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

Abstract

Provided is a photosensitive resin composition, which contains (A) a polymer containing a silicone skeleton and (B) a photoacid generator. The photoacid generator (B) contains (B1) an onium salt photoacid generator and (B2) a photoacid generator other than an onium salt.

Description

Technical Field

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

[0002] Conventionally, as a semiconductor element protective film having photosensitivity and an insulating film for a multilayer printed circuit board, a photosensitive polyimide composition, a photosensitive epoxy resin composition, a photosensitive silicone composition, etc. have been used. As a photosensitive material applied to the protection of such substrates and circuits, a photosensitive silicone composition having particularly excellent flexibility has been proposed (Patent Document 1). This photosensitive silicone composition can be cured at a low temperature and can form a film having excellent reliability such as moisture-resistant adhesiveness, but has a problem of poor chemical resistance to a photoresist stripper having a strong dissolving power for N-methyl-2-pyrrolidone.

[0003] In response to this, a photosensitive silicone composition containing a silicone-based polymer having a silphenylene skeleton as a main component has been proposed (Patent Document 2). With respect to this photosensitive silicone composition, the chemical resistance to a photoresist stripper, etc. is improved, but in a thermal cycle test (repeating 1,000 cycles of holding at -25°C for 10 minutes and holding at 125°C for 10 minutes), there are problems such as the cured product peeling off from the substrate and cracks occurring in the cured product, and further improvement in reliability is desired.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2002-88158

[0007] Patent Document 2: Japanese Unexamined Patent Application Publication No. 2012-1668 Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] In view of the above actual situation, the present invention has been completed, and an object thereof is to provide a photosensitive resin composition, a photosensitive dry film, a laminate using them, and a pattern forming method that can easily form a thick film and a fine pattern, and can form a cured product layer (cured film) having excellent various film properties such as crack resistance and adhesion to substrates, electronic components, semiconductor elements, etc., particularly to the base materials used in circuit boards, and having excellent reliability as a protective film for electrical and electronic components, a film for substrate bonding, etc.

[0010] Means for Solving the Problems

[0011] The inventors of the present invention have conducted repeated in-depth studies to achieve the above object, and as a result, it has been found that: by using a photosensitive resin composition containing a polymer having a silicone skeleton, an onium salt photoacid generator, and a photoacid generator other than the onium salt, the above problems can be solved, and the present invention has been completed.

[0012] Therefore, the present invention provides the following photosensitive resin composition, photosensitive dry film, laminate, and pattern forming method.

[0013] 1. A photosensitive resin composition comprising (A) a polymer having a silicone skeleton and (B) a photoacid generator, and the (B) photoacid generator comprises (B1) an onium salt photoacid generator and (B2) a photoacid generator other than the onium salt.

[0014] 2. The photosensitive resin composition according to 1, wherein the (A) polymer having a silicone skeleton comprises repeating units represented by the following formulas (a1) to (a4) and (b1) to (b4).

[0015] [Chemical formula 1]

[0016]

[0017] [In the formula, R 1 ~R 4 are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. m is an integer of 1 to 600.

[0018] a 1 ~a 4 and b 1 ~b 4 are numbers satisfying 0 ≤ a 1 <1, 0 ≤ a 2 <1, 0 ≤ a 3 <1, 0 ≤ a 4 <1, 0 ≤ b 1 <1, 0 ≤ b 2 <1, 0 ≤ b 3 <1, 0 ≤ b 4 <1, 0 < a 1 + a 2 + a 3 + a 4 <1, 0 < b 1 + b 2 + b 3 + b 4 <1 and a 1 + a 2 + a 3 + a 4 + b 1 + b 2 + b 3 + b 4 = 1.

[0019] X 1 is a divalent group represented by the following formula (X1). X 2 is a divalent group represented by the following formula (X2). X 3 is a divalent group represented by the following formula (X3). X 4 is a divalent group represented by the following formula (X4).

[0020] [Chemical Formula 2]

[0021]

[0022] (In the formula, Z 1 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl. R 11 and R 12 are each independently a hydrogen atom or a methyl group. R 13 and R 14 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. p 1 and p 2 are each independently an integer from 0 to 7. q 1 and q 2 are each independently an integer from 0 to 2.)

[0023] [Chemical Formula 3]

[0024]

[0025] (In the formula, Z 2 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl. R 21 and R 22 are each independently a hydrogen atom or a methyl group. R 23 and R 24 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. r 1 and r 2 are each independently an integer from 0 to 7. s 1 and s 2 are each independently an integer from 0 to 2.)

[0026] [Chemical Formula 4]

[0027]

[0028] (In the formula, R 31 and R 32 are each independently a hydrogen atom or a methyl group. t 1 and t2 Each independently is an integer from 0 to 7.)

[0029] [Chemical Formula 5]

[0030]

[0031] (In the formula, R 41 and R 42 Each independently is a hydrogen atom or a methyl group. R 43 and R 44 Each independently is a monovalent hydrocarbon group having 1 to 8 carbon atoms. u 1 and u 2 Each independently is an integer from 0 to 7. v is an integer from 0 to 600.)]

[0032] 3. The photosensitive resin composition according to 1 or 2, further comprising (C) a crosslinking agent.

[0033] 4. The photosensitive resin composition according to any one of 1 to 3, further comprising (D) a solvent.

[0034] 5. The photosensitive resin composition according to any one of 1 to 4, further comprising (E) a quencher.

[0035] 6. A photosensitive resin film obtained from the photosensitive resin composition according to any one of 1 to 5.

[0036] 7. A photosensitive dry film, comprising: a support film, and the photosensitive resin film according to 6 on the support film.

[0037] 8. A laminate, comprising: a substrate, and the photosensitive resin film according to 6 on the substrate.

[0038] 9. A pattern forming method, comprising:

[0039] (i) A step of forming a photosensitive resin film on a substrate using the photosensitive resin composition according to any one of 1 to 5,

[0040] (ii) A step of exposing the photosensitive resin film, and

[0041] (iii) A step of developing the exposed photosensitive resin film with a developer to form a pattern.

[0042] 10. A pattern forming method, comprising:

[0043] (i') A step of forming a photosensitive resin film on a substrate using the photosensitive dry film according to 7,

[0044] (ii) A step of exposing the photosensitive resin film, and

[0045] (iii) A step of developing the exposed photosensitive resin film with a developer to form a pattern.

[0046] 11. The pattern forming method according to 9 or 10, further comprising (iv) a step of post-curing the photosensitive resin film having the pattern formed thereon at a temperature of 100 to 250 °C.

[0047] Effects of the Invention

[0048] By using the photosensitive resin composition of the present invention, a film can be easily formed. The developed image clarity of the obtained film is excellent, and further, it has excellent performance in microfabrication, and has good reliability (adhesion, crack resistance), developed image clarity, and flexibility. Detailed Description of the Invention

[0049] The photosensitive resin composition of the present invention contains (A) a polymer having a silicone backbone and (B) a photoacid generator. The (B) photoacid generator contains both (B1) a photoacid generator which is an onium salt and (B2) a photoacid generator other than the onium salt.

[0050] [(A) Polymer having a silicone backbone]

[0051] The polymer having a silicone backbone as the component (A) is not particularly limited, and preferably contains repeating units represented by the following formulas (a1) to (a4) and (b1) to (b4) (hereinafter also referred to as repeating units a1 to a4 and b1 to b4, respectively).

[0052] [Chemical Formula 6]

[0053]

[0054] In the formulas (a1) to (a4), R 1 ~R 4 are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. m is an integer of 1 to 600. When m is an integer of 2 or more, each R 3 may be the same or different from each other, and each R 4 may be the same or different from each other. In the repeating units a1 to a4, when there are two or more siloxane units, all the siloxane units may be the same, or may include two or more different siloxane units. In the case of including two or more different siloxane units (i.e., when m is an integer of 2 or more), the siloxane units may be randomly combined, may be alternately combined, and may include blocks of multiple same siloxane units.

[0055] Regarding the above monovalent hydrocarbon groups, they can be linear, branched, or cyclic. Specific examples thereof include alkyl groups such as methyl, ethyl, propyl, hexyl, cyclohexyl, and their structural isomers, and aryl groups such as phenyl. Among these, from the perspective of ease of obtaining raw materials, methyl and phenyl are preferred.

[0056] In formulas (a1) to (a4), m is an integer from 1 to 600, preferably an integer from 1 to 400, and more preferably an integer from 1 to 200.

[0057] In formulas (a1) and (b1), X 1 is a divalent group represented by the following formula (X1).

[0058] [Chemical formula 7]

[0059]

[0060] In formula (X1), Z 1 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl, or fluorene-9,9-diyl. R 11 and R 12 are each independently a hydrogen atom or a methyl group. R 13 and R 14 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. p 1 and p 2 are each independently an integer from 0 to 7. q 1 and q 2 are each independently an integer from 0 to 2.

[0061] Regarding the above alkyl groups, they can be linear, branched, or cyclic. Specific examples thereof include methyl, ethyl, propyl, butyl, and their structural isomers. Regarding the above alkoxy groups, they can be linear, branched, or cyclic. Specific examples thereof include methoxy, ethoxy, propoxy, butoxy, and their structural isomers.

[0062] In formulas (a2) and (b2), X 2 is a divalent group represented by the following formula (X2).

[0063] [Chemical formula 8]

[0064]

[0065] In formula (X2), Z 2 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl, or fluorene-9,9-diyl. R 21 and R 22Each independently represents a hydrogen atom or a methyl group. R 23 and R 24 Each independently represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. r 1 and r 2 Each independently represents an integer from 0 to 7. s 1 and s 2 Each independently represents an integer from 0 to 2. Examples of the above alkyl group and alkoxy group include the same groups as those described above.

[0066] In formulas (a3) and (b3), X 3 represents a divalent group represented by the following formula (X3).

[0067] [Chemical formula 9]

[0068]

[0069] In formula (X3), R 31 and R 32 Each independently represents a hydrogen atom or a methyl group. t 1 and t 2 Each independently represents an integer from 0 to 7.

[0070] In formulas (a4) and (b4), X 4 represents a divalent group represented by the following formula (X4).

[0071] [Chemical formula 10]

[0072]

[0073] In formula (X4), R 41 and R 42 Each independently represents a hydrogen atom or a methyl group. R 43 and R 44 Each independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms. u 1 and u 2 Each independently represents an integer from 0 to 7. v is an integer from 0 to 600, preferably an integer from 0 to 400, more preferably an integer from 0 to 200. Examples of the above monovalent hydrocarbon group include the same groups as those described in the description of R 1 to R 4 In the group represented by formula (X4), when v is an integer of 2 or more, the siloxane units represented by the subscript v may be randomly bonded or alternately bonded, and may include blocks of multiple same siloxane units.

[0074] The polymer having a silicone backbone in component (A) preferably has a weight-average molecular weight (Mw) of 3,000 to 500,000, more preferably 5,000 to 200,000. It should be noted that in the present invention, Mw is a polystyrene conversion measurement value obtained by gel permeation chromatography (GPC) using tetrahydrofuran as an elution solvent.

[0075] In formulas (a1) to (a4) and (b1) to (b4), a 1 ~a 4 and b 1 ~b 4 are numbers satisfying 0 ≤ a 1 < 1, 0 ≤ a 2 < 1, 0 ≤ a 3 < 1, 0 ≤ a 4 < 1, 0 ≤ b 1 < 1, 0 ≤ b 2 < 1, 0 ≤ b 3 < 1, 0 ≤ b 4 < 1, 0 < a 1 +a 2 +a 3 +a 4 < 1, 0 < b 1 +b 2 +b 3 +b 4 < 1 and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 = 1, and preferably satisfy 0 ≤ a 1 ≤ 0.8, 0 ≤ a 2 ≤ 0.8, 0 ≤ a 3 ≤ 0.8, 0 ≤ a 4 ≤ 0.8, 0 ≤ b 1 ≤ 0.95, 0 ≤ b 2 ≤ 0.95, 0 ≤ b 3 ≤ 0.95, 0 ≤ b 4 ≤ 0.95, 0.05 ≤ a 1 +a 2 +a 3 +a 4 ≤ 0.8, 0.2 ≤ b 1 +b 2 +b 3 +b 4 ≤ 0.95 and a 1 +a 2 +a 3 +a 4+b 1 +b 2 +b 3 +b 4 =1, preferably 0≤a 1 ≤0.7, 0≤a 2 ≤0.7, 0≤a 3 ≤0.7, 0≤a 4 ≤0.7, 0≤b 1 ≤0.9, 0≤b 2 ≤0.9, 0≤b 3 ≤0.9, 0≤b 4 ≤0.9、0.1≤a 1 +a 2 +a 3 +a 4 ≤0.7、0.3≤b 1 +b 2 +b 3 +b 4 ≤0.9 and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 =1.

[0076] The polymer containing a silicone skeleton of component (A) preferably has a crosslinking group such as an epoxy group or a hydroxyl group or a reaction point for a crosslinking reaction in the molecule. That is, the polymer preferably contains at least one selected from the repeating units a1 to a3 and at least one selected from the repeating units b1 to b3. In this case, in formulas (a1) to (a4) and (b1) to (b4), a 1 ~a 4 and b 1 ~b 4 Preferably, 0≤a 1 <1, 0≤a 2 <1, 0≤a 3 <1, 0≤a 4 <1、0≤b 1 <1、0≤b 2 <1、0≤b 3 <1、0≤b 4 <1、0<a 1 +a 2 +a 3 <1、0<b 1 +b 2 +b 3 <1 and a 1 +a 2 +a 3+a 4 +b 1 +b 2 +b 3 +b 4 A number equal to 1, more preferably satisfying 0 ≤ a 1 ≤ 0.8, 0 ≤ a 2 ≤ 0.8, 0 ≤ a 3 ≤ 0.8, 0 ≤ a 4 ≤ 0.8, 0 ≤ b 1 ≤ 0.95, 0 ≤ b 2 ≤ 0.95, 0 ≤ b 3 ≤ 0.95, 0 ≤ b 4 ≤ 0.95, 0.05 ≤ a 1 +a 2 +a 3 ≤ 0.8, 0.2 ≤ b 1 +b 2 +b 3 ≤ 0.95 and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 A number equal to 1, further preferably satisfying 0 ≤ a 1 ≤ 0.7, 0 ≤ a 2 ≤ 0.7, 0 ≤ a 3 ≤ 0.7, 0 ≤ a 4 ≤ 0.7, 0 ≤ b 1 ≤ 0.9, 0 ≤ b 2 ≤ 0.9, 0 ≤ b 3 ≤ 0.9, 0 ≤ b 4 ≤ 0.9, 0.1 ≤ a 1 +a 2 +a 3 ≤ 0.7, 0.3 ≤ b 1 +b 2 +b 3 ≤ 0.9 and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 A number equal to 1.

[0077] In particular, the polymer containing a silicone skeleton in component (A) preferably contains repeating units a3 and b3. At this time, in formulas (a1) to (a4) and (b1) to (b4), a 1 ~a4 and b 1 ~b 4 Preferably satisfy 0 ≤ a 1 <1, 0 ≤ a 2 <1, 0 < a 3 <1, 0 ≤ a 4 <1, 0 ≤ b 1 <1, 0 ≤ b 2 <1, 0 < b 3 <1, 0 ≤ b 4 <1, 0 < a 1 +a 2 +a 3 +a 4 <1, 0 < b 1 +b 2 +b 3 +b 4 <1 and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 = 1, and more preferably satisfy 0 ≤ a 1 <0.8, 0 ≤ a 2 <0.8, 0 < a 3 ≤0.8, 0 ≤ a 4 <0.8, 0 ≤ b 1 <0.95, 0 ≤ b 2 <0.95, 0 < b 3 ≤0.95, 0 ≤ b 4 <0.95, 0.05 ≤ a 1 +a 2 +a 3 +a 4 ≤0.8, 0.2 ≤ b 1 +b 2 +b 3 +b 4 ≤0.95 and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 = 1, and further preferably satisfy 0 ≤ a 1 <0.7, 0 ≤ a 2 <0.7, 0 < a 3 ≤0.7, 0 ≤ a 4 <0.7, 0 ≤ b 1< 0.9, 0 ≤ b 2 < 0.9, 0 < b 3 ≤ 0.9, 0 ≤ b 4 < 0.9, 0.1 ≤ a 1 +a 2 +a 3 +a 4 ≤ 0.7, 0.3 ≤ b 1 +b 2 +b 3 +b 4 ≤ 0.9 and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 a number such that = 1.

[0078] Each of the above repeating units may be combined randomly or as a block polymer. In addition, the siloxane units in each repeating unit may be combined randomly and may include blocks of multiple siloxane units of the same type. In addition, in the above silicone resin, the content of silicone (siloxane units) is preferably 30 to 80% by mass.

[0079] (Component (A)) The polymer containing a silicone backbone functions as a component that imparts film-forming ability. In addition, the obtained resin film has good adhesion to laminates, substrates, etc., good pattern-forming ability, crack resistance, and heat resistance.

[0080] (Component (A)) The polymer containing a silicone backbone may be used alone or in combination of two or more.

[0081] [Method for producing a polymer containing a silicone backbone]

[0082] The above polymer containing a silicone backbone can be produced by subjecting at least one selected from the group consisting of the compounds represented by the following formula (1) (hereinafter also referred to as compound (1)), the compounds represented by the following formula (2) (hereinafter also referred to as compound (2)), the compounds represented by the following formula (3) (hereinafter also referred to as compound (3)), the compounds represented by the following formula (4) (hereinafter also referred to as compound (4)), the compounds represented by the following formula (5) (hereinafter also referred to as compound (5)), and the compounds represented by the following formula (6) (hereinafter also referred to as compound (6)) to addition polymerization in the presence of a metal catalyst.

[0083] [Chemical 11]

[0084]

[0085] (wherein, R 1 ~R 4 and m are the same as defined above.)

[0086] [Chemical Formula 12]

[0087]

[0088] (wherein, R 11 ~R 14 , R 21 ~R 24 , R 31 , R 32 , R 41 ~R 44 , Z 1 , Z 2 , p 1 , p 2 , q 1 , q 2 , r 1 , r 2 , s 1 , s 2 , t 1 , t 2 , u 1 , u 2 and v are the same as defined above.)

[0089] As the above metal catalyst, platinum group metal simple substances such as platinum (including platinum black), rhodium, and palladium can be used; platinum chlorides such as H2PtCl4·xH2O, H2PtCl6·xH2O, NaHPtCl6·xH2O, KHPtCl6·xH2O, Na2PtCl6·xH2O, K2PtCl4·xH2O, PtCl4·xH2O, PtCl2, Na2HPtCl4·xH2O (wherein, x is preferably an integer of 0 to 6, particularly preferably 0 or 6.), chloroplatinic acid, and chloroplatinate salts; alcohol-modified chloroplatinic acid (such as those described in the specification of U.S. Patent No. 3,220,972); complexes of chloroplatinic acid and olefins (such as those described in the specifications of U.S. Patent No. 3,159,601, U.S. Patent No. 3,159,662, and U.S. Patent No. 3,775,452); products obtained by supporting platinum group metals such as platinum black and palladium on carriers such as alumina, silica, and carbon; rhodium-olefin complexes; chloro(tris(triphenylphosphine))rhodium (so-called Wilkinson catalyst); complexes of platinum chloride, chloroplatinic acid, or chloroplatinate salts with vinyl-containing siloxanes (particularly vinyl-containing cyclic siloxanes), etc.

[0090] The amount of the above catalyst used is the amount of the catalyst. Generally, relative to 100 parts by mass in total of compounds (1) to (6), it is preferably 0.001 to 0.1 part by mass, more preferably 0.01 to 0.1 part by mass.

[0091] In the above addition polymerization reaction, a solvent can be used as needed. As the solvent, for example, hydrocarbon solvents such as toluene and xylene are preferred.

[0092] Regarding the polymerization temperature, from the viewpoints that the catalyst is not deactivated and the polymerization can be completed in a short time, it is preferably 40 to 150 °C, more preferably 60 to 120 °C. The polymerization time also depends on the type and amount of the resin obtained. In order to prevent the intrusion of moisture into the polymerization system, it is preferably about 0.5 to 100 hours, more preferably 0.5 to 30 hours. After the reaction is completed, in the case where a solvent is used, by distilling it off, a polymer containing a silicone skeleton of component (A) can be obtained.

[0093] There is no particular limitation on the reaction method. For example, the following methods can be cited: First, at least one selected from compounds (3) to (6) is heated, and then a metal catalyst is added thereto. Secondly, compounds (1) and (2) are dropped in over 0.1 to 5 hours.

[0094] Regarding each raw material compound, relative to the total of the alkenyl groups of at least one selected from compounds (3) to (6), the total of the hydrosilyl groups of the compound represented by formula (1) and the compound represented by formula (2) is preferably in a molar ratio of 0.67 to 1.67, more preferably 0.83 to 1.25.

[0095] The Mw of the above polymer containing a silicone skeleton can be controlled by using a monoallyl compound such as o-allylphenol or a monohydrosilane or monohydrosiloxane such as triethylsilane as a molecular weight regulator.

[0096] [(B) Photoacid generator]

[0097] The photoacid generator of component (B) is not particularly limited as long as it decomposes by light irradiation to generate an acid, and it preferably generates an acid by irradiating light with a wavelength of 190 to 500 nm. Since the composition of the present invention has excellent compatibility of the acid generator, a wide variety of acid generators can be used.

[0098] (B) The photoacid generator is used as a curing catalyst. The photoacid generator of component (B) includes (B1) an onium salt photoacid generator (hereinafter also referred to as an onium salt type photoacid generator.) and (B2) a photoacid generator other than an onium salt (hereinafter also referred to as a non-onium salt type photoacid generator.).

[0099] As the (B1) onium salt type photoacid generator, examples include sulfonium salts represented by the following formula (B1-1), iodonium salts represented by the following formula (B1-2), etc.

[0100] [Chemical formula 13]

[0101]

[0102] In formulas (B1-1) and (B1-2), R 101 ~R 105 are each independently an alkyl group having 1 to 12 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms which may have a substituent. A - is a non-nucleophilic counterion.

[0103] As the above alkyl group, it can be linear, branched, or cyclic. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, etc. As the above aryl group, examples include phenyl, naphthyl, biphenyl, etc. As the above aralkyl group, examples include benzyl, phenethyl, etc.

[0104] As the above substituent, examples include an oxo group, a linear, branched, or cyclic alkoxy group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aralkyl group having 7 to 25 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, an arylthio group having 6 to 24 carbon atoms, etc.

[0105] As R 101 ~R 105 , preferred are alkyl groups which may have a substituent such as methyl, ethyl, propyl, butyl, cyclohexyl, norbornyl, adamantyl, 2-oxocyclohexyl, etc.; aryl groups which may have a substituent such as phenyl, naphthyl, biphenyl, 2-, 3-, or 4-methoxyphenyl, ethoxyphenyl, 3- or 4-tert-butoxyphenyl, 2-, 3-, or 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl, terphenyl, biphenoxyphenyl, biphenylthiobphenyl, etc.; aralkyl groups which may have a substituent such as benzyl, phenethyl, etc. Among these, more preferred are aryl groups which may have a substituent and aralkyl groups which may have a substituent.

[0106] Examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; fluoroalkane sulfonate ions such as trifluoromethanesulfonate ion, 1,1,1-trifluoroethanesulfonate ion, and nonafluorobutanesulfonate ion; arylsulfonate ions such as tosylate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion, and 1,2,3,4,5-pentafluorobenzenesulfonate ion; alkanesulfonate ions such as methanesulfonate ion and butanesulfonate ion; fluoroalkanesulfonimide ions such as trifluoromethanesulfonimide ion; fluoroalkanesulfonylmethyl ions such as tris(trifluoromethanesulfonyl)methyl ion; borate ions such as tetraphenylborate ion and tetrakis(pentafluorophenyl)borate ion, etc.

[0107] Specific examples of the onium salt include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyl iodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyl iodonium 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)iodonium hexafluorophosphate, 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, tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(pentafluorophenyl)borate, etc.

[0108] Examples of the non-onium salt type photoacid generator (B2) include diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, sulfonate derivatives, imide sulfonate derivatives, oxime sulfonate derivatives, iminosulfonate derivatives, triazine derivatives, etc.

[0109] Examples of the diazomethane derivative include the compound represented by the following formula (B2-1).

[0110] [Chemical formula 14]

[0111]

[0112] In formula (B2-1), R 111 and R 112 are each independently an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms.

[0113] Regarding the above alkyl group, it may be linear, branched or cyclic. As specific examples, groups similar to those exemplified in the description of R 101 to R 105 can be cited. As the above haloalkyl group, trifluoromethyl, 1,1,1-trifluoroethyl, 1,1,1-trichloroethyl, nonafluorobutyl, etc. can be cited.

[0114] As the above aryl group which may have a substituent, phenyl can be cited; alkoxyphenyl such as 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 3- or 4-tert-butoxyphenyl; alkylphenyl such as 2-, 3- or 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl; haloaryl such as fluorophenyl, chlorophenyl, 1,2,3,4,5-pentafluorophenyl, etc. As the above aralkyl group, benzyl, phenethyl, etc. can be cited.

[0115] As the above glyoxime derivative, a compound represented by the following formula (B2-2) can be cited.

[0116] [Chemical formula 15]

[0117]

[0118] In formula (B2-2), R 121 to R 124 are each independently an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms. In addition, R 123 and R 124 may combine with each other and together with the carbon atom to which they are attached form a ring. In the case of forming a ring, the group formed by the combination of R 123 and R 124 is a linear or branched alkylene group having 1 to 12 carbon atoms.

[0119] As the above alkyl group, haloalkyl group, aryl group which may have a substituent and aralkyl group, groups similar to those exemplified as R 111 and R 112 can be cited. As the above linear or branched alkylene group, methylene, ethylene, propylene, butylene, hexylene, etc. can be cited.

[0120] As the above diazomethane derivatives, specifically, 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, bis(tert-butylsulfonyl)diazomethane, bis(n-pentylsulfonyl)diazomethane, bis(isopentylsulfonyl)diazomethane, bis(sec-pentylsulfonyl)diazomethane, bis(tert-pentylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-pentylsulfonyl)diazomethane, 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane, etc. can be cited.

[0121] As the above glyoxime derivatives, specifically, bis-o-(p-toluenesulfonyl)-α-dimethyglyoxime, bis-o-(p-toluenesulfonyl)-α-diphenylglyoxime, bis-o-(p-toluenesulfonyl)-α-dicyclohexylglyoxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedione glyoxime, bis-(p-toluenesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-α-dimethyglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis-o-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis-o-(methanesulfonyl)-α-dimethyglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethyglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethyglyoxime, bis-o-(tert-butanesulfonyl)-α-dimethyglyoxime, bis-o-(perfluorooctanesulfonyl)-α-dimethyglyoxime, bis-o-(cyclohexanesulfonyl)-α-dimethyglyoxime, bis-o-(phenylsulfonyl)-α-dimethyglyoxime, bis-o-(p-fluorophenylsulfonyl)-α-dimethyglyoxime, bis-o-(p-tert-butylphenylsulfonyl)-α-dimethyglyoxime, bis-o-(xylenesulfonyl)-α-dimethyglyoxime, bis-o-(camphorsulfonyl)-α-dimethyglyoxime, etc. can be cited.

[0122] As the above β-ketosulfone derivatives, specifically, 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane, 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane, etc. can be cited.

[0123] As the above-mentioned disulfone derivatives, specifically, diphenyl disulfone, dicyclohexyl disulfone, etc. can be cited.

[0124] As the above-mentioned nitrobenzyl sulfonate derivatives, specifically, 2,6-dinitrobenzyl p-toluenesulfonate, 2,4-dinitrobenzyl p-toluenesulfonate, etc. can be cited.

[0125] As the above-mentioned sulfonate derivatives, specifically, 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, 1,2,3-tris(p-toluenesulfonyloxy)benzene, etc. can be cited.

[0126] As the above-mentioned imide sulfonate derivatives, specifically, phthalimide trifluoromethanesulfonate, phthalimide toluenesulfonate, 5-norbornene-2,3-dicarboximide trifluoromethanesulfonate, 5-norbornene-2,3-dicarboximide toluenesulfonate, 5-norbornene-2,3-dicarboximide n-butylsulfonate, n-trifluoromethanesulfonyloxynaphthalimide, etc. can be cited.

[0127] As the above-mentioned oxime sulfonate derivatives, specifically, α-(phenylsulfonyloximino)-4-methylphenylacetonitrile, etc. can be cited.

[0128] As the above-mentioned imino sulfonate derivatives, specifically, (5-(4-methylphenyl)sulfonyloximino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-(4-(4-methylphenylsulfonyloxy)phenyl)sulfonyloximino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, etc. can be cited.

[0129] In addition, as the (B2) non-onium salt type photoacid generator, 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane, etc. can also be preferably used.

[0130] In (B) the photoacid generator, as the (B1) onium salt type photoacid generator, sulfonium salts are preferred, and as the (B2) non-onium salt type photoacid generator, diazomethane derivatives are preferred.

[0131] Regarding the content of component (B), from the viewpoint of photocurability, the total of (B1) onium salt type photoacid generator and (B2) non-onium salt type photoacid generator 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 (B) is 0.05 parts by mass or more, there is no need to worry about insufficient acid generation and the crosslinking reaction not proceeding sufficiently, so it is preferred. In addition, if it is 20 parts by mass or less, an increase in the absorbance of the photoacid generator itself can be suppressed, and there is no need to worry about the problem of reduced transparency, so it is preferred. In addition, the content of (B1) onium salt type photoacid generator is preferably more than that of (B2) non-onium salt type photoacid generator. Specifically, relative to 100 parts by mass of (B2) non-onium salt type photoacid generator, it is preferably 125 to 500 parts by mass, more preferably 150 to 300 parts by mass.

[0132] [(C) Crosslinking agent]

[0133] The photosensitive resin composition of the present invention preferably further contains (C) crosslinking agent. The above crosslinking agent is a component that is used to undergo a condensation reaction with the phenolic hydroxyl group of the above component (A) or an alkoxy group represented by R 13 , R 14 , R 23 or R 24 and can facilitate the formation of a pattern, and at the same time further improve the strength of the cured product.

[0134] As the above crosslinking agent, a resin having an Mw of 150 to 10,000, particularly 200 to 3,000, is preferred. If the Mw is 150 or more, sufficient photocurability can be obtained. If it is 10,000 or less, there is no need to worry about deteriorating the heat resistance of the cured composition, so it is preferred.

[0135] In addition, as the above crosslinking agent, nitrogen-containing compounds such as melamine compounds, guanamine compounds, glycoluril compounds, and urea compounds that preferably contain 2 or more hydroxymethyl groups and / or alkoxymethyl groups on average in 1 molecule, amino condensates modified with formaldehyde or formaldehyde-alcohol, phenolic compounds having 2 or more hydroxymethyl groups or alkoxymethyl groups on average in 1 molecule, and epoxy compounds having 2 or more epoxy groups on average in 1 molecule are also preferred.

[0136] As the above melamine compound, a compound represented by the following formula (C1) can be cited.

[0137] [Chemical formula 16]

[0138]

[0139] In formula (C1), R 201 ~R 206Each is independently a hydrogen atom, a hydroxymethyl group, or an alkoxymethyl group having 2 to 5 carbon atoms, and at least one is a hydroxymethyl group or an alkoxymethyl group. Examples of the alkoxymethyl group include a methoxymethyl group and an ethoxymethyl group.

[0140] Examples of the melamine compound represented by the formula (C1) include trimethoxymethylmonohydroxymethylmelamine, dimethoxymethylmonohydroxymethylmelamine, trihydroxymethylmelamine, hexahydroxymethylmelamine, hexamethoxymethylmelamine, and hexaethoxymethylmelamine.

[0141] The melamine compound represented by the formula (C1) can be obtained, for example, by first hydroxymethylating melamine monomers with formaldehyde by a known method and then further alkoxylating them with an alcohol. Further, as the alcohol, a lower alcohol such as an alcohol having 1 to 4 carbon atoms is preferable.

[0142] Examples of the guanamine compound include tetrahydroxymethylguanamine, tetramethoxymethylguanamine, and tetramethoxyethylguanamine.

[0143] Examples of the glycoluril compound include tetrahydroxymethylglycoluril and tetra(methoxymethyl)glycoluril.

[0144] Examples of the urea compound include tetrahydroxymethylurea, tetramethoxymethylurea, tetramethoxyethylurea, tetraethoxymethylurea, and tetrapropoxymethylurea.

[0145] Examples of the amino condensate modified with formaldehyde or formaldehyde-alcohol include a melamine condensate modified with formaldehyde or formaldehyde-alcohol and a urea condensate modified with formaldehyde or formaldehyde-alcohol.

[0146] Examples of the modified melamine condensate include a substance obtained by adding and polycondensing a compound represented by the formula (C1) or its polymer (e.g., oligomers such as dimers and trimers) with formaldehyde by a conventional method until a desired molecular weight is reached.

[0147] Examples of the urea condensate modified with formaldehyde or formaldehyde-alcohol include a methoxymethylated urea condensate, an ethoxymethylated urea condensate, and a propoxymethylated urea condensate.

[0148] The above-mentioned modified urea condensate can be obtained, for example, by hydroxymethylating a urea condensate having a desired molecular weight with formaldehyde by a known method and then further alkoxylating it with an alcohol.

[0149] Examples of the phenolic compound having an average of 2 or more hydroxymethyl groups or alkoxymethyl groups in one molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol and 2,2',6,6'-tetramethoxymethylbisphenol A.

[0150] Examples of the epoxy compound having on average two or more epoxy groups in one molecule include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, novolak type epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin, trisphenane type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene-modified phenol novolak type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, epoxy resin containing a naphthalene ring, glycidyl ester type epoxy resin, alicyclic epoxy resin, heterocyclic type epoxy resin, and the like.

[0151] When component (C) is included, regarding its content, relative to 100 parts by mass of component (A), it is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass. If it is 0.5 parts by mass or more, sufficient curability can be obtained upon light irradiation. If it is 50 parts by mass or less, the proportion of component (A) in the photosensitive resin composition does not decrease, and thus the cured product can exhibit sufficient effects of the present invention. The crosslinking agent of component (C) can be used alone or in combination of two or more.

[0152] [(D) Solvent]

[0153] The photosensitive resin composition of the present invention may further contain (D) solvent. As the above solvent, as long as it is a solvent in which components (A) to (C) and various additives described later can be dissolved, there is no particular limitation. From the viewpoint of excellent solubility of these components, an organic solvent is preferred.

[0154] Examples of the above 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; esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monoterbutyl ether acetate, and γ-butyrolactone. These organic solvents can be used alone or in combination of two or more. Ethyl lactate, cyclohexanone, cyclopentanone, PGMEA, γ-butyrolactone, and their mixed solvents, which have the most excellent solubility for the photoacid generator, are particularly preferred.

[0155] Regarding the usage amount of component (D), from the viewpoints of compatibility and viscosity of the photosensitive resin composition, relative to the total 100 parts by mass of components (A) and (B), it is preferably 50 to 2,000 parts by mass, more preferably 50 to 1,000 parts by mass, and particularly preferably 50 to 100 parts by mass.

[0156] [(E) Quencher]

[0157] The photosensitive resin composition of the present invention may further contain (E) quencher. As the quencher, a compound capable of suppressing the diffusion rate of the acid generated by the photoacid generator during diffusion in the photosensitive resin film is suitable. By incorporating the above-mentioned quencher, the resolution is improved, the change in sensitivity after exposure is suppressed, the substrate dependence or environmental dependence is reduced, and the exposure margin and pattern shape can be improved.

[0158] Examples of the above-mentioned quencher include aliphatic primary, secondary or tertiary amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives, and the like.

[0159] Examples of the above-mentioned aliphatic primary amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-pentylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, hexadecylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, and the like.

[0160] Examples of the above-mentioned aliphatic secondary amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, bis(dodecyl)amine, bis(hexadecyl)amine, N,N-dimethylmethylenediamine, N,N-dimethylethylenediamine, N,N-dimethyltetraethylenepentamine, and the like.

[0161] Examples of the above-mentioned aliphatic tertiary amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tris(dodecyl)amine, tris(hexadecyl)amine, N,N,N',N'-tetramethylmethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyltetraethylenepentamine, and the like.

[0162] Examples of the above-mentioned mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine, and the like.

[0163] Examples of the above-mentioned aromatic amines and heterocyclic amines include aniline derivatives (e.g., aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N,N-dimethyltoluidine, etc.), diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (e.g., oxazole, isoxazole, etc.), thiazole derivatives (e.g., thiazole, isothiazole, etc.), imidazole derivatives (e.g., imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazan derivatives, pyrroline derivatives (e.g., pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidone, N-methyl-2-pyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine, 4-pyridylalkylpyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (e.g., quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives, etc.

[0164] Examples of the above-mentioned nitrogen-containing compounds having a carboxyl group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (e.g., nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine, etc.).

[0165] Examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid, pyridinium p-toluenesulfonate, and the like.

[0166] Examples of the nitrogen-containing compound having a hydroxyl group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, 2-quinolinediol, 3-indolemethanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl)morpholine, 2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine, 1-[2-(2-hydroxyethoxy)ethyl]piperazine, piperidinoethanol, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyquinuclidine, 3-quinuclidinol, 3-tropinol, 1-methyl-2-pyrrolidinoethanol, 1-aziridineethanol, N-(2-hydroxyethyl)phthalimide, N-(2-hydroxyethyl)isonicotinamide, and the like.

[0167] Examples of the amide derivative include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, benzamide, and the like.

[0168] Examples of the imide derivative include phthalimide, succinimide, maleimide, and the like.

[0169] As the above-mentioned quencher, a compound represented by the following formula (E1) can also be used.

[0170] [Chemical formula 17]

[0171] (R 301 )w-N-(R 302 ) 3-w (E1)

[0172] In formula (E1), w is 1, 2, or 3. R 301 is any substituent selected from the substituents represented by the following formulas (E2) to (E4). R 302 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, which may contain an ether bond or a hydroxyl group. In addition, when there are two or more R 301 , two R 301 may combine with each other and form a ring together with the nitrogen atom to which they are attached. In addition, when there are two or more R 301 , they may be the same or different. When there are two or more R 302When there are two or more of them, they may be the same or different.

[0173] [Chemical formula 18]

[0174]

[0175] In formulas (E2) to (E4), R 303 , R 305 and R 308 are each independently a linear or branched alkylene group having 1 to 4 carbon atoms. R 304 and R 307 are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and may contain at least one selected from a hydroxyl group, an ether bond, an ester bond, and a lactone ring. R 306 is a single bond, or a linear or branched alkylene group having 1 to 4 carbon atoms. R 309 is an alkyl group having 1 to 20 carbon atoms, and may contain at least one selected from a hydroxyl group, an ether bond, an ester bond, and a lactone ring.

[0176] Examples of the compound represented by the formula (E1) include tris[2-(methoxymethoxy)ethyl]amine, tris[2-(2-methoxyethoxy)ethyl]amine, tris[2-(2-methoxyethoxymethoxy)ethyl]amine, tris[2-(1-methoxyethoxy)ethyl]amine, tris[2-(1-ethoxyethoxy)ethyl]amine, tris[2-(1-ethoxypropoxy)ethyl]amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane, 4,7,13,18-tetraoxa-1,10-diazabicyclo[8.5.5]eicosane, 1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6, tris(2-formyloxyethyl)amine, tris(2-acetoxyethyl)amine, tris(2-propionyloxyethyl)amine, tris(2-butyryloxyethyl)amine, tris(2-isobutyryloxyethyl)amine, tris(2-valeryloxyethyl)amine, tris(2-pivaloyloxyethyl)amine, N,N-bis(2-acetoxyethyl) 2-(acetoxyacetoxy)ethylamine, tris(2-methoxycarbonyloxyethyl)amine, tris(2-tert-butoxycarbonyloxyethyl)amine, tris[2-(2-oxopropoxy)ethyl]amine, tris[2-(methoxycarbonylmethyl)oxyethyl]amine, tris[2-(tert-butoxycarbonylmethoxy)ethyl]amine, tris[2-(cyclohexyloxycarbonylmethoxy)ethyl]amine, tris(2-methoxycarbonylethyl)amine, tris(2-ethoxycarbonylethyl)amine, N,N-bis(2-hydroxyethyl)-2-(methoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(methoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(ethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(ethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(2-methoxyethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(2-methoxyethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(2-hydroxyethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(2-acetoxyethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-[(methoxycarbonyl)methoxycarbonyl]ethylamine, N,N-bis(2-acetoxyethyl)-2-[(methoxycarbonyl)methoxycarbonyl]ethylamine, N,N-bis(2-hydroxyethyl)-2-(2-oxopropoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(2-oxopropoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(tetrahydrofurfuryloxycarbonyl)ethylamine, N,N-N-bis(2-acetoxyethyl)-2-(tetrahydrofurfuryloxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-[(2-oxotetrahydrofuran-3-yl)oxycarbonyl]ethylamine, N,N-bis(2-acetoxyethyl)-2-[(2-oxotetrahydrofuran-3-yl)oxycarbonyl]ethylamine, N,N-bis(2-hydroxyethyl)-2-(4-hydroxybutoxycarbonyl)ethylamine, N,N-bis(2-formyloxyethyl)-2-(4-formyloxybutoxycarbonyl)ethylamine, N,N-bis(2-formyloxyethyl)-2-(2-formyloxyethoxycarbonyl)ethylamine, N,N-bis(2-methoxyethyl)-2-(methoxycarbonyl)ethylamine, N-(2-hydroxyethyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2-acetoxyethyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2-hydroxyethyl)bis[2-(ethoxycarbonyl)ethyl]amine, N-(2-acetoxyethyl)bis[2-(ethoxycarbonyl)ethyl]amine, N-(3-hydroxy-1-propyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(3-acetoxy-1-propyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2-methoxyethyl)bis[2-(methoxycarbonyl)ethyl]amine, N-butylbis[2-(methoxycarbonyl)ethyl]amine, N-butylbis[2-(2-methoxyethoxycarbonyl)ethyl]amine, N-methylbis(2-acetoxyethyl)amine, N-ethylbis(2-acetoxyethyl)amine, N-methylbis(2-pivaloyloxyethyl)amine, N-ethylbis[2-(methoxycarbonyloxy)ethyl]amine, N-ethylbis[2-(tert-butoxycarbonyloxy)ethyl]amine, tris(methoxycarbonylmethyl)amine, tris(ethoxycarbonylmethyl)amine, N-butylbis(methoxycarbonylmethyl)amine, N-hexylbis(methoxycarbonylmethyl)amine, and β-(diethylamino)-δ-valerolactone, but are not limited thereto.,

[0177] Regarding the content of the component (E), it is 0 to 3 parts by mass with respect to 100 parts by mass of the component (A). When it is contained, from the viewpoint of sensitivity, it is preferably 0.01 to 2 parts by mass, more preferably 0.05 to 1 part by mass. The component (E) can be used alone as 1 kind, or two or more kinds can be used in combination.,

[0178] [Other Additives]

[0179] In addition to the above components, the photosensitive resin composition of the present invention may contain other additives. As other additives, for example, surfactants commonly used to improve coatability can be cited.,

[0180] As the above surfactant, a nonionic surfactant is preferred. For example, fluorosurfactants can be cited. Specifically, perfluoroalkyl polyoxyethylene ethanol, fluoroalkyl esters, perfluoroalkyl amine oxides, fluorine-containing organosiloxane compounds, etc. can be cited. These can use commercially available products. For example, Fluorad (registered trademark) FC-430 (manufactured by 3M Company), Surflon (registered trademark) S-141 and S-145 (manufactured by AGC Seimi Chemical Co., Ltd.), Unidyne (registered trademark) DS-401, DS-4031 and DS-451 (manufactured by Daikin Industries, Ltd.), MEGFAC (registered trademark) F-8151 (manufactured by DIC Corporation), X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. can be cited. Among these, Fluorad FC-430 and X-70-093 are preferred. Regarding the content of the above surfactant, relative to 100 parts by mass of the component (A), 0.01 to 5 parts by mass is preferred.

[0181] The photosensitive resin composition of the present invention may contain a silane coupling agent as other additives. By containing a silane coupling agent, the adhesion of the resin film obtained from the composition to the adherend can be further improved. As the silane coupling agent, a silane coupling agent containing an epoxy group, an amino silane coupling agent containing an aromatic group, etc. can be cited. These can be used alone or in combination of two or more. There is no particular limitation on the content of the above silane coupling agent. When contained, it is preferably 0.01 to 5% by mass in the photosensitive resin composition of the present invention.

[0182] The photosensitive resin composition of the present invention can be prepared by a usual method. For example, by stirring and mixing the above components and then filtering according to need using a filter, etc., the photosensitive resin composition of the present invention can be prepared.

[0183] The photosensitive resin composition of the present invention is suitable for use as a protective film for semiconductor elements, a protective film for wirings, a cover film, a solder resist, a material for an insulating film for through electrodes (for TSV), and an adhesive between laminated substrates in three-dimensional lamination, for example.

[0184] [Pattern formation method using the photosensitive resin composition]

[0185] The pattern formation method using the photosensitive resin composition of the present invention includes:

[0186] (i) A step of forming a photosensitive resin film on a substrate using the photosensitive resin composition of the present invention;

[0187] (ii) A step of exposing the above photosensitive resin film; and

[0188] (iii) A step of developing the above-exposed photosensitive resin film with a developer to form a pattern.

[0189] Step (i) is a step of forming a photosensitive resin film on a substrate using a photosensitive resin composition. Examples of the above substrate include a silicon wafer, a silicon wafer for a through electrode, a silicon wafer thinned by back grinding, a plastic or ceramic substrate, and a substrate having a metal such as Ni or Au on the entire surface or a part of the substrate by an ion sputtering method, a plating method, etc. Sometimes, a substrate having either or both of grooves and holes with an opening width of 10 to 100 μm and a depth of 10 to 120 μm is also used. Furthermore, the opening width and depth of the grooves or holes of the substrate can be measured using a scanning electron microscope.

[0190] As a method for forming the photosensitive resin film, for example, methods such as dipping, spin coating, and roll coating can be used to coat the above photosensitive resin composition on the above substrate, and preheating (pre-baking: PB) can be performed as needed to efficiently carry out the photocuring reaction. The preheating can be performed, for example, at 40 to 140 °C for about 1 minute to 1 hour.

[0191] The coating amount of the above photosensitive resin composition can be appropriately selected according to the purpose, and preferably, the film thickness is 0.1 to 200 μm, preferably 1 to 150 μm.

[0192] To improve the film thickness uniformity at the substrate surface, a solvent can be dropped onto the substrate (pre-wetting method) before coating the photosensitive resin composition. The dropped solvent and its amount can be appropriately selected according to the purpose. As the above solvent, for example, alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, and diols such as PGME are preferred, and the solvent used in the photosensitive resin composition can also be used.

[0193] Next, (ii) the photosensitive resin film is exposed. The exposure is preferably performed with light having a wavelength of 1 to 600 nm, more preferably with light having a wavelength of 10 to 600 nm, and further preferably with light having a wavelength of 190 to 500 nm. As light of such wavelengths, for example, various wavelengths of light generated by a radiation generating device can be cited, such as ultraviolet light such as g-line, h-line, i-line, and far ultraviolet light (248 nm, 193 nm). Among these, light having a wavelength of 248 to 436 nm is particularly preferred. The exposure dose is preferably 10 to 10,000 mJ / cm 2 。

[0194] The exposure can be performed via a photomask. The above photomask can be, for example, a photomask with a desired pattern cut out. Furthermore, the material of the photomask is not particularly limited, and a photomask that shields light of the above wavelength is preferred. For example, a photomask having a light-shielding film such as chromium is preferably used.

[0195] Furthermore, in order to improve the development sensitivity, post-exposure baking (PEB) can be performed. The PEB is preferably set to 0.5 to 10 minutes at 40 to 150 °C. Through PEB, the exposed portions are crosslinked to form an insolubilized pattern that is insoluble in the solvent used as the developer.

[0196] After exposure or after PEB, (iii) develop with a developer to form a pattern. As the developer, for example, alcohols such as IPA, ketones such as cyclohexanone, diols such as PGME, etc. are preferably used, and solvents used in the photosensitive resin composition can also be used. As the developing method, common methods can be cited, such as the method of dipping the substrate on which the pattern is formed in the above-mentioned developer. Then, if necessary, cleaning, rinsing, drying, etc. are performed to obtain a resin film having a desired pattern.

[0197] Furthermore, it is preferable to (iv) post-cure the film on which the pattern is formed using an oven or a hot plate at 100 to 250 °C, preferably 150 to 220 °C. If the post-curing temperature is 100 to 250 °C, the crosslinking density of the photosensitive resin composition is increased, and the remaining volatile components can be removed, which is more preferable from the viewpoints of adhesion to the substrate, heat resistance, strength, electrical properties, and adhesive strength. The post-curing time is preferably 10 minutes to 10 hours, more preferably 10 minutes to 3 hours. If the photosensitive resin composition of the present invention is used, even post-curing at a relatively low temperature of about 200 °C can obtain a film having excellent various film properties. The film thickness of the post-cured film (cured film) is usually 1 to 200 μm, preferably 5 to 50 μm.

[0198] In the case where it is not necessary to form a pattern, for example, in the case where a simple and uniform film is desired to be formed, in step (ii) of the above-mentioned pattern forming method, the film can be formed by exposing with light of an appropriate wavelength without passing through a photomask.

[0199] [Photosensitive dry film]

[0200] The photosensitive dry film of the present invention includes: a support film, and a photosensitive resin film obtained from the above-mentioned photosensitive resin composition on the support film.

[0201] The above-mentioned photosensitive dry film (support film and photosensitive resin film) is solid, and the photosensitive resin film does not contain a solvent, so there is no need to worry about bubbles caused by its volatilization remaining between the inside of the photosensitive resin film and a substrate having irregularities. Considering the flatness, step height coverage, and substrate stacking interval on a substrate having irregularities, there is an appropriate film thickness range. Therefore, the film thickness of the above-mentioned photosensitive resin film is preferably 5 to 200 μm, more preferably 10 to 100 μm.

[0202] In addition, the viscosity ratio of the photosensitive resin film is closely related to its fluidity. The photosensitive resin film can exhibit appropriate fluidity within an appropriate viscosity ratio range, enter into narrow gaps, or enhance the adhesiveness to the substrate through resin softening. Therefore, from the perspective of the fluidity of the photosensitive resin film, the viscosity ratio of the photosensitive resin film is preferably 10 to 5,000 Pa·s, more preferably 30 to 2,000 Pa·s, and further preferably 50 to 300 Pa·s at a temperature of 80 to 120°C. It should be noted that in the present invention, the viscosity ratio is a measured value obtained using a rotational viscometer.

[0203] When the photosensitive dry film of the present invention is bonded to a substrate with irregularities (for example, a substrate having either or both of grooves and holes with an opening width of 10 to 100 μm and a depth of 10 to 120 μm), the photosensitive resin film follows the irregularities and is coated, enabling high flatness. In particular, the photosensitive resin film of the present invention is characterized by its flexibility, thus enabling even higher flatness. Furthermore, if the photosensitive resin film is bonded to the substrate in a vacuum environment, the generation of gaps between them can be more effectively prevented.

[0204] Secondly, the photosensitive dry film of the present invention can be manufactured by coating the photosensitive resin composition on a substrate, drying it, and forming a photosensitive resin film. As a manufacturing apparatus for the photosensitive dry film, a film coater generally used for manufacturing pressure-sensitive adhesive products can be used. Examples of the film coater include a beveled wheel coater, a beveled wheel reverse coater, a multi-functional coater, a die coater, a lip coater, a lip reverse coater, a direct gravure coater, an offset gravure coater, a three-roll bottom reverse coater, a four-roll bottom reverse coater, etc.

[0205] When the support film is unwound from the unwind shaft of the film coater and passes through the coater head of the film coater, the photosensitive resin composition is coated on the support film with a specified thickness, and then passed through a hot air circulation oven at a specified temperature and time to be dried on the support film, forming a photosensitive resin film, thereby obtaining a photosensitive dry film. Additionally, if necessary, the photosensitive dry film and a protective film unwound from another unwind shaft of the film coater are passed through a laminating roller with a specified pressure. After laminating the photosensitive resin film on the support film and the protective film, it is wound around the winding shaft of the film coater, thereby enabling the manufacture of a photosensitive dry film with a protective film. In this case, as the temperature, it is preferably 25 to 150°C, as the time, it is preferably 1 to 100 minutes, and as the pressure, it is preferably 0.01 to 5 MPa.

[0206] The above-mentioned support film may be a single-layer film composed of a single film, or a multi-layer film formed by laminating multiple polymer films. As the material of the above-mentioned film, synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate can be cited. From the aspect of having appropriate flexibility, mechanical strength, and heat resistance, polyethylene terephthalate is preferred. In addition, these films can be products subjected to various treatments such as corona treatment and coating with a release agent. These can use commercially available products. For example, Cerapeel WZ(RX), Cerapeel BX8(R) (manufactured by Toray Film Processing Co., Ltd.), E7302, E7304 (manufactured by Toyobo Co., Ltd.), Purex G31, Purex G71T1 (manufactured by Teijin DuPont Films Co., Ltd.), PET38X1-A3, PET38X1-V8, PET38X1-X08 (manufactured by Nippa Co., Ltd.), etc. can be cited.

[0207] As the above-mentioned protective film, the same film as the above-mentioned support film can be used, and polyethylene terephthalate and polyethylene having appropriate flexibility are preferred. These can use commercially available products. As polyethylene terephthalate, the products already exemplified can be cited. As polyethylene, for example, GF-8 (manufactured by Tamapoly Co., Ltd.), PE film type 0 (manufactured by Nippa Co., Ltd.), etc. can be cited.

[0208] Regarding the thickness of the above-mentioned support film and protective film, from the viewpoints of the stability of manufacturing the photosensitive dry film and preventing winding and so-called curling with respect to the core, 10 to 100 μm is preferred, and 25 to 50 μm is more preferred.

[0209] [Pattern formation method using a photosensitive dry film]

[0210] The pattern formation method using a photosensitive dry film includes:

[0211] (i') A step of forming a photosensitive resin film on a substrate using the photosensitive dry film of the present invention,

[0212] (ii) A step of exposing the above-mentioned photosensitive resin film, and

[0213] (iii) A step of developing the above-mentioned exposed photosensitive resin film with a developer to form a pattern.

[0214] First, in step (i'), a photosensitive resin film is formed on a substrate using a photosensitive dry film. Specifically, the photosensitive resin film of the photosensitive dry film is pasted onto the substrate, thereby forming a photosensitive resin film on the substrate. When a protective film is laminated on the photosensitive dry film, after peeling the protective film from the photosensitive dry film, the photosensitive resin film of the photosensitive dry film is pasted onto the substrate. Pasting can be performed using, for example, a film pasting device.

[0215] As the above-mentioned substrate, the same substrates as those described in the pattern forming method using a photosensitive resin composition can be cited. As the above-mentioned film pasting device, a vacuum laminator is preferred. For example, the protective film of the above-mentioned photosensitive dry film is peeled off, and for the exposed photosensitive resin film, in a vacuum chamber with a specified vacuum degree, using a pasting roller with a specified pressure, it is closely adhered to the above-mentioned substrate on a table at a specified temperature. Further, as the above-mentioned temperature, 60 to 120°C is preferred, as the above-mentioned pressure, 0 to 5.0 MPa is preferred, and as the above-mentioned vacuum degree, 50 to 500 Pa is preferred.

[0216] In order to obtain a photosensitive resin film with a desired thickness, the film can be pasted multiple times as needed. The number of pasting times is, for example, about 1 to 10 times, and a photosensitive resin film with a thickness of 10 to 1,000 μm, particularly about 100 to 500 μm, can be obtained.

[0217] In order to efficiently perform the photocuring reaction of the above-mentioned photosensitive resin film and to improve the adhesion between the photosensitive resin film and the substrate, preheating (pre-baking) can be performed as needed. Regarding pre-baking, for example, it can be performed at 40 to 140°C for about 1 minute to 1 hour.

[0218] Similar to the case of the pattern forming method using the above-mentioned photosensitive resin composition, the photosensitive resin film pasted on the substrate can form a pattern by the process of (ii) exposing the above-mentioned photosensitive resin film, (iii) developing the exposed photosensitive resin film with a developer, and (iv) performing post-curing treatment as needed. Further, regarding the support film of the photosensitive dry film, depending on the process, it is peeled off before pre-baking or PEB, or removed by other methods.

[0219] For the films obtained from the above-mentioned photosensitive resin composition and photosensitive dry film, they have excellent heat resistance, flexibility, electrical insulation, mechanical properties, and adhesion to substrates, etc., and are suitable for use as films for protecting electrical and electronic components such as semiconductor elements and films for bonding substrates.

[0220] [Method for bonding substrates]

[0221] Furthermore, the photosensitive resin composition and the photosensitive dry film of the present invention can also be used as a substrate adhesive for bonding two substrates. As a method for bonding substrates, the following method can be cited: Under conditions of suitable heat and pressure, a substrate having a film formed using the photosensitive resin composition or the photosensitive dry film of the present invention is bonded to a second substrate via the film. That is, the above-mentioned film becomes an adhesive layer. Sometimes, either one or both of the substrate having the film formed and the second substrate are made into chips by cutting or the like.

[0222] As the bonding conditions, it is preferable that the heating temperature is 50 to 200°C and the heating time is 1 to 60 minutes. As a bonding device, a wafer bonding device is used, and wafers under reduced pressure can be bonded while applying a load, or a flip-chip bonding device can also be used for chip-wafer or chip-chip bonding.

[0223] By performing post-curing treatment on the bonded (adhered) substrate under the same conditions as the above-mentioned step (iv), the crosslinking density of the above-mentioned film increases, and the substrate adhesion can be improved. By adopting post-curing treatment, the bonding strength of the adhesive layer formed between the substrates is improved, resulting in permanent bonding. Furthermore, through the heating during bonding, a crosslinking reaction occurs, and no side reaction accompanied by degassing occurs in the above-mentioned crosslinking reaction. Therefore, especially when used as a substrate adhesive, no bonding defects (voids) are induced.

[0224] [Laminate]

[0225] The laminate of the present invention includes a substrate and the above-mentioned photosensitive resin film on the substrate. As the above-mentioned substrate, the same substrates as those described in the pattern formation method using the photosensitive resin composition can be cited, and a substrate having irregularities (for example, a substrate having any one or both of grooves and holes with an opening width of 10 to 100 μm and a depth of 10 to 120 μm) is particularly preferred. The laminate having the above-mentioned photosensitive resin film formed thereon becomes a laminate with excellent adhesion between the substrate and the film, and in the case where the substrate has irregularities, it becomes a laminate with high flatness.

[0226] Examples

[0227] Synthesis examples, examples, and comparative examples are shown below to illustrate the present invention more specifically, but the present invention is not limited to the following examples. In the following synthesis examples, regarding the Mw of each polymer, TSKgel Super HZM-H (manufactured by Tosoh Corporation) was used as the column, and under the analysis conditions of a flow rate of 0.6 mL / minute, an elution solvent of tetrahydrofuran, and a column temperature of 40°C, GPC measurement was performed using monodisperse polystyrene as the standard.

[0228] Compounds (S-1) to (S-6) used in the following synthesis examples are as follows.

[0229] [Chemical Formula 19]

[0230]

[0231] [1] Synthesis of Polymers Containing a Silicon Skeleton

[0232] [Synthesis Example 1-1] Synthesis of Resin 1

[0233] 84.0 g (0.2 mol) of compound (S-1), 39.7 g (0.15 mol) of compound (S-2), and 46.5 g (0.25 mol) of compound (S-3) were added to a 3 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser. Then, 2,000 g of toluene was added, and the mixture was heated to 70 °C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 38.8 g (0.20 mol) of compound (S-5) and compound (S-6) (y 1 = 38) 553.4 g (0.20 mol) (total amount of hydrosilyl groups / total amount of alkenyl groups = 1 / 1 (molar ratio)) were added dropwise over 1 hour. After the addition was completed, the mixture was heated to 100 °C and aged for 6 hours. Then, toluene was distilled off under reduced pressure from the reaction solution to obtain Resin 1. It was confirmed by 1 1H-NMR (manufactured by Bruker) that Resin 1 contained repeating units a1, b1, a2, b2, a3, b3, a4, and b4. The Mw of Resin 1 was 38,000, and the silicone content was 67.2% by mass.

[0234] [Synthesis Example 1-2] Synthesis of Resin 2

[0235] 53.0 g (0.20 mol) of compound (S-2), 172.0 g (0.40 mol) of compound (S-4), and 9.3 g (0.05 mol) of compound (S-3) were added to a 3 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser. Then, 2,000 g of toluene was added, and the mixture was heated to 70 °C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 29.1 g (0.15 mol) of compound (S-5) and compound (S-6) (y 1 = 8) 430.5 g (0.7 mol) (total amount of hydrosilyl groups / total amount of alkenyl groups = 1 / 1 (molar ratio)) were added dropwise over 1 hour. After the addition was completed, the mixture was heated to 100 °C and aged for 6 hours. Then, toluene was distilled off under reduced pressure from the reaction solution to obtain Resin 2. It was confirmed by 1 1H-NMR (manufactured by Bruker) that Resin 2 contained repeating units a1, b1, a2, b2, a3, b3, a4, and b4. The Mw of Resin 2 was 35,000, and the silicone content was 53.6% by mass.

[0236] [Synthesis Example 1-3] Synthesis of Resin 3

[0237] After adding 84.0 g (0.20 mol) of compound (S-1) and 132.5 g (0.50 mol) of compound (S-2) to a 3 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device, and a reflux condenser, 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 58.2 g (0.30 mol) of compound (S-5) and compound (S-6) (y 1 = 38) 830.1 g (0.3 mol) (total of hydrosilyl groups / total of alkenyl groups = 1 / 1 (molar ratio)) were added dropwise over 1 hour. After the addition was completed, the mixture was heated to 100°C and aged for 6 hours. Then, toluene was distilled off under reduced pressure from the reaction solution to obtain Resin 3. It was confirmed by 1 1H-NMR (manufactured by Bruker) that Resin 3 contained repeating units a1, b1, a3, b3, a4, and b4. The Mw of Resin 3 was 32,000, and the silicone content was 75.5% by mass.

[0238] [Synthesis Example 1-4] Synthesis of Resin 4

[0239] After adding 132.5 g (0.50 mol) of compound (S-2), 107.5 g (0.25 mol) of compound (S-4), and 18.6 g (0.10 mol) of compound (S-3) to a 3 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device, and a reflux condenser, 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 9.7 g (0.05 mol) of compound (S-5) and compound (S-6) (y 1 = 8) 276.7 g (0.45 mol) (total of hydrosilyl groups / total of alkenyl groups = 1 / 1 (molar ratio)) were added dropwise over 1 hour. After the addition was completed, the mixture was heated to 100°C and aged for 6 hours. Then, toluene was distilled off under reduced pressure from the reaction solution to obtain Resin 4. It was confirmed by 1 1H-NMR (manufactured by Bruker) that Resin 4 contained repeating units a2, b2, a3, b3, a4, and b4. The Mw of Resin 4 was 36,000, and the silicone content was 58.4% by mass.

[0240] [2] Synthesis of Acrylic Resin

[0241] [Synthesis Example 2-1] Synthesis of Acrylic Resin 1

[0242] In a flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer, 1 g of 2,2'-azobisisobutyronitrile (AIBN), 70 g of PGMEA, and 70 g of toluene were charged. Next, 32.6 g of acrylic acid and 40 g of methacrylic acid were added. After sufficient stirring under a nitrogen atmosphere, the temperature was raised to 80°C, and while maintaining the reaction temperature at 80°C ± 2°C, stirring was carried out for 6 hours to obtain a solution of acrylic resin 1. PGMEA was added to the resulting solution so that the concentration of acrylic resin 1 became 60% by mass. The Mw of acrylic resin 1 was 15,000.

[0243] [Synthesis Example 2-2] Synthesis of Acrylic Resin 2

[0244] In a flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer, 1 g of AIBN, 70 g of PGMEA, and 70 g of toluene were charged. Next, 25 g of acrylic acid and 43.9 g of methyl acrylate were added. After sufficient stirring under a nitrogen atmosphere, the temperature was raised to 80°C, and while maintaining the reaction temperature at 80°C ± 2°C, stirring was carried out for 6 hours to obtain a solution of acrylic resin 2. PGMEA was added to the resulting solution so that the concentration of acrylic resin 2 became 60% by mass. The Mw of acrylic resin 2 was 17,000.

[0245] [3] Preparation of Photosensitive Resin Composition

[0246] [Examples 1 to 8, Comparative Examples 1 to 4]

[0247] According to the blending amounts described in Table 1, the respective components were blended, and then, after stirring, mixing, and dissolving at room temperature, precision filtration was carried out using a 1.0 μm filter made of Teflon (registered trademark) to obtain the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 4.

[0248] [Table 1]

[0249]

[0250] The photoacid generators PAG-1 to PAG-6, crosslinking agents CL-1, CL-2, and quencher AM-1 described in Table 1 are as follows.

[0251] ·PAG-1 to PAG-6

[0252] [Chemical Formula 20]

[0253]

[0254] [Chemical Formula 21]

[0255]

[0256] ·CL-1, CL-2

[0257] [Chemical formula 22]

[0258]

[0259] ·AM-1

[0260] [Chemical formula 23]

[0261]

[0262] [4] Preparation of photosensitive dry film

[0263] Using a die coater as a film coater and a polyethylene terephthalate film (38 μm thick) as a support film, the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 4 were respectively coated on the above support film. Next, it was dried by passing through a hot air circulation oven (4 m long) set at 100 °C for 5 minutes to form a photosensitive resin film on the support film, and a photosensitive dry film was obtained. From the above photosensitive resin film, a polyethylene film (40 μm thick) as a protective film was laminated with a pressure of 1 MPa using a laminating roller to produce a photosensitive dry film with a protective film. The film thicknesses of the respective photosensitive resin films are shown in Table 2. It should be noted that the film thickness was measured using an optical interference film thickness measuring machine (manufactured by SCREEN Semiconductor Solutions Co., Ltd.).

[0264] [5] Evaluation of resin film

[0265] (1) Evaluation of pattern formability

[0266] For the above photosensitive dry film, the protective film was peeled off, and using a vacuum laminator TEAM-100RF (manufactured by Takatori Corp.), the degree of vacuum in the vacuum chamber was set to 80 Pa, and the photosensitive resin film on the support film was closely adhered to a silicon substrate with unevenness. The temperature condition was set to 100 °C. After returning to normal pressure, the above substrate was taken out from the vacuum laminator, and the support film was peeled off. Next, in order to improve the adhesion to the substrate, pre-baking was performed on a hot plate at 110 °C for 5 minutes. For the obtained photosensitive resin film, in order to form line and space patterns and contact hole patterns, it was exposed using a contact aligner exposure device under the exposure condition of 365 nm via a mask. After exposure, PEB was performed on a hot plate at 130 °C for 5 minutes, cooled, and spray developed with PGMEA for 300 seconds to form a pattern.

[0267] For the photosensitive resin film on the substrate on which the pattern has been formed by the above method, using an oven, post-cure for 2 hours while purging with nitrogen at 180°C. Then, using a scanning electron microscope (SEM), observe the cross-sections of the formed contact hole patterns of 100 μm, 80 μm, 60 μm, 40 μm, and 20 μm, and set the smallest hole pattern with the hole penetrating to the bottom of the film as the limit resolution clarity. Furthermore, from the obtained cross-sectional photos, evaluate the perpendicularity of the 40-μm contact hole pattern, mark the perpendicular pattern as ◎, the slightly inverted conical shape as ○, the inverted conical shape as △, and the poor opening as X. The results are shown in Table 2.

[0268] (2) Evaluation of reliability (adhesion, crack resistance)

[0269] Using a spin coater, coat each of the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 4 on a silicon wafer so that the thickness becomes 10 μm. To remove the solvent, heat on a hot plate at 100°C for 3 minutes and dry.

[0270] For the entire surface of the composition coated on the wafer, without passing through a mask, use a mask aligner MA8 of SUSS MicroTec to irradiate light (wavelength 365 nm) with a high-pressure mercury lamp as the light source, perform PEB at 140°C for 5 minutes, and immerse in PGMEA for 5 minutes. Heat the remaining film after this operation in an oven at 190°C for 1 hour to obtain a resin film.

[0271] Use a dicing saw equipped with a cutting blade (DAD685 manufactured by DISCO Corporation, spindle speed: 40,000 rpm, cutting speed: 20 mm / second) to cut the obtained wafer to obtain a test piece of 10 mm × 10 mm square. Supply the obtained test pieces (10 pieces each) to a thermal cycle test (repeat 1,000 cycles of holding at -25°C for 10 minutes and holding at 125°C for 10 minutes), and use an optical microscope to confirm the peeling state of the resin film from the wafer and the presence or absence of cracks after the thermal cycle test. Mark the case where no peeling or cracking occurs as good, the case where one or more peelings occur as peeling, and the case where one or more cracks occur as cracking. The results are shown in Table 2.

[0272] (3) Evaluation of heat resistance

[0273] Measure the mass of the test piece before the test in the reliability evaluation, then place the test piece in an oven heated to 200°C for 1,000 hours, take out the test piece from the oven, and measure the mass. Judge the case where the mass change rate before and after the test is less than 0.5% as good, and the case where the mass change rate before and after the test is 0.5% or more as bad. The results are shown in Table 2.

[0274] [Table 2]

[0275]

Claims

1. A photosensitive resin composition comprising (A) a polymer having a silicone skeleton and (B) a photoacid generator, wherein the photoacid generator (B) comprises (B1) an onium salt photoacid generator and (B2) a photoacid generator other than an onium salt. The photoacid generator other than the onium salt is an oxime derivative, a β-ketosulfone derivative, a disulfone derivative, a nitrobenzyl sulfonate derivative, a sulfonate derivative, an imide sulfonate derivative, an oxime sulfonate derivative, an imino sulfonate derivative, or a triazine derivative. (A) The polymer having a silicone skeleton comprises repeating units represented by the following formulas (a1) to (a4) and (b1) to (b4). [Chemical formula 1] In the formula, R 1 ~R 4 each independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, and m is an integer of 1 to 600. a 1 ~a 4 and b 1 ~b 4 To satisfy 0 ≤ a 1 <1, 0 ≤ a 2 <1, 0 ≤ a 3 <1, 0 ≤ a 4 <1, 0 ≤ b 1 <1, 0 ≤ b 2 <1, 0 ≤ b 3 <1, 0 ≤ b 4 <1, 0 < a 1 +a 2 +a 3 +a 4 <1, 0 < b 1 +b 2 +b 3 +b 4 <1 and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 = 1 of the numbers, X 1 is a divalent group represented by the following formula (X1), X 2 is a divalent group represented by the following formula (X2), X 3 is a divalent group represented by the following formula (X3), X 4 is a divalent group represented by the following formula (X4), [Chemical formula 2] In the formula, Z 1 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl, R 11 and R 12 are each independently a hydrogen atom or a methyl group, R 13 and R 14 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, p 1 and p 2 are each independently an integer from 0 to 7, q 1 and q 2 are each independently an integer from 0 to 2, [Chemical formula 3] In the formula, Z 2 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl, R 21 and R 22 are each independently a hydrogen atom or a methyl group, R 23 and R 24 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, r 1 and r 2 are each independently an integer from 0 to 7, s 1 and s 2 are each independently an integer from 0 to 2, [Chemical formula 4] In the formula, R 31 and R 32 are each independently a hydrogen atom or a methyl group, t 1 and t 2 are each independently an integer from 0 to 7. [Chemical formula 5] 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 monovalent hydrocarbon group having 1 to 8 carbon atoms, u 1 and u 2 are each independently an integer from 0 to 7, and v is an integer from 0 to 600.

2. The photosensitive resin composition according to claim 1, wherein the photoacid generator other than the onium salt is an oxime derivative, a β-ketosulfone derivative, a nitrobenzyl sulfonate derivative, a sulfonate derivative, an imide sulfonate derivative, or a triazine derivative.

3. The photosensitive resin composition according to claim 1 or 2, further comprising (C) a crosslinking agent.

4. The photosensitive resin composition according to any one of claims 1 to 3, further comprising (D) a solvent.

5. The photosensitive resin composition according to any one of claims 1 to 4, further comprising (E) a quencher.

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

7. Photosensitive dry film, which comprises: A support film, and the photosensitive resin film according to claim 6 on the support film.

8. A laminate comprising: A substrate, and the photosensitive resin film according to claim 6 on the substrate.

9. A pattern forming method comprising: (i) a step of forming a photosensitive resin film on a substrate using the photosensitive resin composition according to any one of claims 1 to 5, (ii) a step of exposing the photosensitive resin film, and (iii) a step of developing the exposed photosensitive resin film with a developer to form a pattern.

10. A pattern forming method comprising: (i') a step of forming a photosensitive resin film on a substrate using the photosensitive dry film according to claim 7, (ii) a step of exposing the photosensitive resin film, and (iii) a step of developing the exposed photosensitive resin film with a developer to form a pattern.

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

Images