbon atoms or a saturated hydrocarbon oxygen group with 1 to 4 carbon atoms; p1 and p2 are each independently an integer from 0 to 7; q1 and q2 are each independently an integer from 0 to 2; and the dashed lines represent bond connections.) (In the formula, Y represents a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl; R21 and R22 are each independently a hydrogen atom or a methyl group; R23 and R24 are each independently a saturated hydrocarbon group with 1 to 4 carbon atoms or a saturated hydrocarbon oxygen group with 1 to 4 carbon atoms; r1 and r2 are each independently an integer from 0 to 7; s1 and s2 are each independently an integer from 0 to 2; and the dashed lines represent bond connections.) (In the formula, R31 and R32 are each independently a hydrogen atom or a methyl group, t1 and t2 are each independently an integer from 0 to 7, and the dashed lines represent bond connections.) (In the formula, R 41 and R 42 are each independently a hydrogen atom or a methyl group, R 43 and R 44 are each independently a hydrocarbon group with 1 to 8 carbon atoms, u 1 and u 2 are each independently an integer from 0 to 7, v is an integer from 0 to 600, and the dashed line represents the bond). 4. In any of the photosensitive resin compositions described in 1 to 3, the content of epoxy compound in component (B) is 3 to 100 parts by mass relative to 100 parts by mass of component (A). 5. A photosensitive resin composition as described in any one of 1 to 4, wherein it further comprises (D) a crosslinking agent. 6. The photosensitive resin composition of 5, wherein (D) the crosslinking agent is selected from at least one of the following: nitrogen-containing compounds selected from melamine compounds, guanidine compounds, glycourea compounds and urea compounds containing an average of two or more hydroxymethyl and / or alkoxymethyl groups per molecule; amine condensates modified by formaldehyde or formaldehyde-alcohol; phenolic compounds having an average of two or more hydroxymethyl or alkoxymethyl groups per molecule; and epoxy compounds having an average of two or more epoxy groups per molecule. 7. A photosensitive resin composition of any one of 1 to 6, wherein it further comprises (E) a solvent. 8. A photosensitive resin film obtained from a photosensitive resin composition as described in any one of 1 to 7. 9. A photosensitive dry film comprising a support film and a photosensitive resin film as described in 8 on the support film. 10. A method for forming a graphic, comprising: (i) The step of forming a photosensitive resin film on a substrate using any one of the photosensitive resin compositions described in 1 to 7. (ii) The step of exposing the aforementioned photosensitive resin film, and (iii) The step of developing the aforementioned exposed photosensitive resin film with a developing solution to form a pattern. 11. A method for forming a graphic, comprising: (i') The step of forming a photosensitive resin film on a substrate using a photosensitive dry film as shown in 9. (ii) The step of exposing the aforementioned photosensitive resin film, and (iii) The step of developing the aforementioned exposed photosensitive resin film with a developing solution to form a pattern. 12. The pattern forming method of 10 or 11, further comprising (iv) a step of post-curing the photosensitive resin film for which the pattern is formed by development at a temperature of 100 to 250°C. 13. Any photosensitive resin composition as described in any of 1 to 7 is a material for a protective film for electrical and electronic components. 14. The photosensitive resin composition of any one of 1 to 7 is a substrate bonding film used to bond two substrates. [Invention Effects]

[0009] The photosensitive resin composition of this invention can form films with a wide range of film thicknesses, and furthermore, by means of the pattern forming method described later, fine patterns with excellent verticality can be easily formed from thick films. Films obtained using the photosensitive resin composition and photosensitive dry film of this invention exhibit excellent heat resistance and low warpage of the substrate. Furthermore, they demonstrate excellent adhesion, flexibility, and crack resistance to substrates, electronic components, semiconductor elements, and especially substrates used in circuit boards, as well as excellent electrical properties such as low dielectric constant and low dielectric loss tangent, and excellent copper migration resistance. Moreover, the aforementioned films have high reliability as insulating protective films and can be appropriately used as film forming materials for protecting various electrical and electronic components such as circuit boards, semiconductor elements, and display elements, as well as film forming materials for substrate bonding. Implementation

[0010] [Photosensitive Resin Composition]

[0011] The photosensitive resin composition of the present invention contains (A) a polysiloxane resin having an acid crosslinkable group, (B) an epoxy compound having a specific structure, and (C) a photoacid generator.

[0012] [(A) Polysiloxane Resin Having an Acid Crosslinkable Group] The polysiloxane resin of component (A) contains an acid crosslinkable group in the molecule. Here, the so-called acid crosslinkable group refers to a group in which functional groups are directly or chemically bonded via a crosslinking agent by the action of an acid. As the aforementioned acid crosslinkable group, an epoxy group and a phenolic hydroxyl group are preferred. The epoxy group and the phenolic hydroxyl group may include only one of them, or may include both.

[0013] The aforementioned polysiloxane resin having an acid crosslinkable group is preferably represented by the following formula (A).

[0014] In formula (A), R 1 to R 4 are each independently a hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms. k is an integer of 1 to 600, preferably an integer of 1 to 400, more preferably an integer of 1 to 200. a and b represent the composition ratio (mole ratio) of each repeating unit, and satisfy 0 < a < 1, 0 < b < 1, and a + b = 1. X is a divalent organic group containing an epoxy group and / or a phenolic hydroxyl group.

[0015] The aforementioned hydrocarbon group may be any of linear, branched, and cyclic types. As specific examples thereof, alkyl groups such as methyl, ethyl, propyl, hexyl, and structural isomers thereof; cycloaliphatic saturated hydrocarbon groups such as cyclohexyl; aryl groups such as phenyl, etc. Among these, methyl and phenyl are preferred because raw materials are easily available.

[0016] As the polysiloxane resin represented by formula (A), it is particularly preferred to contain repeating units represented by the following formulas (a1) to (a4) and (b1) to (b4) (hereinafter simply referred to as repeating units a1 to a4 and b1 to b4). (In the formula, R 1 to R 4 and k are the same as above).

[0017] In formulas (a1) and (b1), X 1 is a divalent group represented by the following formula (X1). (In the formula, the dotted line is a bonding bond).

[0018] In formula (X1), Y1 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl, or fluorene-9,9-diyl. R11 and R12 are each independently a hydrogen atom or a methyl group. R13 and R14 are each independently a saturated hydrocarbon group with 1 to 4 carbon atoms or a saturated hydrocarbon oxygen group with 1 to 4 carbon atoms. p1 and p2 are each independently an integer from 0 to 7. q1 and q2 are each independently an integer from 0 to 2.

[0019] The aforementioned saturated hydrocarbon group can be any of straight-chain, branched, or cyclic. Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, and their structural isomers; and cyclic saturated hydrocarbon groups such as cyclopropyl and cyclobutyl. Similarly, the aforementioned saturated hydrocarbon oxygen group can be any of straight-chain, branched, or cyclic. Specific examples include alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, and their structural isomers; and cyclic saturated hydrocarbon oxygen groups such as cyclopropoxy and cyclobutoxy.

[0020] In equations (a2) and (b2), X2 is a divalent base expressed by the following equation (X2). (In the formula, the dashed lines represent the bond).

[0021] In formula (X2), Y2 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl, or fluorene-9,9-diyl. R21 and R22 are each independently a hydrogen atom or a methyl group. R23 and R24 are each independently a saturated hydrocarbon group or a saturated hydroxyl group with 1 to 4 carbon atoms. r1 and r2 are each independently an integer from 0 to 7. s1 and s2 are each independently an integer from 0 to 2. Examples of the aforementioned saturated hydrocarbon groups and saturated hydroxyl groups are the same as those exemplified in the description of R13 and R14.

[0022] In equations (a3) ​​and (b3), X3 is a divalent base expressed by the following equation (X3). (In the formula, the dashed lines represent the bond).

[0023] In formula (X3), R31 and R32 are each independently a hydrogen atom or a methyl group. t1 and t2 are each independently an integer from 0 to 7.

[0024] In equations (a4) and (b4), X4 is a divalent base expressed by the following equation (X4). (In the formula, the dashed lines represent the bond).

[0025] In formula (X4), R41 and R42 are each independently a hydrogen atom or a methyl group. R43 and R44 are each independently a hydrocarbon group having 1 to 8 carbon atoms. u1 and u2 are each independently an integer from 0 to 7. v is an integer from 0 to 600, preferably an integer from 0 to 400, and more preferably an integer from 0 to 200. The examples of the aforementioned hydrocarbon groups are the same as those exemplified in the description of R1 to R4.

[0026] (A) The polysiloxane resin of component (A) preferably has a weight average molecular weight (Mw) of 3,000 to 500,000, more preferably 5,000 to 200,000. Furthermore, in this invention, Mw is a value determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as the dissolution solvent, based on the polystyrene conversion.

[0027] In equations (a1)~(a4) and (b1)~(b4), a1~a4 and b1~b4 represent the composition ratio (more ratio) of each repeating unit, and satisfy 0≦a1<1, 0≦a2<1, 0≦a3<1, 0≦a4<1, 0≦b1<1, 0≦b2<1, 0≦b3<1, 0≦b4<1, 0

[0028] The aforementioned repeating units can be random bonds or block polymer bonds. Furthermore, when there are two or more siloxane units in each repeating unit, all siloxane units can be identical, or they can contain two or more different siloxane units. When containing two or more different siloxane units, the siloxane units can be randomly bonded, or they can contain blocks of multiple identical siloxane units. Additionally, in the aforementioned polysiloxane resin, the polysiloxane (siloxane unit) content is preferably 30-80% by mass.

[0029] (A) The polysiloxane resin in component A functions as a membrane-forming agent. The resulting resin film exhibits good adhesion to laminates, substrates, etc., good pattern-forming ability, crack resistance, and heat resistance.

[0030] (A) The polysiloxane resin of component A can be used alone or in combination of two or more types.

[0031] ​[(A) Manufacturing method of polysiloxane] (A) The polysiloxane resin of component (A) can be manufactured by addition polymerization of at least one of the following compounds: a compound represented by formula (1), a compound represented by formula (2), a compound represented by formula (3), a compound represented by formula (4) and a compound represented by formula (5), and a compound represented by formula (6) as needed, in the presence of a metal catalyst. (In the formula, R1~R4 and k are the same as above).

[0032] (In the formula, R11~R14, R21~R24, R31, R32, R41~R44, Y1, Y2, p1, p2, q1, q2, r1, r2, s1, s2, t1, t2, u1, u2 and v are the same as above).

[0033] As the aforementioned metal catalyst, platinum group metal monomers such as platinum (including platinum black), rhodium, and palladium can be used; H₂PtCl₄·xH₂O, H₂PtCl₆·xH₂O, NaHPtCl₆·xH₂O, KHPtCl₆·xH₂O, Na₂PtCl₆·xH₂O, K₂PtCl₄·xH₂O, PtCl₄·xH₂O, PtCl₂, Na₂HPtCl₄·xH₂O Platinum chloride, platinum chloride acid, and platinum chloride salts, etc., such as 2O (where x is preferably an integer from 0 to 6, and particularly preferably 0 or 6); alcohol-modified platinum chloride acid (e.g., as described in U.S. Patent No. 3,220,972); complexes of platinum chloride acid and olefins (e.g., as described in U.S. Patent Nos. 3,159,601, 3,159,662, and 3,775,452); platinum group metals such as platinum black or palladium supported on a support such as alumina, silicon oxide, or carbon; rhodium-olefin complexes; trichlorotriphenylphosphine rhodium (so-called Wilson catalyst); complexes of platinum chloride, platinum chloride acid, or platinum chloride salts with vinyl siloxanes (especially vinyl cyclic siloxanes), etc.

[0034] The amount of catalyst used is the amount of catalyst, which is usually relative to 100 parts by mass of the raw material compound, preferably 0.001 to 0.1 parts by mass, and more preferably 0.01 to 0.1 parts by mass.

[0035] In the aforementioned addition polymerization reaction, a solvent may be used as needed. Preferably, a hydrocarbon solvent such as toluene or xylene is preferred.

[0036] The polymerization temperature, based on the viewpoint of not deactivating the catalyst and completing polymerization in a short time, is preferably 40~150℃, more preferably 60~120℃. The polymerization time depends on the type and amount of resin obtained, but to prevent moisture intrusion into the polymerization system, it is preferably about 0.5~100 hours, more preferably 0.5~30 hours. After the reaction is complete, when using solvent, it can be distilled off to obtain the polysiloxane resin of component (A).

[0037] The reaction method is not particularly limited, but when reacting, for example, at least one of the compounds represented by formula (1), formula (2), formula (3), formula (4) and formula (5) with a compound represented by formula (6) as needed, the method is as follows: first, at least one of the compounds represented by formula (3), formula (4) and formula (5) is mixed with a compound represented by formula (6) as needed and heated, then a metal catalyst is added to the mixture, and then the compounds represented by formula (1) and formula (2) are added dropwise over a period of 0.1 to 5 hours.

[0038] Each compound is formulated relative to at least one of the compounds selected from the compounds represented by formula (3), the compounds represented by formula (4) and the compounds represented by formula (5) as needed, and the total number of alkenyl groups in the compounds represented by formula (6), the total number of hydrosilyl groups in the compounds represented by formula (1) and the compounds represented by formula (2), in molar ratios preferably 0.67 to 1.67, more preferably 0.83 to 1.25.

[0039] The molecular weight (Mw) of the resulting resin can be controlled by using monoallyl compounds such as o-allylphenol or monohydrosilanes or monohydrosiloxanes such as triethylhydrosilane as molecular weight regulators.

[0040] [(B) Epoxy compounds] The epoxy compound of component (B) is represented by the following formula (B).

[0041] In formula (B1), R51 to R55 are each independently a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms. The aforementioned saturated hydrocarbon group can be linear, branched, or cyclic. Specific examples include alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl, and their structural isomers; and cyclic saturated hydrocarbon groups having 3 to 6 carbon atoms such as cyclohexyl. R51 to R55 are preferably hydrogen atoms, methyl, or ethyl, and more preferably hydrogen atoms or methyl.

[0042] The aforementioned alicyclic epoxide compound is preferably as shown below.

[0043] As the aforementioned alicyclic epoxy compound, commercially available products can be used, such as WHR-991S manufactured by Nippon Kayaku Co., Ltd.

[0044] The content of component (B) is preferably 3 to 100 parts by weight, more preferably 3 to 75 parts by weight, and even more preferably 5 to 50 parts by weight, relative to 100 parts by weight of component (A). If the content of component (B) is within the aforementioned range, a better coating film will be obtained when the dry film is formed. Component (B) can be used alone or in combination of two or more.

[0045] [(C) Photoacid Generator] (C) The photoacid generating agent in component (C) is not particularly limited to those that generate acid through decomposition by light irradiation, but it is preferred that it generates acid through decomposition by light with a wavelength of 190-500 nm. The aforementioned photoacid generating agent serves as a curing catalyst. Because the photosensitive resin composition of the present invention has excellent compatibility with photoacid generating agents, a wide range of photoacid generating agents can be used.

[0046] Examples of photoacid generators include, for example, onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfonamide derivatives, dioxime derivatives, nitrophenyl sulfonate derivatives, sulfonate derivatives, amide sulfonate derivatives, oxime sulfonate derivatives, imino sulfonate derivatives, etc.

[0047] Examples of the aforementioned monium salts include strontium salts represented by the following formula (C1) and monium salts represented by the following formula (C2).

[0048] In formulas (C1) and (C2), R101 to R105 are each independently a saturated hydrocarbon group with 1 to 12 carbon atoms that may have substituents, an aryl group with 6 to 12 carbon atoms that may have substituents, or an aralkyl group with 7 to 12 carbon atoms that may have substituents. A- is a non-nucleophilic counterion.

[0049] The aforementioned saturated hydrocarbon group can be any of straight-chain, branched, or cyclic. Specific 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. Examples of aryl groups include phenyl, naphthyl, and biphenyl. Examples of aralkyl groups include benzyl and phenethyl.

[0050] Examples of the aforementioned substituents include oxo groups, saturated hydrocarbon groups with 1 to 12 carbon atoms, saturated alkyloxy groups with 1 to 12 carbon atoms, aryl groups with 6 to 24 carbon atoms, aralkyl groups with 7 to 25 carbon atoms, aryloxy groups with 6 to 24 carbon atoms, and arylthio groups with 6 to 24 carbon atoms. Furthermore, the hydrocarbon portion of the aforementioned saturated hydrocarbon groups and saturated alkyloxy groups can be linear, branched, or cyclic. Specific examples are the same as those exemplified as saturated hydrocarbon groups represented by R 101 to R 105.

[0051] R101 to R105 are preferably saturated hydrocarbon groups having substituents such as methyl, ethyl, propyl, butyl, cyclohexyl, norbornyl, adamantyl, 2-oxocyclohexyl, etc.; aryl groups may have substituents 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, triphenyl, biphenoxyphenyl, biphenylthiophenyl, etc.; and aralkyl groups may have substituents such as benzyl, phenethyl, etc. Among these, aryl groups and aralkyl groups that may have substituents are more preferred.

[0052] Examples of non-nucleophilic counterions include halide ions such as chloride ions and bromide ions; fluoroalkyl sulfonate ions such as trifluoromethanesulfonate ions, 1,1,1-trifluoroethanesulfonate ions, and nonafluorobutanesulfonate ions; aryl sulfonate ions such as toluenesulfonate ions, benzenesulfonate ions, 4-fluorobenzenesulfonate ions, and 1,2,3,4,5-pentafluorobenzenesulfonate ions; alkyl sulfonate ions such as methanesulfonate ions and butanesulfonate ions; fluoroalkyl sulfonate ions such as trifluoromethanesulfonylimide ions; fluoroalkyl sulfonyl methyl ions such as tri(trifluoromethanesulfonyl)methyl ions; borate ions such as tetraphenylborate ions and tetra(pentafluorophenyl)borate ions; and phosphate ions such as hexafluorophosphate ions and tri(pentafluoroethyl)trifluorophosphate ions.

[0053] Examples of the aforementioned diazomethane derivatives include compounds represented by the following formula (C3).

[0054] In formula (C3), R111 and R112 are each independently a saturated hydrocarbon group with 1 to 12 carbon atoms, a halogenated saturated hydrocarbon group with 1 to 12 carbon atoms, and may have a substituent of an aryl group with 6 to 12 carbon atoms or an aralkyl group with 7 to 12 carbon atoms.

[0055] The aforementioned saturated hydrocarbon group can be any of the following: linear, branched, or cyclic. Specific examples are the same as those exemplified as saturated hydrocarbon groups represented by R 101 to R 105. Examples of the aforementioned halogenated saturated hydrocarbon groups include trifluoromethyl, 1,1,1-trifluoroethyl, 1,1,1-trichloroethyl, and nonafluorobutyl.

[0056] Examples of aryl groups that may have substituents include phenyl; alkoxyphenyl groups such as 2-, 3-, or 4-methoxyphenyl, 2-, 3-, or 4-ethoxyphenyl, and 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.

[0057] Examples of the aforementioned onium salts include diphenyltrifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyltrifluoromethanesulfonate, diphenyltrifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyltrifluoromethanesulfonate, triphenylstrontium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylstrontium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)phenylstrontium trifluoromethanesulfonate, and trifluoromethanesulfonate. Tris(p-tert-butoxyphenyl) strontium, triphenyl strontium p-toluenesulfonic acid, diphenyl strontium p-toluenesulfonic acid (p-tert-butoxyphenyl) strontium p-toluenesulfonic acid, bis(p-tert-butoxyphenyl) strontium p-toluenesulfonic acid, tris(p-tert-butoxyphenyl) strontium p-toluenesulfonic acid, triphenyl strontium nonafluorobutanesulfonic acid, triphenyl strontium butanesulfonic acid, trimethyl strontium trifluoromethanesulfonic acid, trimethyl strontium p-toluenesulfonic acid, cyclohexyl trifluoromethanesulfonic acid Cyclohexyl(2-oxocyclohexyl) strontium, p-toluenesulfonic acid cyclohexylmethyl(2-oxocyclohexyl) strontium, dimethylphenyltrifluoromethanesulfonate strontium, p-toluenesulfonic acid dimethylphenyl strontium, dicyclohexyltrifluoromethanesulfonate strontium, p-toluenesulfonic acid dicyclohexylphenyl strontium, bis(4-tert-butylphenyl) strontium hexafluorophosphate, 4-(phenylthio)phenyl diphenyl strontium tri(pentafluoroethyl) trifluorophosphate, diphenyl( 4-Thiophenoxyphenyl) strontium hexafluoroantimonate, [4-(4-biphenylthio)phenyl]-4-biphenylphenyl strontium tri(trifluoromethanesulfonyl)methyl, triphenylstrontium tetra(fluorophenyl)borate, tri[4-(4-acetylatedphenyl)thiophenyl]strontium tetra(fluorophenyl)borate, triphenylstrontium tetra(pentafluorophenyl)borate, tri[4-(4-acetylatedphenyl)thiophenyl]strontium tetra(pentafluorophenyl)borate, etc.

[0058] Specific examples of the aforementioned diazomethane derivatives include bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylbenzenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(dibutylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, and bis(isopropylsulfonyl)diazomethane. Diazomethane, bis(tert-butylsulfonyl)diazomethane, bis(n-pentylsulfonyl)diazomethane, bis(isopentylsulfonyl)diazomethane, bis(dipentylsulfonyl)diazomethane, bis(tert-pentylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-pentylsulfonyl)diazomethane, 1-tert-butylsulfonyl-1-(tert-butylsulfonyl)diazomethane, etc.

[0059] Examples of the aforementioned dioxime derivatives include bis-o-(p-toluenesulfonyl)-α-dimethyldioxime, bis-o-(p-toluenesulfonyl)-α-diphenyldioxime, bis-o-(p-toluenesulfonyl)-α-dicyclohexyldioxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedionedioxime, and bis-(p-toluenesulfonyl)-2-methyldioxime. 3,4-Pentanedione oxime, bis-o-(n-butanesulfonyl)-α-dimethyl oxime, bis-o-(n-butanesulfonyl)-α-diphenyl oxime, bis-o-(n-butanesulfonyl)-α-dicyclohexyl oxime, bis-o-(n-butanesulfonyl)-2,3-pentanedione oxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedione oxime Dioxime, bis-o-(methanesulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-o-(terbutanesulfonyl)-α-dimethylglyoxime, bis-o-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-o-(cyclo... Hexanesulfonyl)-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, bis-o-(camphorsulfonyl)-α-dimethylglyoxime, etc.

[0060] Examples of the aforementioned β-ketosulfonate derivatives include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane.

[0061] Examples of the aforementioned di-di ...

[0062] Examples of the aforementioned nitrobenzyl sulfonate derivatives include 2,6-dinitrobenzyl p-toluenesulfonic acid and 2,4-dinitrobenzyl p-toluenesulfonic acid.

[0063] Examples of the aforementioned sulfonate derivatives include 1,2,3-tris(methanesulfonoxy)benzene, 1,2,3-tris(trifluoromethanesulfonoxy)benzene, and 1,2,3-tris(p-toluenesulfonoxy)benzene.

[0064] Examples of the aforementioned nitrilo-imino sulfonate derivatives include phthalimino-trifluoromethane sulfonate, phthalimino-toluene sulfonate, 5-norbornene-2,3-dicarboxynitrilo-trifluoromethane sulfonate, 5-norbornene-2,3-dicarboxynitrilo-toluene sulfonate, 5-norbornene-2,3-dicarboxynitrilo-n-butane sulfonate, and n-trifluoromethylsulfoxynaphthylimide.

[0065] Examples of the aforementioned oxime sulfonate derivatives include α-(phenylsmoxyimino)-4-methylphenylacetonitrile and α-(p-toluenesmoxyimino)-p-methoxyphenylacetonitrile.

[0066] Examples of the aforementioned iminosulfonate derivatives include (5-(4-methylphenyl)sulfonoxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile and (5-(4-(4-methylphenylsulfonoxy)phenylsulfonoxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, etc.

[0067] Additionally, 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane, etc., may also be used appropriately.

[0068] (C) The content of component (C) is preferably 0.05 to 20 parts by mass, more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of component (A). If the content of component (C) is 0.05 parts by mass or more, sufficient acid will be generated to allow the cross-linking reaction to proceed fully. If it is 20 parts by mass or less, the increase in absorbance of the photoacid generator itself can be suppressed, and there will be no problem of reduced transparency, which is therefore better. Component (C) can be used alone or in combination of two or more.

[0069] [(D) Crosslinking agent] The photosensitive resin composition of the present invention preferably includes a crosslinking agent as component (D). The aforementioned crosslinking agent is a component that can easily form a pattern by inducing a condensation reaction with the phenolic hydroxyl groups or saturated hydroxyl groups represented by R13, R14, R23 or R24 ​​in the aforementioned component (A), and can further improve the strength of the cured product.

[0070] As the aforementioned crosslinking agent, it is preferably a melamine compound, guanidine compound, glycourea compound or urea compound containing an average of two or more hydroxymethyl and / or alkoxymethyl groups per molecule; an amino condensate modified with formaldehyde or formaldehyde-alcohol; a phenolic compound having an average of two or more hydroxymethyl or alkoxymethyl groups per molecule; and an epoxy compound having an average of two or more epoxy groups per molecule.

[0071] An example of the aforementioned melamine compound is one represented by the following formula (D).

[0072] In formula (D), R 201 to R 206 are each independently a hydroxymethyl group, a saturated hydroxyl group with 2 to 5 carbon atoms, or a hydrogen atom, but at least one of them is a hydroxymethyl group or a saturated hydroxyl group. Examples of the aforementioned saturated hydroxyl groups include alkoxymethyl groups such as methoxymethyl and ethoxymethyl.

[0073] Examples of melamine compounds represented by formula (D) include trimethoxymethyl monohydroxymethyl melamine, dimethoxymethyl monohydroxymethyl melamine, trihydroxymethyl melamine, hexahydroxymethyl melamine, hexamethoxymethyl melamine, and hexaethoxymethyl melamine.

[0074] The melamine compound represented by formula (D) can be obtained, for example, by modifying the melamine monomer by hydroxymethylation with formaldehyde using conventional methods, or by further modifying it by alkoxylation with an alcohol. The aforementioned alcohol is preferably a lower alcohol, such as an alcohol having 1 to 4 carbon atoms.

[0075] Examples of the aforementioned guanidine compounds include tetrahydroxymethylguanidine, tetramethoxymethylguanidine, and tetramethoxyethylguanidine.

[0076] Examples of the aforementioned glycourea compounds include tetrahydroxymethylglycourea and tetra(methoxymethyl)glycourea.

[0077] Examples of the aforementioned urea compounds include tetrahydroxymethyl urea, tetramethoxymethyl urea, tetramethoxyethyl urea, tetraethoxymethyl urea, and tetrapropoxymethyl urea.

[0078] Examples of the aforementioned amino condensates modified with formaldehyde or formaldehyde-alcohol include melamine condensates modified with formaldehyde or formaldehyde-alcohol and urea condensates modified with formaldehyde or formaldehyde-alcohol.

[0079] Examples of modified melamine condensates include compounds represented by formula (D) or their polymers (such as dimers, trimers, or oligomers) obtained by addition condensation polymerization with formaldehyde until the desired molecular weight is reached. Furthermore, conventional methods can be used for the aforementioned addition condensation polymerization. Moreover, the modified melamine represented by formula (D) can be used alone or in combination of two or more types.

[0080] Examples of urea condensates modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensates, ethoxymethylated urea condensates, and propoxymethylated urea condensates.

[0081] The aforementioned modified urea condensate can be obtained by, for example, conventional methods, by hydroxymethylating the urea condensate of the desired molecular weight with formaldehyde, or by further alkoxylating it with an alcohol.

[0082] Examples of phenolic compounds that have an average of two or more hydroxymethyl or alkoxymethyl groups in one molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol and 2,2',6,6'-tetramethoxymethylbisphenol A.

[0083] Examples of epoxy compounds having an average of two or more epoxy groups per molecule include bisphenol-type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin; phenolic varnish-type epoxy resins such as phenolic varnish-type epoxy resin and cresolic varnish-type epoxy resin; triphenol alkane-type epoxy resin; biphenyl-type epoxy resin; dicyclopentadiene-modified phenolic varnish-type epoxy resin; phenolic aryl alkyl-type epoxy resin; biphenyl aryl alkyl-type epoxy resin; epoxy resin containing a naphthalene ring; glycidyl ester-type epoxy resin; alicyclic epoxy resin; and heterocyclic epoxy resin.

[0084] When component (D) is present, its content relative to 100 parts by mass of component (A) is preferably 0.5 to 50 parts by mass, and more preferably 1 to 30 parts by mass. If it is 0.5 parts by mass or more, sufficient curing property is obtained upon light irradiation; if it is 50 parts by mass or less, the cured product can exhibit sufficient effect because the proportion of component (A) in the photosensitive resin composition is not reduced. Component (D) can be used alone or in combination with two or more other components.

[0085] [(E) solvent] The photosensitive resin composition of the present invention may further include a solvent as component (E). As for the aforementioned solvent, there are no particular limitations on whether it is a solvent that can dissolve components (A) to (D) and the various additives described later, but organic solvents are preferred because of the excellent solubility of such components.

[0086] Examples of the aforementioned 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, tributyl acetate, tributyl propionate, propylene glycol monotert-butyl ether acetate, and γ-butyrolactone. Ideally, solvents with the best solubility for photoacid generators, such as ethyl lactate, cyclohexanone, cyclopentanone, PGMEA, γ-butyrolactone, and mixtures thereof, can be used. These organic solvents can be used individually or in mixtures of two or more.

[0087] The content of component (E) is preferably 50 to 2,000 parts by weight, more preferably 50 to 1,000 parts by weight, and especially preferably 50 to 100 parts by weight, relative to 100 parts by weight of component (A). Component (E) may be used alone or in combination with two or more other components.

[0088] [Other Additives] In addition to the aforementioned components, the photosensitive resin composition of this invention may contain other additives. Examples of such additives include surfactants commonly used to improve coatability.

[0089] As for the aforementioned surfactants, nonionic surfactants are preferred, such as fluorinated surfactants, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkylamine oxides, and fluorinated organosilicon compounds. Commercially available surfactants can be used, such as Fluorad FC-430 (manufactured by 3M), Surflon S-141 and S-145 (manufactured by AGC Chemical), Unidyne DS-401, DS-4031, and DS-451 (manufactured by Daikin Industries), Megafac F-8151 (manufactured by DIC), and X-70-093 (manufactured by Shin-Etsu Chemical Industry). Among these, Fluorad FC-430 and X-70-093 are preferred. The content of the aforementioned surfactant is preferably 0.05 to 1 part by mass relative to 100 parts by mass of component (A).

[0090] The photosensitive resin composition of the present invention may also include a silane coupling agent as another additive. By including a silane coupling agent, the adhesion of the film obtained from the composition to the substrate can be further improved. Examples of silane coupling agents include epoxy-containing silane coupling agents and amino-silane coupling agents containing aromatic groups. One of these can be used alone, or two or more can be used in combination. The content of the aforementioned silane coupling agent is not particularly limited, but when included, it is preferably 0.01 to 5% by mass in the photosensitive resin composition of the present invention.

[0091] The photosensitive resin composition of the present invention is prepared by conventional methods. For example, the aforementioned components are stirred and mixed, and then the solids are filtered out as needed using a filter or the like to prepare the photosensitive resin composition of the present invention.

[0092] The photosensitive resin composition of the present invention, thus modulated, can be preferably used as a material for, for example, a protective film for semiconductor elements, a protective film for wiring, a cover film, a solder mask, or an insulating film for through electrodes (for TSV), and further as an adhesive between stacked substrates in a three-dimensional stack.

[0093] [Patterning Method Using Photosensitive Resin Composition] The present invention provides a pattern forming method using a photosensitive resin composition, comprising: (i) The step of forming a photosensitive resin film on a substrate using the photosensitive resin composition of the present invention. (ii) The step of exposing the aforementioned photosensitive resin film, and (iii) The step of developing the aforementioned exposed photosensitive resin film with a developing solution to form a pattern.

[0094] Step (i) is the step of forming a photosensitive resin film on a substrate using the aforementioned photosensitive resin composition. Examples of the aforementioned substrate include, for instance, a silicon wafer, a silicon wafer for through electrodes, a silicon wafer thinned by back-side grinding, a plastic or ceramic substrate, or a substrate having metals such as Ni or Au on its entire surface or a portion thereof by ion sputtering or plating. Furthermore, substrates with uneven surfaces may sometimes be used.

[0095] An example of a method for forming a photosensitive resin film is to coat the aforementioned photosensitive resin composition onto a substrate and then preheat (pre-baking) it as needed. Conventional coating methods can be used, such as dip coating, spin coating, and roll coating. The coating amount of the aforementioned photosensitive resin composition can be appropriately selected according to the purpose, but the film thickness of the resulting photosensitive resin film is preferably 0.1 to 200 μm, more preferably 1 to 150 μm.

[0096] To improve the uniformity of film thickness on the substrate surface, a solvent can be dropped onto the substrate before coating the photosensitive resin composition (pre-wetting method). The solvent to be dropped and its amount can be appropriately selected according to the purpose. As the aforementioned solvent, alcohols such as isopropanol (IPA), ketones such as cyclohexanone, and diols such as PGME are preferred, but solvents used in the photosensitive resin composition can also be used.

[0097] To facilitate the photocuring reaction, pre-baking can be performed as needed to evaporate the solvents. Pre-baking can be carried out, for example, at 40-140°C for about 1 minute to 1 hour.

[0098] Next, (ii) the aforementioned photosensitive resin film is exposed. Exposure is preferably performed with light of wavelength 10-600 nm, more preferably with light of wavelength 190-500 nm. Examples of such wavelengths include light of various wavelengths generated by a radiation generating device, such as ultraviolet light (248 nm, 193 nm), gamma rays, hamma rays, i-rays, etc. Of these, light of wavelength 248-436 nm is particularly preferred. The exposure intensity is preferably 10-10,000 mJ / cm².

[0099] Exposure can be performed through a photomask. The aforementioned photomask can be, for example, a material with the desired pattern running through it. Furthermore, the material of the photomask is not particularly limited, but it is preferably a material that blocks the aforementioned wavelengths of light; for example, a material containing chromium is preferred as a light-shielding film.

[0100] Furthermore, to improve development sensitivity, post-exposure heating (PEB) can be performed. PEB is preferably performed at 40~150°C for 0.5~10 minutes. Through PEB, the exposed areas are cross-linked to form an insoluble pattern that is insoluble in the organic solvent used as a developer.

[0101] After exposure or PEB, (iii) the photosensitive resin film is developed using a developing solution to form a pattern. Preferably, the developing solution is an organic solvent such as an alcohol like IPA, a ketone like cyclohexanone, or a diol like PGME, but solvents used in the photosensitive resin composition may also be used. An example of the developing method is a conventional method, such as immersing the patterned substrate in the aforementioned developing solution. The non-exposed areas are dissolved and removed by developing with an organic solvent, thus forming the pattern. Then, as needed, washing, rinsing, and drying are performed to obtain a resin film with the desired pattern.

[0102] Then, (iv) the patterned film is cured using an oven or heating plate, preferably at 100-250°C, more preferably at 150-220°C. A curing temperature of 100-250°C increases the crosslinking density of the photosensitive resin composition, removes residual volatile components, and is preferable from the perspective of substrate adhesion, heat resistance, strength, electrical properties, and thus adhesive strength. The curing time is preferably 10 minutes to 10 hours, more preferably 10 minutes to 3 hours. Using the photosensitive resin composition of this invention, films with excellent film properties can be obtained even at relatively low curing temperatures of around 200°C. The thickness of the cured film (cured film) is typically 1-200 μm, preferably 5-50 μm.

[0103] When it is not necessary to form a pattern, for example, when it is only necessary to form a uniform film, in step (ii) of the aforementioned pattern forming method, the film can be formed by exposing the film to light of an appropriate wavelength without separating it from the aforementioned photomask.

[0104] [Substrate bonding method] The photosensitive resin composition of this invention can also be used as an adhesive for bonding two substrates. An example of a substrate bonding method is to bond a substrate with a film formed from the photosensitive resin composition of this invention to a second substrate under appropriate heat and pressure conditions to form an adhesive bond between the two substrates. Either or both of the substrate with the film and the second substrate can also be wafer-sized by dicing or other processing methods. Preferably, the bonding conditions are a heating temperature of 50-200°C for 1-60 minutes. As a bonding apparatus, a wafer holder is used to bond wafers together under reduced pressure while applying a load, or wafer-to-wafer or wafer-to-wafer bonding is performed using a flip-chip holder. The adhesive layer formed between the substrates is further strengthened by a subsequent curing process, described later, to achieve a permanent bond.

[0105] By subjecting the substrate to post-curing treatment under the same conditions as in step (iv) above, the cross-linking density of the aforementioned film can be increased, thereby improving the substrate adhesion. Furthermore, the heating during bonding induces a cross-linking reaction. Since no side reaction accompanied by degassing occurs during the aforementioned cross-linking reaction, it does not cause bonding defects (pores), especially when used as a substrate adhesive.

[0106] [Photosensitive dry film] The photosensitive dry film of the present invention comprises a support film and a photosensitive resin film obtained from the aforementioned photosensitive resin composition on the support film.

[0107] The aforementioned photosensitive dry film (support film and photosensitive resin film) is a solid. Since the photosensitive resin film does not contain solvent, there is no risk of residual air bubbles inside the aforementioned photosensitive resin film and between the uneven substrate due to its evaporation.

[0108] The thickness of the aforementioned photosensitive resin film, based on the viewpoints of flatness, step coverage, and substrate stacking spacing on a substrate with unevenness, is preferably 5~200μm, and more preferably 10~100μm.

[0109] Furthermore, the viscosity and flowability of the aforementioned photosensitive resin film are closely related. By maintaining appropriate flowability within a suitable viscosity range, the photosensitive resin film can penetrate deep into narrow gaps or soften the resin to enhance adhesion to the substrate. Therefore, based on its flowability, the viscosity of the aforementioned photosensitive resin film at 80-120°C is preferably 10-5,000 Pa·s, more preferably 30-2,000 Pa·s, and even more preferably 50-300 Pa·s. The viscosity in this invention is measured using a rotational viscometer.

[0110] When the photosensitive dry film of the present invention is adhered to a substrate with uneven surfaces, the photosensitive resin film follows the aforementioned unevenness and is covered, achieving high flatness. In particular, the aforementioned photosensitive resin film, due to its low viscoelasticity, can achieve even higher flatness. Furthermore, when the aforementioned photosensitive resin film is adhered to the aforementioned substrate under vacuum conditions, the occurrence of such gaps can be more effectively prevented.

[0111] The photosensitive dry film of the present invention can be manufactured by coating the aforementioned photosensitive resin composition onto a support film and drying it to form a photosensitive resin film. As the manufacturing apparatus for the aforementioned photosensitive dry film, a film coater generally used for manufacturing adhesive products can be used. Examples of the aforementioned film coater include, for example, a notched wheel coater, a notched wheel reverse coater, a multi-coater, a die-nose coater, a lip die coater, a lip die reverse coater, a direct gravure coater, an offset gravure coater, a three-bottom reverse coater, and a four-bottom reverse coater.

[0112] The support film is wound from the roll-out shaft of the aforementioned film coater. As it passes through the coating head of the film coater, the aforementioned photosensitive resin composition is coated onto the support film to a predetermined thickness. Then, it is passed through a hot air circulating oven at a specific temperature and time, whereby the support film dries to form a photosensitive resin film, thus producing a photosensitive dry film. Alternatively, if necessary, the photosensitive dry film, together with a protective film wound from another roll-out shaft of the aforementioned film coater, is passed through a laminating roller under specific pressure. This laminates the aforementioned photosensitive resin film and protective film on the support film, and then the film is wound onto the take-up shaft of the aforementioned film coater, thus producing a photosensitive dry film with a protective film attached. In this case, the preferred temperature is 25~150°C, the preferred time is 1~100 minutes, and the preferred pressure is 0.01~5 MPa.

[0113] The aforementioned support membrane can be a single-layer membrane made of a single membrane, or a multilayer membrane made of multiple laminated membranes. Examples of membrane materials include synthetic resin membranes such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Among these, polyethylene terephthalate is preferred based on its moderate flexibility, mechanical strength, and heat resistance. These membranes can undergo various treatments such as corona treatment or release agent coating. Commercially available products can be used, such as Selapee WZ(RX), Selapee BX8(R) (manufactured by Toray Film Processing Co., Ltd.), E7302, E7304 (manufactured by Toyobo Co., Ltd.), Peulex G31, Peulex G71T1 (manufactured by DuPont Film Co., Ltd.), PET38×1-A3, PET38×1-V8, PET38×1-X08 (manufactured by NIPPA Co., Ltd.), etc.

[0114] As the aforementioned protective film, the same material as the aforementioned support film can be used, but from the viewpoint of having moderate flexibility, polyethylene terephthalate and polyethylene are preferred. These can be commercially available products; examples of polyethylene terephthalate are already shown, and examples of polyethylene include GF-8 (manufactured by Tamapoly), PE film type 0 (manufactured by NIPPA), etc.

[0115] The thickness of the aforementioned support film and protective film, based on the stability of photosensitive dry film manufacturing and the winding habits of the core, and from the perspective of preventing shrinkage, is preferably 10~100μm, and more preferably 25~50μm.

[0116] [Patterning Method Using Photosensitive Dry Film] The pattern formation method using a photosensitive dry film of the present invention includes: (i') The step of forming a photosensitive resin film on a substrate using the photosensitive dry film of the present invention. (ii) The step of exposing the aforementioned photosensitive resin film, and (iii) The step of developing the aforementioned exposed photosensitive resin film with a developing solution to form a pattern.

[0117] First, in step (I'), a photosensitive resin film is formed on the substrate using a photosensitive dry film. Specifically, a photosensitive resin film is formed on the substrate by attaching the photosensitive resin film of the photosensitive dry film to the substrate. Furthermore, if the aforementioned photosensitive dry film has a protective film, the photosensitive resin film of the photosensitive dry film is attached to the substrate after the protective film is peeled off from the photosensitive dry film. Attachment can be performed, for example, using a film attachment apparatus.

[0118] The substrate mentioned above is an example of the same substrate described in the pattern forming method using a photosensitive resin composition. The film lamination apparatus mentioned above is preferably a vacuum laminator. For example, the protective film of the aforementioned photosensitive dry film is peeled off, and the aforementioned photosensitive resin film is exposed in a vacuum chamber with a specific vacuum level. Then, using an attachment roller with a specific pressure, the film is adhered to the aforementioned substrate on a stage with a specific temperature. The aforementioned temperature is preferably 60~120°C, the aforementioned pressure is preferably 0~5.0 MPa, and the aforementioned vacuum level is preferably 50~500 Pa.

[0119] To obtain the necessary thickness of the photosensitive resin film, the film can be applied multiple times as needed. For example, applying the film 1 to 10 times can yield a photosensitive resin film with a thickness of 10 to 1,000 μm, especially 100 to 500 μm.

[0120] To effectively carry out the photocuring reaction of the aforementioned photosensitive resin film and to improve the adhesion between the photosensitive resin film and the substrate, pre-baking can be performed as needed. Pre-baking can be performed, for example, at 40~140°C for about 1 minute to 1 hour.

[0121] The photosensitive resin film attached to the substrate, similar to the pattern forming method using the aforementioned photosensitive resin composition, is formed by (ii) exposing the aforementioned photosensitive resin film, (iii) developing the exposed photosensitive resin film with a developer to form a pattern, and, as needed, by (iv) post-curing treatment. Furthermore, the support film of the photosensitive dry film can be peeled off before pre-baking or before PEB, or removed in other ways, depending on the process.

[0122] The film obtained from the aforementioned photosensitive resin composition and photosensitive dry film has excellent heat resistance, flexibility, electrical insulation, mechanical properties and adhesion to substrates, and can be appropriately used as a protective film for electrical and electronic components such as semiconductor devices and a film for bonding substrates. [Example]

[0123] The following describes the invention in more detail with examples of synthesis, embodiments, and comparative examples, but the invention is not limited to the following embodiments. Mw was determined by GPC using a TSKgel Super HZM-H (manufactured by TOSOH) column, with a flow rate of 0.6 mL / min, THF solvent dissolution, and a column temperature of 40°C, using monodisperse polystyrene as the standard.

[0124] The compounds (S-1) to (S-6) used in the synthesis examples are shown below.

[0125] [1] Synthesis of polysiloxane resin [Synthesis example 1] In a 3L flask equipped with a stirrer, thermometer, nitrogen purging device and backflow cooler, 215.0 g (0.5 moles) of compound (S-6) was added, followed by 2,000 g of toluene, and the mixture was heated to 70°C. Subsequently, 1.0 g of a toluene solution of platinum chloride (platinum concentration 0.5% by mass) was added, and 67.9 g (0.35 moles) of compound (S-4) and 453.0 g (0.15 moles) of compound (S-5) (y 1=40, manufactured by Shin-Etsu Chemical Co., Ltd.) were added dropwise over 1 hour (total of hydrosilanes / total of alkyl groups = 1 / 1 (mole ratio)). After the addition was complete, the mixture was heated to 100°C and aged for 6 hours. Toluene was then removed from the reaction solution by vacuum distillation to obtain polysiloxane resin A-1. Polysiloxane resin A-1 was confirmed to contain repeating units a1, a2, b1, and b2 by 1H-NMR (Bruker assay). The Mw of polysiloxane resin A-1 was 62,000, and the polysiloxane content was 61.6% by mass.

[0126] [Synthesis example 2] In a 3L flask equipped with a stirrer, thermometer, nitrogen purging device and backflow cooler, 53.00g (0.20 moles) of compound (S-2) and 117.6g (0.30 moles) of compound (S-1) were added, followed by 2,000g of toluene, and the mixture was heated to 70°C. Subsequently, 1.0 g of a platinum chloride toluene solution (platinum concentration 0.5% by mass) was added, and 48.5 g (0.25 moles) of compound (S-4) and 755.0 g (0.25 moles) of compound (S-5) (y 1=40, manufactured by Shin-Etsu Chemical Co., Ltd.) were added dropwise over 1 hour (total of hydrosilanes / total of alkenes = 1 / 1 (mole ratio)). After the addition was complete, the mixture was heated to 100°C and aged for 6 hours. Toluene was then removed from the reaction solution by vacuum distillation to obtain polysiloxane resin A-2. Polysiloxane resin A-2 was confirmed to contain repeating units a1, a3, a4, b1, b3, and b4 by 1H-NMR (Bruker). The Mw of polysiloxane resin A-2 was 83,000, and the polysiloxane content was 77.5% by mass.

[0127] [Synthesis example 3] In a 3L flask equipped with a stirrer, thermometer, nitrogen purging device and backflow cooler, 27.9g (0.15 mol) of compound (S-3), 19.6g (0.05 mol) of compound (S-1) and 129.0g (0.30 mol) of compound (S-6) were added, followed by the addition of 2,000g of toluene, and the mixture was heated to 70°C. Subsequently, 1.0 g of a platinum chloride toluene solution (platinum concentration 0.5% by mass) was added, and 87.3 g (0.45 moles) of compound (S-4) and 79.3 g (0.05 moles) of compound (S-5) (y 1=20, manufactured by Shin-Etsu Chemical Co., Ltd.) were added dropwise over 1 hour (total hydrosilene groups / total alkenyl groups = 1 / 1 (mole ratio). After the addition was complete, the mixture was heated to 100°C and aged for 6 hours. Toluene was then removed from the reaction solution by vacuum distillation to obtain polysiloxane resin A-3. Polysiloxane resin A-3 was confirmed to contain repeating units a1, a2, a4, b1, b2, and b4 by 1H-NMR (Bruker assay). The Mw of polysiloxane resin A-3 was 24,000, and the polysiloxane content was 31.2% by mass.

[0128] [2] Modulation of photosensitive resin composition [Examples 1-7 and Comparative Examples 1-20] Each component was prepared according to the preparation amounts recorded in Tables 1-3, and then dissolved by stirring at room temperature. The mixture was then precisely filtered using a 1.0 μm Teflon (registered trademark) filter to prepare the photosensitive resin compositions of Examples 1-7 and Comparative Examples 1-20.

[0129]

[0130]

[0131]

[0132] In Tables 1-3, the epoxy compounds B-1 to B-11 are listed below.

[0133]

[0134]

[0135]

[0136] In Tables 1-3, the photoacid generator PAG-1 is listed below.

[0137] In Tables 1-3, the crosslinking agent CL-1 is listed below.

[0138] In Tables 2 and 3, resin A'-1 is as follows.

[0139] [3] Preparation of photosensitive dry film A die coater was used as the thin film coater. A polyethylene terephthalate film (38 μm thick) was used as the support film. The photosensitive resin compositions listed in Tables 1-3 were coated onto the support film. Next, the film was dried in a hot air circulating oven (4 m long) set at 100°C for 5 minutes to form a photosensitive resin film on the support film, obtaining a photosensitive dry film. A polyethylene film (50 μm thick) as a protective film was then laminated onto the aforementioned photosensitive resin film using a laminating roller at a pressure of 1 MPa to produce a photosensitive dry film with a protective film. The thickness of each photosensitive resin film was 150 μm. The thickness of the photosensitive resin film was measured using an optical interferometric film thickness measuring machine (FILMETRICS F50-EXR).

[0140] [4] Evaluation of resin film (1) Graphic formation and evaluation The protective film of the aforementioned photosensitive dry film with a protective film was peeled off using a TEAM-100RF vacuum laminator (manufactured by TAKATORI). The vacuum level in the vacuum chamber was set to 80 Pa. The photosensitive resin film on the support film was adhered tightly to the migration test substrate (a comb-shaped electrode substrate with copper conductive material, a conductive part spacing and width of 10 μm, and a conductive part thickness of 4 μm). The temperature condition was set to 100°C. After returning to normal pressure, the substrate was removed from the vacuum laminator, and the support film was peeled off. Then, to improve adhesion to the substrate, a hot plate was used for preheating at 120°C for 5 minutes. To form line and spacing patterns and contact hole patterns on the resulting photosensitive resin film, a spacer mask was used, and exposure was performed using a contact alignment type exposure device at a wavelength of 365 nm. After exposure, the film was subjected to PEB treatment at 140°C for 5 minutes on a hot plate, then cooled, and spray-developed with PGMEA for 300 seconds to form the pattern.

[0141] The photosensitive resin film on the substrate with the pattern formed by the aforementioned method was cured in an oven at 200°C for 2 hours, followed by post-curing while blowing nitrogen gas. Subsequently, the cross-sections of the formed 300μm, 150μm, 100μm, and 50μm contact hole patterns were observed using a scanning electron microscope (SEM). The smallest hole pattern with holes penetrating to the bottom of the film was taken as the limiting resolution. Furthermore, the perpendicularity of the 300μm contact hole pattern was evaluated from the obtained cross-sectional photographs. A perpendicular pattern was marked with ◎, an inverted cone shape or a slight base was marked with ○, an inverted cone shape or a strong base was marked with △, and a poor opening was marked with ×. The results are shown in Tables 4-6.

[0142] (2) Evaluation of electrical characteristics (copper migration) The copper migration test was conducted using a substrate patterned by method (1) as a substrate for copper migration evaluation. The copper migration test was conducted at a temperature of 130°C, a humidity of 85%, and an applied voltage of 10V, with a maximum duration of 2,000 hours to determine the time that caused the short circuit. The results are shown in Tables 4-6.

[0143] (3) Evaluation of warping stress The fabricated film was laminated onto an 8-inch silicon wafer using a film laminator (TAKATORI TEAM-100). Preheating was performed at 120°C for 5 minutes using a hot plate. Subsequently, without a mask, exposure was performed using a contact alignment exposure device at a wavelength of 365nm. The film was then cured in an oven at 200°C for 2 hours. Warpage stress (25°C) was measured using a thin film stress meter (Topon Technology FLX-2320-S). The results are shown in Tables 4-6.

[0144] (4) Reliability (adhesion, crack resistance) evaluation The protective film of the aforementioned photosensitive dry film with a protective film was peeled off. Using a vacuum laminator TEAM-100RF (manufactured by TAKATORI), the vacuum level in the vacuum chamber was set to 80 Pa. The photosensitive resin film on the support film was then attached to a CCL substrate with a 10mm × 10mm square silicon wafer. The temperature was set to 100°C. After returning to normal pressure, the substrate was removed from the vacuum laminator, and the support film was peeled off. Then, to improve adhesion to the substrate, it was preheated at 120°C for 5 minutes using a hot plate. The resulting photosensitive resin film was exposed at a wavelength of 365nm using a contact alignment exposure device without a mask. After exposure, it was PEB cured at 140°C for 5 minutes using a hot plate, then cooled, and post-cured in an oven at 200°C while blowing nitrogen for 2 hours. Then, using a cutting saw equipped with a cutting blade (DISCO DAD685, spindle speed 40,000 rpm, cutting speed 20 mm / s), test pieces of 20 mm × 20 mm were obtained with a 5 mm outer edge of the silicon wafer. Ten test pieces were obtained each time for thermal cycling testing (1,500 cycles of holding at -40°C for 10 minutes and at 125°C for 10 minutes) to confirm whether the resin film had peeled off from the wafer or cracked after the thermal cycling test. No peeling or cracking was recorded as ○, even one peeling was recorded as ×, and even one crack was recorded as ×. Furthermore, the presence or absence of peeling and cracking was confirmed by top-down observation using an optical microscope and by cross-sectional SEM observation. The results are shown in Tables 4-6.

[0145] (5) Evaluation of the following force The warpage stress measurement substrate prepared in step (3) was cut into 2mm × 2mm square pieces using a cutting saw (DISCO DAD685) equipped with a cutting blade. A 2mm × 2mm square wafer was bonded to a separately prepared 15mm × 15mm square silicon wafer (substrate) at 150°C with a 50mN load using an interlayer resin film. The wafer was then heated at 180°C for 2 hours to harden the resin film, yielding a test piece. Five test pieces were fabricated sequentially for adhesion testing. The adhesion test was performed using an adhesion testing machine (Dage series 4000-PXY, Dage Corporation) to measure the resistance applied when the semiconductor wafer (2mm × 2mm) was peeled from the substrate (15mm × 15mm square silicon wafer), evaluating the adhesion of the resin film layer. The test conditions were a test speed of 200μm / s and a test height of 50μm. The results are shown in Tables 4-6. Furthermore, the numerical value is the average of the measured values ​​of 5 test pieces. The higher the value, the higher the adhesion.

[0146] (6) Evaluation of heat resistance The test piece prepared in (5) for the adhesion test was placed in an oven heated to 200°C for 1,000 hours. The test piece was then removed from the oven and subjected to the same adhesion test as in (5). The results are shown in Tables 4-6.

[0147] (7) Evaluation of specific dielectric constant and dielectric loss tangent The protective film of the aforementioned photosensitive dry film with a protective coating was peeled off, and exposure was performed using a contact alignment exposure device at a wavelength of 365 nm without the masking layer. Then, post-curing was carried out in an oven at 200°C while being purged with nitrogen for 2 hours. After removing the film from the oven and peeling off the support film, the specific dielectric constant (10 GHz, 25°C) and dielectric loss tangent (10 GHz, 25°C) were measured. The specific dielectric constant and dielectric loss tangent were measured using a cavity resonator method with an AET-manufactured device. The results are shown in Tables 4-6.

[0148] (8) Evaluation of softness The hardened film prepared in (7) is wound onto a plastic cylinder with an outer diameter of 8.5 cm. After standing for 10 seconds, the film is restored and the presence of any abnormalities is checked. Any cracks or other defects are marked as "×", and no changes are marked as "○".

[0149]

[0150]

[0151]

[0152] From the above results, the photosensitive resin composition and photosensitive dry film of the present invention can be easily formed into fine vertical patterns in thick films, demonstrating sufficient characteristics as a photosensitive material. Furthermore, the photosensitive resin film obtained in this way exhibits excellent flexibility, low dielectric constant and low dielectric loss tangent, high adhesion, high heat resistance, high copper migration resistance, and low substrate warpage. Its reliability as an insulating protective film, including crack resistance and adhesion, is high, making it suitable as a forming material for protective films of various electrical and electronic components such as circuit boards, semiconductor devices, and display devices. According to the present invention, photosensitive resin compositions and photosensitive dry films with even higher reliability can be provided.

Claims

1. A photosensitive resin composition comprising: (A) a polysiloxane resin containing an acid crosslinking group represented by the following formula (A), (B) an epoxy compound represented by the following formula (B), and (C) a photoacid generator, (wherein, R1 to R4 are each independently a hydrocarbon group having 1 to 8 carbon atoms, k is an integer from 1 to 600, a and b represent the composition ratio (molar ratio) of each repeating unit, and satisfy 0 < a < 1, 0 < b < 1 and a + b = 1, and X is a divalent organic group containing an epoxy group and / or a phenolic hydroxyl group), (wherein, R51 to R55 are each independently a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms).

2. The photosensitive resin composition of claim 1, wherein (A) the polysiloxane resin comprises repeating units represented by the following formulas (a1)~(a4) and (b1)~(b4), [where R1~R4 are each independently a hydrocarbon group with 1~8 carbon atoms, k is an integer from 1 to 600, a1~a4 and b1~b4 represent the composition ratio (molar ratio) of each repeating unit, and satisfy 0≦a1<1, 0≦a2<1, 0≦a3<1, 0≦a4<1, 0≦b1<1, 0≦b2<1, 0≦b3<1, 0≦b4<1, 0 < The numbers a1+a2+a3<1, 0<b1+b2+b3<1, and a1+a2+a3+a4+b1+b2+b3+b4=1, where X1 is a binary base expressed by the following formula (X1), X2 is a binary base expressed by the following formula (X2), X3 is a binary base expressed by the following formula (X3), and X4 is a binary base expressed by the following formula (X4). (In the formula, Y1 represents a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl, or fluorene-9,9-diyl; R11 and R12 are each independently a hydrogen atom or a methyl group; R13 and R14 are each independently a saturated hydrocarbon group with 1 to 4 carbon atoms or a saturated hydrocarbon oxygen group with 1 to 4 carbon atoms; p1 and p2 are each independently an integer from 0 to 7; q1 and q2 are each independently an integer from 0 to 2; and the dashed lines represent bond connections.) (In the formula, Y2 represents a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl; R21 and R22 are each independently a hydrogen atom or a methyl group; R23 and R24 are each independently a saturated hydrocarbon group with 1 to 4 carbon atoms or a saturated hydrocarbon oxygen group with 1 to 4 carbon atoms; r1 and r2 are each independently an integer from 0 to 7; s1 and s2 are each independently an integer from 0 to 2; and the dashed lines represent bond connections.) (In the formula, R31 and R32 are each independently a hydrogen atom or a methyl group; t1 and t2 are each independently an integer from 0 to 7; and the dashed lines represent bond connections.) (In the formula, R41 and R42 are each independently a hydrogen atom or a methyl group, R43 and R44 are each independently a hydrocarbon group with 1 to 8 carbon atoms, u1 and u2 are each independently an integer from 0 to 7, v is an integer from 0 to 600, and the dashed line represents the bond).

3. In the photosensitive resin composition of claim 1 or 2, the content of epoxy compound in component (B) is 3 to 100 parts by mass relative to 100 parts by mass of component (A).

4. The photosensitive resin composition of claim 1 or 2, wherein it further comprises (D) a crosslinking agent.

5. The photosensitive resin composition of claim 4, wherein (D) the crosslinking agent is selected from at least one of the following: nitrogen-containing compounds selected from melamine compounds, guanidine compounds, glycourea compounds and urea compounds containing an average of two or more hydroxymethyl and / or alkoxymethyl groups per molecule; amine condensates modified by formaldehyde or formaldehyde-alcohol; phenolic compounds having an average of two or more hydroxymethyl or alkoxymethyl groups per molecule; and epoxy compounds having an average of two or more epoxy groups per molecule.

6. The photosensitive resin composition of claim 1 or 2, wherein it further comprises (E) a solvent.

7. A photosensitive resin film obtained from a photosensitive resin composition as claimed in any one of claims 1 to 6.

8. A photosensitive dry film comprising a support film and a photosensitive resin film as claimed in claim 7 on the support film.

9. A pattern forming method comprising (i) forming a photosensitive resin film on a substrate using a photosensitive resin composition as claimed in any one of claims 1 to 6, (ii) exposing the aforementioned photosensitive resin film, and (iii) developing the aforementioned exposed photosensitive resin film using a developing solution to form a pattern.

10. A pattern forming method comprising (i') forming a photosensitive resin film on a substrate using a photosensitive dry film as claimed in claim 8, (ii) exposing the aforementioned photosensitive resin film, and (iii) developing the aforementioned exposed photosensitive resin film using a developing solution to form a pattern.

11. The pattern forming method of claim 9 or 10, further comprising (iv) a step of post-curing the photosensitive resin film for which the pattern is formed by development at a temperature of 100 to 250°C.

12. The photosensitive resin composition of any one of claims 1 to 6 is a material for a protective film for electrical and electronic components.

13. The photosensitive resin composition of any one of claims 1 to 6 is a material for a substrate bonding film used to bond two substrates.